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Sample records for catalyst precursor anions

  1. The role of catalyst precursor anions in coal gasification

    SciTech Connect

    Abotsi, G.M.K.

    1992-08-28

    The aims of the proposed project are to enrich our understanding of the roles of various aqueous soluble catalyst precursor anions on the surface electrical properties of coal and to ascertain the influence of the surface charge on the adsorption, dispersion, and activities of calcium and potassium. These goals will be achieved by impregnating a North Dakota lignite (PSOC 1482) and its demineralized derivative with calcium or potassium catalyst precursors containing acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sub 3}{sup {minus}}), sulfate (SO{sub 4}{sup 2{minus}}), and carbonate (CO{sub 3}{sup 2{minus}}) anions. Catalyst loading will be conducted under well-controlled conditions of solution pH and ionic strength. In the last quarter, the surface charge properties of the coal was determined as a function of acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sup 3}{sup {minus}}), carbonate (CO{sub 3}{sup 2{minus}}) or sulfate (SO{sub 4}{sup 2{minus}})concentration using the respective potassium salts of these anions. In general, low anion concentrations (10{sup {minus}3} or 10{sup {minus}2} mol/L) had little effect on the zeta potentials of the coals. However, the surface charge densities of the coal become less negative at 10-1 mol/L of the nitrate, carbonate or sulfate anions. These trends suggest that the surface charge density of the coal is controlled by the adsorption of potassium ions (K{sup +}) onto the coal particles. The net negative charge on the coal panicles creates a repulsive force between the anions and the coal surface and prevents the anions from exerting any significant effect on the coal's electrokinetic properties.

  2. The role of catalyst precursor anions in coal gasification. Third quarterly report

    SciTech Connect

    Abotsi, G.M.K.

    1992-08-28

    The aims of the proposed project are to enrich our understanding of the roles of various aqueous soluble catalyst precursor anions on the surface electrical properties of coal and to ascertain the influence of the surface charge on the adsorption, dispersion, and activities of calcium and potassium. These goals will be achieved by impregnating a North Dakota lignite (PSOC 1482) and its demineralized derivative with calcium or potassium catalyst precursors containing acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sub 3}{sup {minus}}), sulfate (SO{sub 4}{sup 2{minus}}), and carbonate (CO{sub 3}{sup 2{minus}}) anions. Catalyst loading will be conducted under well-controlled conditions of solution pH and ionic strength. In the last quarter, the surface charge properties of the coal was determined as a function of acetate (CH{sub 3}COO{sup {minus}}), chloride (Cl{sup {minus}}), nitrate (NO{sup 3}{sup {minus}}), carbonate (CO{sub 3}{sup 2{minus}}) or sulfate (SO{sub 4}{sup 2{minus}})concentration using the respective potassium salts of these anions. In general, low anion concentrations (10{sup {minus}3} or 10{sup {minus}2} mol/L) had little effect on the zeta potentials of the coals. However, the surface charge densities of the coal become less negative at 10-1 mol/L of the nitrate, carbonate or sulfate anions. These trends suggest that the surface charge density of the coal is controlled by the adsorption of potassium ions (K{sup +}) onto the coal particles. The net negative charge on the coal panicles creates a repulsive force between the anions and the coal surface and prevents the anions from exerting any significant effect on the coal`s electrokinetic properties.

  3. The role of catalyst precursor anions in coal gasification. Final technical report, September 1991--June 1994

    SciTech Connect

    Abotsi, G.M.K.

    1995-01-01

    The utilization of coal is currently limited by several factors, including the environmental impacts of coal use and the lack of cost-effective technologies to convert coal into useful gaseous and liquid products. Several catalysts have been evaluated for coal gasification and liquefaction. The activities of the catalysts are dependent on many factors such as the method of catalyst addition to the coal and the catalyst precursor type. Since catalyst addition to coal is frequently conducted in aqueous solution, the surface chemistry of colloidal coal particles will be expected to exert an influence on catalyst uptake. However, the effects of the various coal gasification catalyst precursors on the interfacial properties of coal during catalyst loading from solution has received little attention. The aim of this study is to ascertain the influence of the metal salts (i): calcium acetate (Ca(OOCCH{sub 3}){sub 2}), calcium chloride (CaCl{sub 2}) or calcium nitrate (Ca(NO{sub 3}){sub 2}) and (ii): potassium acetate (KOOCCH{sub 3}), potassium chloride (KCl), potassium nitrate (KNO{sub 3}), potassium carbonate (K{sub 2}CO{sub 3}) and potassium sulfate (K{sub 2}SO{sub 4}) on the electrokinetic and adsorptive properties of coal and determine the relationship, if any, between coal surface electrokinetic properties, and catalyst loading and eventually its effects on the reactivities of coal chars.

  4. Hydroxy double salt anion exchange kinetics: effects of precursor structure and anion size.

    PubMed

    Kandare, Everson; Hossenlopp, Jeanne M

    2005-05-01

    (1)H NMR spectroscopy and powder X-ray diffraction have been used to explore the details of anion exchange reactions of two layered hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA), nickel zinc hydroxy acetate (NZA), and a related layered material, zinc hydroxy acetate (ZHA), at room temperature (21-22 degrees C). Reactions that followed Avrami-Erofe'ev kinetics with respect to temporal profiles for acetate release, ZCA with butyrate (k = 1.7 x 10(-3) s(-1)), and octanoate (k = 0.79 x 10(-3) s(-1)) anions, as well as ZHA with octanoate (k = 2.6 x 10(-3) s(-1)), demonstrate that rate constants for acetate release are influenced by the exchange anion relative size as well as by the solid precursor structure/composition. The reaction of NZA with octanoate deviated from expected Avrami-Erofe'ev behavior, with evidence for an intermediate species in the solid phase that may influence the rate of acetate release into solution. The reaction of ZCA with formate anions exhibited a unique zeroth-order kinetics release of acetate, providing the possibility of developing tunable nanostructured anion release sources by use of variations in the size of the exchange species. PMID:16851994

  5. Supported Oxide Catalysts from Chelating Precursors

    NASA Astrophysics Data System (ADS)

    Prieto-Centurion, Dario

    Supported Fe catalysts and, in particular, Fe and substituted MFI zeolites have attracted industrial and academic attention due to their ability to promote selective catalytic reduction of NOx and selective partial oxidation of hydrocarbons. It is generally accepted that some form of highly dispersed, binuclear or atomically-isolated metal species are involved in the selective processes catalyzed these materials. Several studies have sought to reproduce the structures and reactivity of these substituted zeolites on dierent supports. Given that specialized reagents or preparation conditions that are required in some of these preparation methods, and that multiple surface structures are often formed, this dissertation aimed to develop a route to highly dispersed supported transition metals using commonly available reactants and synthesis routes. Described here is a straightforward and effective procedure to control dispersion and surface speciation of Fe on SiO2 and CeO2 through incipient wetness impregnation (IWI) of the support with aqueous, anionic complexes of Fe3+ and ethylenediaminetetraacetic acid (EDTA) followed by oxidative heat-treatment. On SiO2, this method preferentially creates isolated surface structures up to loading of 0.9 Fe nm-2 if using alkali counter-cations. This isolated species display classic 'single-site' behavior|constant turn over frequency (TOF) with increasing Fe surface density|in the oxidation of adamantane with H 2O2, indicating active sites are equally accessible and equally active within this range of surface density. Additionally, TOF increases linearly with electronegativity of the alkali counter-cation, suggesting electronic promotion. Conversely, IWI of unprotected Fe3+ produces agglomerates less active in this reaction. On CeO2, the sterics and negative charge imparted on Fe 3+ by EDTA4- inhibits incorporation of Fe into surface vacancies. Instead, formation of two-dimensional oligomeric structures which can undergo Fe3+-Fe2

  6. Spectroscopic studies of alumina-supported nickel catalysts precursors. Part I. Catalysts prepared from acidic solutions

    NASA Astrophysics Data System (ADS)

    Pasieczna-Patkowska, S.; Ryczkowski, J.

    2007-04-01

    Nickel alumina-supported catalysts were prepared from acidic solutions of nickel nitrate by the CIM and DIM methods (classical and double impregnation, respectively). The catalysts exhibited different nickel species due to the existence of various metal-support interaction strengths. As a consequence, the reducibility and other surface properties changed as a function of the preparation method. The aim of this work was to study the interaction between the metal precursor and the alumina surface by means of FT-IR (Fourier transform infrared) and FT-IR/PAS (FT-IR photoacoustic spectroscopy).

  7. Precursor anion states in dissociative electron attachment to chlorophenol isomers

    NASA Astrophysics Data System (ADS)

    Kossoski, F.; Varella, M. T. do N.

    2016-07-01

    We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl ∗ , one σOH ∗ , and three π∗ shape resonances. We show that electron capture into the two lower lying π∗ orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π∗ resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 ∗ anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl ∗ state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl ∗ resonance and destabilizing the σOH ∗ resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH ∗ orbital.

  8. Precursor anion states in dissociative electron attachment to chlorophenol isomers.

    PubMed

    Kossoski, F; Varella, M T do N

    2016-07-28

    We report a theoretical study on low-energy (<10 eV) elastic electron scattering from chlorophenol isomers, namely, para-chlorophenol (pCP), meta-chlorophenol (mCP), and ortho-chlorophenol (oCP). The calculations were performed with the Schwinger multichannel method with pseudopotentials, and analysis of the computed integral cross sections and virtual orbitals revealed one σCCl (∗), one σOH (∗), and three π(∗) shape resonances. We show that electron capture into the two lower lying π(∗) orbitals initiates dissociative processes that lead to the elimination of the chloride ion, accounting for the two overlapping peaks where this fragment was observed. Despite the relatively small differences on the energetics of the π(∗) resonances, a major isomeric effect was found on their corresponding autodetachment lifetimes, which accounts for the observed increasing cross sections in the progression pCP < mCP < oCP. In particular, dissociation from the π1 (∗) anion of pCP is largely suppressed because of the unfavorable mixing with the σCCl (∗) state. We found the intramolecular hydrogen bond present in oCP to have the opposite effects of stabilizing the σCCl (∗) resonance and destabilizing the σOH (∗) resonance. We also suggest that the hydrogen abstraction observed in chlorophenols and phenol actually takes place by a mechanism in which the incoming electron is directly attached to the dissociative σOH (∗) orbital. PMID:27475364

  9. 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.

  10. Time-resolved CIDEP study of the photogenerated camphorquinone radical anion: a case of dual singlet and triplet precursors

    SciTech Connect

    Depew, M.C.; Wan, J.K.S.

    1986-12-04

    Photoreduction of camphorquinone in 2-propanol produced electron spin polarized camphorquinone radical anions. The time-resolved electron spin resonance spectra of the spin-polarized radical anions provided the first evidence of dual singlet and triplet precursors in the CIDEP phenomenon. With the results from fluorescence quenching experiments, the time dependence of the CIDEP spectra can be accounted for qualitatively by the changes of the relative contributions to the polarization among the singlet pair, F and triplet pairs, and the triplet mechanisms.

  11. Fabrication of CdS nanowires with increasing anionic precursor by SILAR method

    NASA Astrophysics Data System (ADS)

    Dariani, R. S.; Salehi, F.

    2016-05-01

    CdS nanowires were fabricated on glass substrate at room temperature by SILAR method with cadmium nitrate cationic and sodium sulfide anionic precursors. The deposition were done at different S:Cd concentration ratios of 1:1, 3:1, 5:1, and 7:1. Nanowires growth procedure was studied in the mentioned concentrations. The number of immersion cycles was kept constant at 15 cycles. EDX analysis showed that in all stoichiometric ratios, S/Cd composition ratio remains at about unity. Our results indicated that S:Cd concentration ratio of 7:1 had the longest nanowires with hexagonal structure. The main objective of this paper was to produce CdS nanowires with increasing concentration of sulfur.

  12. 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

  13. 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.

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

    DOEpatents

    Chung, Hoon Taek; Zelenay, Piotr

    2015-10-27

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

  15. 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.

  16. Cell performance of Pd-Sn catalyst in passive direct methanol alkaline fuel cell using anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Kim, Jandee; Momma, Toshiyuki; Osaka, Tetsuya

    Direct methanol alkaline fuel cell (DMAFC) using anion exchange membrane (AEM) was operated in passive condition. Cell with AEM exhibits a higher open circuit voltage (OCV) and superior cell performance than those in cell using Nafion. From the concentration dependences of methanol, KOH in fuel and ionomer in anode catalyst layer, it is found that the key factors are to improve the ionic conductivity at the anode and to form a favorable ion conductive path in catalyst layer in order to enhance the cell performance. In addition, by using home-made Pd-Sn/C catalyst as a cathode catalyst on DMAFC, the membrane electrode assembly (MEA) using Pd-Sn/C catalyst as cathode exhibits the higher performance than the usual commercially available Pt/C catalyst in high methanol concentration. Therefore, the Pd-Sn/C catalyst with high tolerance for methanol is expected as the promising oxygen reduction reaction (ORR) catalyst in DMAFC.

  17. 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).

  18. Thermal Decomposition of Bulk K-CoMoSx Mixed Alcohol Catalyst Precursors and Effects on Catalyst Morphology and Performance

    SciTech Connect

    Menart, M. J.; Hensley, J. E.; Costelow, K. E.

    2012-09-26

    Cobalt molybdenum sulfide-type mixed alcohol catalysts were synthesized via calcination of precipitated bulk sulfides and studied with temperature programmed decomposition analysis. Precursors containing aqueous potassium were also considered. Precipitates thermally decomposed in unique events which released ammonia, carbon dioxide, and sulfur. Higher temperature treatments led to more crystalline and less active catalysts in general with ethanol productivity falling from 203 to 97 g (kg cat){sup -1} h{sup -1} when the calcination temperature was increased from 375 to 500 C. The addition of potassium to the precursor led to materials with crystalline potassium sulfides and good catalytic performance. In general, less potassium was required to promote alcohol selectivity when added before calcination. At calcination temperatures above 350 C, segregated cobalt sulfides were observed, suggesting that thermally decomposed sulfide precursors may contain a mixture of molybdenum and cobalt sulfides instead of a dispersed CoMoS type of material. When dimethyl disulfide was fed to the precursor during calcination, crystalline cobalt sulfides were not detected, suggesting an important role of free sulfur during decomposition.

  19. Effect of Iron and Cobalt Catalysts on The Growth of Carbon Nanotubes from Palm Oil Precursor

    NASA Astrophysics Data System (ADS)

    Suriani, A. B.; Asli, N. A.; Salina, M.; Mamat, M. H.; Aziz, A. A.; Falina, A. N.; Maryam, M.; Shamsudin, M. S.; Nor, Roslan Md; Abdullah, S.; Rusop, M.

    2013-06-01

    Catalysts which are typically a transition metal is mandatory and plays an important role in the production of CNT. In this work, the effect of iron (Fe) and cobalt (Co) nitrate catalyst on the growth of carbon nanotubes (CNT) were systematically studied. Green bio-hydrocarbon precursor namely palm oil was used as a precursor. The synthesis was done using thermal chemical vapour deposition method at temperature of 750°C for 15 min synthesis time. The Fe and Co solution were spin-coated separately on silicon substrate at speed of 3000 rev.min-1. The CNT characteristics were analyzed using field emission scanning electron microscopy and micro-Raman spectroscopy. The experimental results revealed that CNT properties were strongly affected by the catalyst type. CNT catalyzed by Co yields large diameter, crooked tube and lower quality, whereas CNT produced by Fe catalyst results in the smallest diameter and reasonably good graphitization. As a conclusion, Fe was considered as the optimum catalyst for better CNT structure and crystallinity. This was due to efficient, uniform and stable Fe catalytic activity as compared to Co catalyst in producing CNT.

  20. Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts

    PubMed Central

    Sinha, Amritanshu; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    We have found that Mo(NAr)(CHR′)(NPh2)2 (R′ = t-Bu or CMe2Ph) and Mo(NAr′)(CHCMe2Ph)(NPh2)2 (Ar = 2,6-i-Pr2C6H3; Ar′ = 2,6-Me2C6H3) can be prepared through addition of two equivalents of LiNPh2 to Mo(NR″)(CHR′)(OTf)2(dme) species (R″ = Ar or Ar′ dme = 1,2-dimethoxyethane), although yields are low. A high yield route consists of addition of LiNPh2 to bishexafluro-t-butoxide species. An X-ray structure of Mo(NAr)(CHCMe2Ph)(NPh2)2 reveals that the two diphenylamido groups are oriented in a manner that allows an 18 electron count to be achieved. The diphenylamido complexes react readily with t-BuOH and (CF3)2MeCOH, but not readily with the sterically demanding biphenol H2[Biphen] (Biphen2- = 3,3′-Di-t-butyl-5,5′,6,6′-tetramethyl-1,1′-Biphenyl-2,2′-diolate). The diphenylamido complexes do react with various 3,3′-disubstituted binaphthols to yield binaphtholate catalysts that can be prepared in situ and employed for a simple asymmetric ring-closing metathesis reaction. In several cases conversions and enantioselectivities were comparable to reactions in which isolated catalysts were employed. PMID:19030118

  1. Anodic Deposition of a Robust Iridium-Based Water-Oxidation Catalyst from Organometallic Precursors

    SciTech Connect

    Blakemore, James D; Schley, Nathan D; Olack, G.; Incarvito, Christopher D; Brudvig, Gary W; Crabtree, Robert H

    2011-01-01

    Artificial photosynthesis, modeled on natural light-driven oxidation of water in Photosystem II, holds promise as a sustainable source of reducing equivalents for producing fuels. Few robust water-oxidation catalysts capable of mediating this difficult four-electron, four-proton reaction have yet been described. We report a new method for generating an amorphous electrodeposited material, principally consisting of iridium and oxygen, which is a robust and long-lived catalyst for water oxidation, when driven electrochemically. The catalyst material is generated by a simple anodic deposition from Cp*Ir aqua or hydroxo complexes in aqueous solution. This work suggests that organometallic precursors may be useful in electrodeposition of inorganic heterogeneous catalysts.

  2. CO2/H2 Methanation Reactivity of Nickel Oxide Based Catalyst Prepared from Different Nickel Salt Precursors

    NASA Astrophysics Data System (ADS)

    Razali, M. H.; Buang, N. A.; Bakar, W. A. W. A.

    2010-03-01

    The catalytic activity of NiO based catalyst prepared from different salt precursors of acetate, nitrate and sulphate salts were investigated towards CO2/H2 methanation reaction, in order to study the effect of type of precursor on the reactivity of the catalyst prepared. Results obtained showed that the NiO based catalyst prepared from nitrate precursor gave highest catalytic activity with 80.03% methanation of CO2 at 500° C of the reaction temperature. Characterization techniques such as FTIR, XRD and SEM were carried out to see the effect of various physical properties of the NiO based catalyst obtained from different salts precursors used, which contributed in a good CO2/H2 methanation reactivity of the catalyst.

  3. An evaluation of Pt sulfite acid (PSA) as precursor for supported Pt catalysts

    SciTech Connect

    Regalbuto, J.R.; Ansel, O.; Miller, J.T.

    2010-11-12

    As a catalyst precursor, platinum sulfite acid (PSA) is easy to use and not relatively expensive, and is a potentially attractive precursor for many types of supported catalysts. The ultimate usefulness for many catalyst applications will depend on the extent that Pt can be dispersed and sulfur eliminated. To our knowledge, there exists no detailed characterization in the catalysis literature of PSA and the nanoparticulate Pt phases derived from it during catalyst pretreatment. To this end a series of supports including alumina, silica, magnesia, niobia, titania, magnesia and carbon were contacted with PSA solutions and subsequently analyzed with extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) analysis, and x-ray photoelectron spectroscopy (XPS) to characterize the Pt species formed upon impregnation, calcination, and reduction. While all catalysts show retention of some S, reasonably small particle sizes with relatively little Pt-S can in some instances be produced using PSA. The amount of retained sulfur appears to decrease with decreasing surface acidity, although even the most acidic supports (niobia and silica) display some storage of S even while only Pt-O bands are observed after calcination or reoxidation. More sulfur was eliminated by high temperature calcinations followed by reduction in hydrogen, at the expense of increasing Pt particle size.

  4. Tuning the metal-support interaction by structural recognition of cobalt-based catalyst precursors.

    PubMed

    Larmier, Kim; Chizallet, Céline; Raybaud, Pascal

    2015-06-01

    Controlling the nature and size of cobalt(II) polynuclear precursors on γ-alumina and silica-alumina supports represents a challenge for the synthesis of optimal cobalt-based heterogeneous catalysts. By density functional theory (DFT) calculations, we show how after drying the interaction of cobalt(II) precursor on γ-alumina is driven by a structural recognition phenomenon, leading to the formation of an epitaxial Co(OH)2 precipitate involving a Co-Al hydrotalcite-like interface. On a silica-alumina surface, this phenomenon is prevented due to the passivation effect of silica domains. This finding opens new routes to tune the metal-support interaction at the synthesis step of heterogeneous catalysts. PMID:25906826

  5. Alumoxane precursors to designer catalysts and catalyst supports: Catalytic oxidation of dichloromethane

    SciTech Connect

    Cook, R.L.; Wong, C.; Harlan, C.J.; Kareiva, A.; Barron, A.R.

    1997-12-31

    Carboxylato-alumoxanes are aluminum-oxygen macromolecules consisting of a boehmite-like core surrounded by a sheath of carboxylate groups. The alumoxanes may be processed like organic polymers yet when fired are readily transformed into ceramic oxides. The alumoxanes can be precisely doped at room temperature in aqueous solution with a range of metal cations to prepare novel catalyst and catalyst support materials. The ease of introduction of multiple cations into the alumina lattice via the alumoxane approach provides a method for fine-tuning catalyst support properties and the fabrication of new catalyst materials themselves. Manganese-doped alumina (Mn-Al{sub 2}O{sub 3}), formed via the doping of an alumoxane with Mn at room temperature, is presented as an example where the alumoxane route provides enhanced catalytic performance over traditional approaches for the low temperature catalytic oxidation of chlorinated hydrocarbons (CHCs). The Mn-Al{sub 2}O{sub 3} formed from the Mn-doped alumoxane is compared with MnO{sub 2}/Al{sub 2}O{sub 3} prepared by the incipient wetness method, and commercial Pt/Al{sub 2}O{sub 3} for the oxidation/destruction of dichloromethane (CH{sub 2}Cl{sub 2}).

  6. Methanol-reforming reaction over copper-containing catalysts: the effects of anions and copper loading in the preparation of the catalysts by kneading method

    SciTech Connect

    Kobayashi, H.; Takezawa, N.; Minochi, C.

    1981-06-01

    Methanol-reforming reaction CH/sub 3/OH + H/sub 2/O = 3H/sub 2/ + CO/sub 2/ was carried out over copper-containing catalysts which were prepared from hydroxides of copper or from the hydroxide kneaded with various metal oxides. The specific activity (activity per weight of copper used) either of supported or support-free catalyst was markedly increased when the hydroxide was prepared from alkali solution with addition of copper salt solution at higher pH or when the weight percentage of copper on the support was decreased. However, other kinetic parameters such as activation energy and selectivity of the reaction were unaffected by the preparation of the catalyst unless copper chloride was employed as a starting material of the hydroxide preparation at lower pH. DTA, ir, XPS, AES and other chemical analyses of the catalysts revealed that hydroxide ion in the hydroxide precipitate prepared at lower pH exchanged in part with the anionic group of its starting material during the course of the preparation. The anion or its fragment was found to be strongly held on the surface and inhibited the reaction to a great extent. On the other hand, the anion held was markedly decreased when the catalyst was prepared at higher pH. This catalyst was found to be highly active for the title reaction. The surface areas of metallic copper were considerably increased when copper was kneaded with the support. This gave rise to the increase in the specific activity of the catalyst.

  7. Chemical Vapor Deposition of Nanocarbon on Electroless NiB Catalyst Using Ethanol Precursor

    NASA Astrophysics Data System (ADS)

    Tanaka, Toru; Sato, Tomomi; Karasawa, Yusuke; Ueno, Kazuyoshi

    2011-05-01

    Nanocarbon materials have been expected as post-Cu interconnect materials for large-scale integrated circuits (LSIs). In this paper, we present a nanocarbon deposition process using electroless plated NiB as the catalyst, which features conformal deposition on patterned dielectric surfaces. It was found that carbon nanotubes (CNTs) and graphitic films were deposited on the electroless NiB by atmospheric pressure chemical vapor deposition (CVD) using ethanol as the precursor. The graphitic quality estimated from the Raman spectra of the nanocarbon on the NiB catalyst was equivalent to that on a sputter-deposited pure Ni catalyst. The nanocarbon shape was dependent on NiB thickness, and CNTs were grown on 10-nm-thick NiB and graphitic films were grown on 30 nm or thicker NiB. The deposition temperature can be lowered to 505 °C, although the graphitic quality was degraded. It is considered that the electroless catalysts can be effective for nanocarbon deposition on patterned dielectric surfaces.

  8. Ni-based heterogeneous catalyst from a designed molecular precursor for the efficient electrochemical water oxidation.

    PubMed

    Kuznetsov, Denis A; Konev, Dmitry V; Komarova, Natal'ya S; Ionov, Andrey M; Mozhchil, Rais N; Fedyanin, Ivan V

    2016-07-28

    Bimetallic Ni-Mo alkoxide was synthesized and exploited as the single-source precursor for the solution-processed deposition of the mixed-oxide layers on different conducting surfaces. Upon potential cycling in 1 M NaOH, these composites convert, in situ, into highly porous NiOx/NiOOH catalysts characterized by the high electrocatalytic activity for water oxidation under both basic (pH 13.6) and near neutral (pH 9.2) conditions. PMID:27354324

  9. Directed deposition of silicon nanowires using neopentasilane as precursor and gold as catalyst

    PubMed Central

    Kämpken, Britta; Wulf, Verena; Auner, Norbert; Winhold, Marcel; Huth, Michael; Rhinow, Daniel

    2012-01-01

    Summary In this work the applicability of neopentasilane (Si(SiH3)4) as a precursor for the formation of silicon nanowires by using gold nanoparticles as a catalyst has been explored. The growth proceeds via the formation of liquid gold/silicon alloy droplets, which excrete the silicon nanowires upon continued decomposition of the precursor. This mechanism determines the diameter of the Si nanowires. Different sources for the gold nanoparticles have been tested: the spontaneous dewetting of gold films, thermally annealed gold films, deposition of preformed gold nanoparticles, and the use of “liquid bright gold”, a material historically used for the gilding of porcelain and glass. The latter does not only form gold nanoparticles when deposited as a thin film and thermally annealed, but can also be patterned by using UV irradiation, providing access to laterally structured layers of silicon nanowires. PMID:23019549

  10. A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion.

    PubMed

    Transue, Wesley J; Velian, Alexandra; Nava, Matthew; Martin-Drumel, Marie-Aline; Womack, Caroline C; Jiang, Jun; Hou, Gao-Lei; Wang, Xue-Bin; McCarthy, Michael C; Field, Robert W; Cummins, Christopher C

    2016-06-01

    Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH(⧧) = 25.5 kcal/mol and ΔS(⧧) = -2.43 eu and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high-temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3(-), for which structural data have been obtained in a single-crystal X-ray diffraction study. Negative-ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3(-) has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods. PMID:27171847

  11. One-Step Liquid-Phase Synthesis of Carbon Nanotubes with Catalyst Precursors of Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Yamagiwa, Kiyofumi; Kikitsu, Tomoka; Yamashita, Shunsuke; Kuwano, Jun

    2011-01-01

    This paper describes a simple, low cost one-step liquid-phase process for the synthesis of highly aligned carbon nanotube (CNT) arrays (HACNTAs). Highly pure HACNTAs were grown on a stainless steel substrate by resistance-heating in methanol solution containing one of the organometallic complex catalyst precursors, ferrocene Fe(C5H5)2 and iron pentacarbonyl Fe(CO)5. Effects of the catalyst precursors on the formation and morphologies of HACNTAs were examined. A small amount of non-aligned multi-walled CNTs (MWCNTs) were grown from 1 mM Fe(C5H5)2 methanol solution. Highly pure HACNTAs composed of MWCNTs were readily grown from 10 and 40 mM Fe(C5H5)2 methanol solutions by this one-step liquid-phase process. From the Fe(CO)5 methanol solution, HACNTAs were prepared even at a very low Fe(CO)5 concentration of 0.01 mM, which was about 1/1000 lower than that of Fe(C5H5)2. The optimal low concentration is attributed to the low decomposition temperature of Fe(CO)5.

  12. Enhanced photodegradation of pentachlorophenol by single and mixed nonionic and anionic surfactants using graphene-TiO₂ as catalyst.

    PubMed

    Zhang, Yaxin; He, Xin; Zeng, Guangming; Chen, Tan; Zhou, Zeyu; Wang, Hongtao; Lu, Wenjing

    2015-11-01

    The photodegradation of pentachlorophenol (PCP) in a surfactant-containing (single and mixed) complex system using graphene-TiO2 (GT) as catalyst was investigated. The objective was to better understand the behavior of surfactants in a GT catalysis system for its possible use in remediation technology of soil contaminated by hydrophobic organic compounds (HOCs). In a single-surfactant system, surfactant molecules aggregated on GT via hydrogen bonding and electrostatic force; nonideal mixing between nonionic and anionic surfactants rendered GT surface with mixed admicelles in a mixed surfactant system. Both effects helped incorporating PCP molecules into surfactant aggregates on catalyst surface. Hence, the targeted pollutants were rendered easily available to photo-yielded oxidative radicals, and photodegradation efficiency was significantly enhanced. Finally, real soil washing-photocatalysis trials proved that anionic-nonionic mixed surfactant soil washing coupled with graphene-TiO2 photocatalysis can be one promising technology for HOC-polluted soil remediation. PMID:26194233

  13. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

    PubMed

    Kügler, Merle; Scholz, Julius; Kronz, Andreas; Siewert, Inke

    2016-04-28

    Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER. PMID:26986849

  14. Particle size, precursor, and support effects in the hydrogenolysis of alkanes over supported rhodium catalysts

    SciTech Connect

    Coq, B.; Dutartre, R.; Figueras, F.; Tazi, T. )

    1990-04-01

    A series of Rh catalysts of widely varying dispersion has been prepared using {gamma}-alumina as support and Rh acetylacetonate (Rh(acac){sub 3}) as precursor. The hydrogenolyses of n-hexane (nH), methylcyclopentane (MCP), and 2,2,3,3-tetramethylbutane (TeMB) were investigated as model reactions. Clear dependence of turnover frequency on Rh particle size is observed for nH and MCP hydrogenolysis, but only slight changes of selectivities occur with these alkanes. By contrast, large modifications of both specific activity and selectivity appear when TeMB is reacted. TeMB hydrogenolysis is thus a reliable tool for studying modifications of the surface structure of rhodium particles. This probe was used to investigate the effects of precursor and support on rhodium catalysts. The effect of chlorine is appreciable and shifts the selectivity of TeMB hydrogenolysis toward that of large particles. This is attributed to a different morphology of the rhodium particles. When the effect of dispersion of the metal is taken into account, no support effect is observed when SiO{sub 2} or ZrO{sub 2} is used as support. The different properties of rhodium on MgO can also be attributed to a different morphology of the particles. For Rh/TiO{sub 2} prepared from RhCl{sub 3} {center dot} 3H{sub 2}O, the catalytic properties are similar to those of Rh/Al{sub 2}O{sub 3} of moderate dispersion whatever temperature is used for reduction. Rh/TiO{sub 2} prepared from Rh(acac){sub 3} and reduced at 573 and 773 K simulates the catalytic properties of particles smaller than indeed observed. This effect can be interpreted by a partial coverage of the Rh surface by TiO{sub x} species (SMSI). This SMSI effect disappears upon reduction at 873 K.

  15. 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 (1catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  16. Diacetylenes with Ionic-Liquid-Like Substituents: Associating a Polymerizing Cation with a Polymerizing Anion in a Single Precursor for the Synthesis of N-Doped Carbon Materials.

    PubMed

    Fahsi, Karim; Dumail, Xavier; Dutremez, Sylvain G; van der Lee, Arie; Vioux, André; Viau, Lydie

    2016-01-26

    Imidazolium- and benzimidazolium-substituted diacetylenes with bromide or nitrogen-rich dicyanamide and tricyanomethanide anions were synthesized and used as precursors for the preparation of N-doped carbon materials. On pyrolysis under argon at 800 °C both halide precursors afforded graphite-like structures with nitrogen contents of about 8.5%. When the dicyanamide and tricyanomethanide precursors were thermolyzed at the same temperature, graphite-like structures were obtained that exhibit nitrogen contents in the range 17-20 wt%; thereby, the benefit of associating a polymerizing cation with a polymerizing anion in a single precursor was demonstrated. On pyrolysis at 1100 °C the nitrogen contents of the latter pyrolysates remain high (ca. 6 wt%). Adsorption measurements with krypton at 77 K indicated that the materials are nonporous. The highest electrical conductivity was observed for a pyrolysate with one of the lowest nitrogen contents, which also has the highest degree of graphitization. Thus, the quest for N-rich carbons with high electrical conductivities should include both maximization of the nitrogen content and optimization of the degree of graphitization. Crystallographic investigation of the precursors and spectroscopic characterization of the pyrolysates prepared by heating at 220 °C indicate that construction of the final carbon framework does not involve the intermediate formation of a polydiacetylene. PMID:26695842

  17. Catalyst-Free and Regioconvergent Substitution Reactions of Bromothiophenes with a BH3-Substituted Phosphide Anion.

    PubMed

    Imamoto, Tsuneo; Horiuchi, Yumi; Tamura, Ken; Sugiya, Masashi; Masu, Hyuma

    2016-08-19

    A range of bromothiophenes reacted with lithium boranato(tert-butyl)methylphosphide in the absence of transition-metal catalysts under mild conditions to provide the same 2,5-disubstituted and 2-monosubstituted products regardless of the substitution patterns of the starting bromothiophenes. PMID:27509360

  18. Effects of different manganese precursors as promoters on catalytic performance of CuO-MnOx/TiO2 catalysts for NO removal by CO.

    PubMed

    Sun, Chuanzhi; Tang, Yingjie; Gao, Fei; Sun, Jingfang; Ma, Kaili; Tang, Changjin; Dong, Lin

    2015-06-28

    Two different precursors, manganese nitrate (MN) and manganese acetate (MA), were employed to prepare two series of catalysts, i.e., xCuyMn(N)/TiO2 and xCuyMn(A)/TiO2, by a co-impregnation method. The catalysts were characterized by XRD, LRS, CO-TPR, XPS and EPR spectroscopy. The results suggest that: (1) both xCuyMn(N)/TiO2 and xCuyMn(A)/TiO2 catalysts exhibit much higher catalytic activities than an unmodified Cu/TiO2 catalyst in the NO + CO reaction. Furthermore, the activities of catalysts modified with the same amount of manganese are closely dependent on manganese precursors. (2) The enhancement of activities for Mn-modified catalysts should be attributed to the formation of the surface synergetic oxygen vacancy (SSOV) Cu(+)-□-Mn(y+) in the reaction process. Moreover, since the formation of the SSOV (Cu(+)-□-Mn(3+)) in the xCuyMn(N)/TiO2 catalyst is easier than that (Cu(+)-□-Mn(2+)) in the xCuyMn(A)/TiO2 catalyst, the activity of the xCuyMn(N)/TiO2 catalyst is higher than that of the xCuyMn(A)/TiO2 catalyst. This conclusion is well supported by the XPS and EPR results. PMID:26027847

  19. Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

    PubMed

    Kita, Yusuke; Hida, Shoji; Higashihara, Kenya; Jena, Himanshu Sekhar; Higashida, Kosuke; Mashima, Kazushi

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. PMID:27088539

  20. Nickel-carbon nanocomposites prepared using castor oil as precursor: A novel catalyst for ethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Carreño, Neftalí L. V.; Garcia, Irene T. S.; Raubach, Cristiane W.; Krolow, Mateus; Santos, Cláudia C. G.; Probst, Luiz F. D.; Fajardo, Humberto V.

    A novel and simple method to prepare nickel-based catalysts for ethanol steam reforming is proposed. The present method was developed using castor oil as a precursor. The results clarify that the nickel-carbon (Ni/C) catalyst has a high activity for ethanol steam reforming. It was observed that the catalytic behavior could be modified according to the experimental conditions employed. Moreover, it is interesting to note that the increase in the catalytic activity of the Ni/C nanocomposite over time, at 500 and 600 °C of reaction temperature, may be associated with the formation of filamentous carbon. The preliminary results indicate that the novel methodology used, led to the obtainment of materials with important properties that can be extended to applications in different catalytic process.

  1. Influence of the metal precursor on the catalytic behavior of Pt/ceria catalysts in the preferential oxidation of CO in the presence of H₂ (PROX).

    PubMed

    Jardim, Erika O; Rico-Francés, Soledad; Coloma, Fernando; Anderson, James A; Silvestre-Albero, Joaquín; Sepúlveda-Escribano, Antonio

    2015-04-01

    The effect of the metal precursor (presence or absence of chlorine) on the preferential oxidation of CO in the presence of H2 over Pt/CeO2 catalysts has been studied. The catalysts are prepared using (Pt(NH3)4)(NO3)2 and H2PtCl6, as precursors, in order to ascertain the effect of the chlorine species on the chemical properties of the support and on the catalytic behavior of these systems in the PROX reaction. The results show that chloride species exert an important effect on the redox properties of the oxide support due to surface chlorination. Consequently, the chlorinated catalyst exhibits a poorer catalytic activity at low temperatures compared with the chlorine-free catalyst, and this is accompanied by a higher selectivity to CO2 even at high reaction temperatures. It is proposed that the CO oxidation mechanism follows different pathways on each catalyst. PMID:25531415

  2. Recent Advances in Solid Catalysts Obtained by Metalloporphyrins Immobilization on Layered Anionic Exchangers: A Short Review and Some New Catalytic Results.

    PubMed

    Nakagaki, Shirley; Mantovani, Karen Mary; Machado, Guilherme Sippel; Castro, Kelly Aparecida Dias de Freitas; Wypych, Fernando

    2016-01-01

    Layered materials are a very interesting class of compounds obtained by stacking of two-dimensional layers along the basal axis. A remarkable property of these materials is their capacity to interact with a variety of chemical species, irrespective of their charge (neutral, cationic or anionic). These species can be grafted onto the surface of the layered materials or intercalated between the layers, to expand or contract the interlayer distance. Metalloporphyrins, which are typically soluble oxidation catalysts, are examples of molecules that can interact with layered materials. This work presents a short review of the studies involving metalloporphyrin immobilization on two different anionic exchangers, Layered Double Hydroxides (LDHs) and Layered Hydroxide Salts (LHSs), published over the past year. After immobilization of anionic porphyrins, the resulting solids behave as reusable catalysts for heterogeneous oxidation processes. Although a large number of publications involving metalloporphyrin immobilization on LDHs exist, only a few papers have dealt with LHSs as supports, so metalloporphyrins immobilized on LHSs represent a new and promising research field. This work also describes new results on an anionic manganese porphyrin (MnP) immobilized on Mg/Al-LDH solids with different nominal Mg/Al molar ratios (2:1, 3:1 and 4:1) and intercalated with different anions (CO₃(2-) or NO₃(-)). The influence of the support composition on the MnP immobilization rates and the catalytic performance of the resulting solid in cyclooctene oxidation reactions will be reported. PMID:26938518

  3. Structural characterization of alumina-supported Rh catalysts: effects of ceriation and zirconiation by using metal-organic precursors.

    PubMed

    Kroner, Anna B; Newton, Mark A; Tromp, Moniek; Russell, Andrea E; Dent, Andrew J; Evans, John

    2013-10-21

    The effects of the addition of ceria and zirconia on the structural properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ-Al2O3) are studied. Ceria and zirconia are deposited by using two preparation methods. Method I involves the deposition of ceria on γ-Al2O3 from Ce(acac)3, and the rhodium metal is subsequently added, whereas method II is based on a controlled surface reaction technique, that is, the decomposition of metal-organic M(acac)x (in which M=Ce, x=3 and M=Zr, x=4) on Rh/γ-Al2O3. The structures of the prepared catalyst materials are characterized ex situ by using N2 physisorption, transmission electron microscopy, high-angle annular dark-field scanning transmission election microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure spectroscopy (XAFS). All supported rhodium systems readily oxidize in air at room temperature. By using ceriated and zirconiated precursors, a larger rhodium-based metallic core fraction is obtained in comparison to the undoped rhodium catalysts, suggesting that ceria and zirconia protect the rhodium particles against extensive oxidation. XPS results indicate that after the calcination and reduction treatments, a small amount of chlorine is retained on the support of all rhodium catalysts. EXAFS analysis shows significant Rh-Cl interactions for Rh/Al2O3 and Rh/CeOx /Al2O3 (method I) catalysts. After reaction with H2/He in situ, for series of samples with 1.6 wt % Rh, the EXAFS first shell analysis affords a mean size of approximately 30 atoms. A broader spread is evident with a 4 wt % rhodium loading (ca. 30-110 atoms), with the incorporation of zirconium providing the largest particle sizes. PMID:23943563

  4. A novel semiconductor compatible path for nano-graphene synthesis using CBr4 precursor and Ga catalyst

    PubMed Central

    Wang, S. M.; Gong, Q.; Li, Y. Y.; Cao, C. F.; Zhou, H. F.; Yan, J. Y.; Liu, Q. B.; Zhang, L. Y.; Ding, G. Q.; Di, Z. F.; Xie, X. M.

    2014-01-01

    We propose a novel semiconductor compatible path for nano-graphene synthesis using precursors containing C-Br bonding and liquid catalyst. The unique combination of CBr4 as precursor and Ga as catalyst leads to efficient C precipitation at a synthesis temperature of 200°C or lower. The non-wetting nature of liquid Ga on tested substrates limits nano-scale graphene to form on Ga droplets and substrate surfaces at low synthesis temperatures of T ≤ 450°C and at droplet/substrate interfaces by C diffusion via droplet edges when T ≥ 400°C. Good quality interface nano-graphene is demonstrated and the quality can be further improved by optimization of synthesis conditions and proper selection of substrate type and orientation. The proposed method provides a scalable and transfer-free route to synthesize graphene/semiconductor heterostructures, graphene quantum dots as well as patterned graphene nano-structures at a medium temperature range of 400–700°C suitable for most important elementary and compound semiconductors. PMID:24722194

  5. Continuous biodiesel production in a fixed bed reactor packed with anion-exchange resin as heterogeneous catalyst.

    PubMed

    Ren, Yanbiao; He, Benqiao; Yan, Feng; Wang, Hong; Cheng, Yu; Lin, Ligang; Feng, Yaohui; Li, Jianxin

    2012-06-01

    A continuous biodiesel production from the transesterification of soybean oil with methanol was investigated in a fixed bed reactor packed with D261 anion-exchange resin as a heterogeneous catalyst. The conversion to biodiesel achieved 95.2% within a residence time 56 min under the conditions: reaction temperature of 323.15K, n-hexane/soybean oil weight rate of 0.5, methanol/soybean oil molar ratio of 9:1 and feed flow rate of 1.2 ml/min. The resin can be regenerated in-situ and restored to the original activity to achieve continuous production after the resin deactivation. The product obtained was mainly composed of methyl esters. No glycerol in the product was detected due to the resin adsorbing glycerol in the fixed bed, which solved the issue of glycerol separation from biodiesel. It is believed that the fixed bed reactor with D261 has a potential commercial application in the transesterification of triglyceride. PMID:22138595

  6. Carbon supported Ag nanoparticles as high performance cathode catalyst for H2/O2 anion exchange membrane fuel cell

    PubMed Central

    Xin, Le; Zhang, Zhiyong; Wang, Zhichao; Qi, Ji; Li, Wenzhen

    2013-01-01

    A solution phase-based nanocapsule method was successfully developed to synthesize non-platinum metal catalyst—carbon supported Ag nanoparticles (Ag/C). XRD patterns and TEM image show Ag nanoparticles with a small average size (5.4 nm) and narrow size distribution (2–9 nm) are uniformly dispersed on the carbon black Vulcan XC-72 support. The intrinsic activity and pathway of oxygen reduction reaction (ORR) on the Ag/C and commercial Pt/C were investigated using rotating ring disk electrode (RRDE) tests at room temperature. The results confirmed that the 4-electron pathway of ORR proceeds on small Ag nanoparticles, and showed comparable ORR activities on the self-prepared Ag/C and a commercial Pt/C. A single H2-O2 anion exchange membrane fuel cell (AEMFC) with the Ag/C cathode catalyst exhibited an open circuit potential of 0.98 V and a peak power density of 190 mW/cm2 at 80°C. PMID:24790944

  7. The acrylation of glycerol over solid base catalysts: A precursor to functionalized lipids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Transesterification of lipids using lipases is a common strategy used to incorporate novel acids into triacylglycerides. This approach, however, is limited to acids with pKa’s similar to common fatty acids. To overcome this limitation, we have used heterogeneous basic catalysts for the synthesis o...

  8. Characterization and reactivity of nanoscale La(Co,Cu)O{sub 3} perovskite catalyst precursors for CO hydrogenation

    SciTech Connect

    Nguyen Tien-Thao; Alamdari, Houshang; Kaliaguine, Serge

    2008-08-15

    The characterization of La(Co,Cu)O{sub 3} perovskites has been performed by several techniques including XRD, BET, H{sub 2}-TPR, O{sub 2}-TPO, TPRS, and the solids tested as catalysts for the hydrogenation of CO. The reducibility of the perovskites is strongly affected by the preparation route, calcination temperature, catalyst morphology, and the amount of remnant alkali. Compared with the citrate-derived perovskite, LaCoO{sub 3} sample prepared by mechano-synthesis has various distinct Co{sup 3+} ions in perovskite lattice, which are reduced at different temperatures. Under typical conditions, the reduction of cobalt ions occurs in two consecutive steps: Co{sup 3+}/Co{sup 2+} and Co{sup 2+}/Co{sup 0}, while the intra-lattice copper ions are directly reduced from Cu{sup 2+} to Cu{sup 0}. The reducibility of cobalt ions is promoted by the presence of metallic copper, which is formed at a lower reduction temperature. The re-oxidation of the reduced lanthanum cobaltite perovskite could regenerate the original structure, whereas that of the reduced Co-Cu-based samples is less reversible under the same experimental conditions. The cobalt atom in the reduced perovskites plays an important role in the dissociation of CO, but the presence of a neighboring copper along with remnant sodium ions on the catalyst surface has remarkably affected the reactivity of cobalt for CO hydrogenation. The addition of copper into the perovskite framework leads to a change in the product distribution of CO hydrogenation and a decrease in reaction temperature. An increased copper content leads to a substantial decline in the rate of methanation and an increase in the formation of higher alcohols. A close proximity between cobalt and copper sites on the Na{sup +}-modified catalyst surface of the reduced nanocrystalline Co-Cu-based perovskites plays a crucial role in the synthesis of higher alcohols from syngas. - Graphical abstract: The ground La(Co,Cu)O{sub 3} perovskite precursors were

  9. Delamination of layered zeolite precursors under mild conditions: synthesis of UCB-1 via fluoride/chloride anion-promoted exfoliation.

    PubMed

    Ogino, Isao; Nigra, Michael M; Hwang, Son-Jong; Ha, Jeong-Myeong; Rea, Thomas; Zones, Stacey I; Katz, Alexander

    2011-03-16

    New material UCB-1 is synthesized via the delamination of zeolite precursor MCM-22 (P) at pH 9 using an aqueous solution of cetyltrimethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium chloride at 353 K. Characterization by powder X-ray diffraction, transmission electron microscopy, and nitrogen physisorption at 77 K indicates the same degree of delamination in UCB-1 as previously reported for delaminated zeolite precursors, which require a pH of greater than 13.5 and sonication in order to achieve exfoliation. UCB-1 consists of a high degree of structural integrity via (29)Si MAS NMR and Fourier transform infrared spectroscopies, and no detectable formation of amorphous silica phase via transmission electron microscopy. Porosimetry measurements demonstrate a lack of hysteresis in the N(2) adsorption/desorption isotherms and macroporosity in UCB-1. The new method is generalizable to a variety of Si:Al ratios and leads to delaminated zeolite precursor materials lacking amorphization. PMID:21341663

  10. Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in PEM fuel cells

    PubMed Central

    Herranz, Juan; Jaouen, Frédéric; Lefèvre, Michel; Kramm, Ulrike I.; Proietti, Eric; Dodelet, Jean-Pol; Bogdanoff, Peter; Fiechter, Sebastian; Abs-Wurmbach, Irmgard; Bertrand, Patrick; Arruda, Thomas M.; Mukerjee, Sanjeev

    2013-01-01

    The high cost of proton-exchange-membrane fuel cells would be considerably reduced if platinumbased catalysts were replaced by iron-based substitutes, which have recently demonstrated comparable activity for oxygen reduction, but whose cause of activity decay in acidic medium has been elusive. Here, we reveal that the activity of Fe/N/C-catalysts prepared through a pyrolysis in NH3 is mostly imparted by acid-resistant FeN4-sites whose turnover frequency for the O2 reduction can be regulated by fine chemical changes of the catalyst surface. We show that surface N-groups protonate at pH 1 and subsequently bind anions. This results in decreased activity for the O2 reduction. The anions can be removed chemically or thermally, which restores the activity of acid-resistant FeN4-sites. These results are interpreted as an increased turnover frequency of FeN4-sites when specific surface N-groups protonate. These unprecedented findings provide new perspective for stabilizing the most active Fe/N/C-catalysts known to date. PMID:24179561

  11. Selenium-containing organic nanoparticles as silent precursors for ultra-sensitive thiol-responsive transmembrane anion transport.

    PubMed

    Lang, Chao; Zhang, Xin; Dong, Zeyuan; Luo, Quan; Qiao, Shanpeng; Huang, Zupeng; Fan, Xiaotong; Xu, Jiayun; Liu, Junqiu

    2016-02-01

    An anion transporter with a selenoxide group was able to form nanoparticles in water, whose activity was fully turned off due to the aggregation effect. The formed nanoparticles have a uniform size and can be readily dispersed in water at high concentrations. Turn-on of the nanoparticles by reducing molecules is proposed to be a combined process, including the reduction of selenoxide to selenide, disassembly of the nanoparticles and location of the transporter to the lipid membrane. Accordingly, a special acceleration phase can be observed in the turn-on kinetic curves. Since turn-on of the nanoparticles is quantitatively related to the amount of reductant, the nanoparticles can be activated in a step-by-step manner. Due to the sensibility of this system to thiols, cysteine can be detected at low nanomolar concentrations. This ultra-sensitive thiol-responsive transmembrane anion transport system is quite promising in biological applications. PMID:26783054

  12. Selenium-containing organic nanoparticles as silent precursors for ultra-sensitive thiol-responsive transmembrane anion transport

    NASA Astrophysics Data System (ADS)

    Lang, Chao; Zhang, Xin; Dong, Zeyuan; Luo, Quan; Qiao, Shanpeng; Huang, Zupeng; Fan, Xiaotong; Xu, Jiayun; Liu, Junqiu

    2016-01-01

    An anion transporter with a selenoxide group was able to form nanoparticles in water, whose activity was fully turned off due to the aggregation effect. The formed nanoparticles have a uniform size and can be readily dispersed in water at high concentrations. Turn-on of the nanoparticles by reducing molecules is proposed to be a combined process, including the reduction of selenoxide to selenide, disassembly of the nanoparticles and location of the transporter to the lipid membrane. Accordingly, a special acceleration phase can be observed in the turn-on kinetic curves. Since turn-on of the nanoparticles is quantitatively related to the amount of reductant, the nanoparticles can be activated in a step-by-step manner. Due to the sensibility of this system to thiols, cysteine can be detected at low nanomolar concentrations. This ultra-sensitive thiol-responsive transmembrane anion transport system is quite promising in biological applications.An anion transporter with a selenoxide group was able to form nanoparticles in water, whose activity was fully turned off due to the aggregation effect. The formed nanoparticles have a uniform size and can be readily dispersed in water at high concentrations. Turn-on of the nanoparticles by reducing molecules is proposed to be a combined process, including the reduction of selenoxide to selenide, disassembly of the nanoparticles and location of the transporter to the lipid membrane. Accordingly, a special acceleration phase can be observed in the turn-on kinetic curves. Since turn-on of the nanoparticles is quantitatively related to the amount of reductant, the nanoparticles can be activated in a step-by-step manner. Due to the sensibility of this system to thiols, cysteine can be detected at low nanomolar concentrations. This ultra-sensitive thiol-responsive transmembrane anion transport system is quite promising in biological applications. Electronic supplementary information (ESI) available: Synthetic procedure and

  13. Performance of supported catalysts based on a new copper vanadate-type precursor for catalytic oxidation of toluene.

    PubMed

    Palacio, L A; Silva, E R; Catalão, R; Silva, J M; Hoyos, D A; Ribeiro, F R; Ribeiro, M F

    2008-05-01

    A new copper vanadate precursor with the formula NH(4)[Cu(2.5)V(2)O(7)(OH)(2)] . H(2)O was synthesized and deposited on two different supports, ZSM-5 and amorphous SiO(2), by a hydrothermal method or by mechanical mixture. The catalytic behaviour was evaluated in the total oxidation of toluene and the characterization was performed by H(2)-temperature-programmed reduction (H(2)-TPR), thermogravimetric analysis, elemental analysis, UV-vis diffuse reflectance spectroscopy and X-ray diffraction. It was found that the copper vanadate phase comprises two mixed oxides, one of them crystalline, the Ziesite phase, and the other one amorphous. The supported catalysts presented a content of copper vanadate phase of about 9-11 wt.%. The copper vanadate deposited on ZSM-5 by the hydrothermal method evidences the best performance in the oxidation of toluene. This behaviour can be associated with the smaller size and higher dispersion of the particles on the support, which was confirmed by their better reducibility and higher band gap energy value compared with the other series of studied catalysts. PMID:17942223

  14. Self-assembled 3D-hierarchical structure Cu2ZnSnS4 photocathodes by tuning anion ratios in precursor solution

    NASA Astrophysics Data System (ADS)

    Wen, Xin; Luo, Wenjun; Guan, Zhongjie; Shao, Hansen; Fu, Gao; Zhou, Yong; Zou, Zhigang

    2016-03-01

    Cu2ZnSnS4 (CZTS) is one of the most promising light capture materials for solar cells or solar fuels. Construction of 3D hierarchical structure is very important for efficient optoelectronic devices. It is challenging to directly fabricate 3D hierarchical structure CZTS film by a facile solution method. Herein, we present a one-step sol-gel method for fabrication of CZTS thin films with 3D hierarchical structures. For the first time, it is found that the morphologies of thin films can be adjusted between dense, porous and 3D hierarchical structures by tuning anion ratios of Cl-/Ac- in precursor solution. Further analysis suggests the formation of intermediate phases of SnO2 nanoparticles and SnS2 nanosheets by tuning ratios of Cl-/Ac- in precursor solution, which has important effects on the formation of different nanostructures of CZTS. This study can deepen understanding of anion’ effect on morphologies of samples using a solution method and forms a reference to prepare novel nanostructures of other materials.

  15. Enhanced nanoscale catalyst precursor powders generated using a flow-through hydrothermal process

    SciTech Connect

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

    1994-08-01

    A novel flow-through hydrothermal process, termed the Rapid Thermal Decomposition of precursors in Solution (RTDS), has been used to generate large quantities of ultra-fine, nano-crystalline hematite ({alpha}-Fe{sub 2}O{sub 3}), 6-line ferrihydrite (5Fe{sub 2}O{sub 3}{center_dot}9H{sub 2}O) and ferric oxyhydroxysulfate powders. The heterogeneous catalytic activity of these powders towards C-C bond scission in the model compound naphthyl bibenzylmethane and in the first-stage liquefaction of Blind Canyon seam coal was investigated. The effects of the crystalline phase and the agglomerate size of these powders on their catalytic activity are reported.

  16. Microwave-hydrothermal synthesis and characterization of nanostructured copper substituted ZnM2O4 (M = Al, Ga) spinels as precursors for thermally stable Cu catalysts.

    PubMed

    Conrad, Franziska; Massue, Cyriac; Kühl, Stefanie; Kunkes, Edward; Girgsdies, Frank; Kasatkin, Igor; Zhang, Bingsen; Friedrich, Matthias; Luo, Yuan; Armbrüster, Marc; Patzke, Greta R; Behrens, Malte

    2012-03-21

    Nanostructured Cu(x)Zn(1-x)Al(2)O(4) with a Cu:Zn ratio of ¼:¾ has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al(2)O(3)-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m(2) g(-1)). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen and the accessible metallic Cu(0) surface area of the reduced catalyst was 8 m(2) g(-1). The catalytic performance of the material in CO(2) hydrogenation and methanol steam reforming was compared with conventionally prepared Cu/ZnO/Al(2)O(3) reference catalysts. The observed lower performance of the spinel-based samples is attributed to a lack of synergetic interaction of the Cu nanoparticles with ZnO due to the incorporation of Zn(2+) in the stable spinel lattice. Despite its lower performance, however, the nanostructured nature of the spinel catalyst was stable after thermal treatment up to 500 °C in contrast to other Cu-based catalysts. Furthermore, a large fraction of the re-oxidized copper migrates back into the spinel upon calcination of the reduced catalyst, thereby enabling a regeneration of sintered catalysts after prolonged usage at high temperatures. Similarly prepared samples with Ga instead of Al exhibit a more crystalline catalyst with a spinel particle size around 20 nm. The slightly decreased Cu(0) surface area of 3.2 m(2) g(-1) due to less copper incorporation is not a significant drawback for the methanol steam reforming. PMID:22327266

  17. Engineering Vertically Aligned Carbon Nanotube Growth by Decoupled Thermal Treatment of Precursor and Catalyst

    SciTech Connect

    Meshot, E.; Plata, D; Tawfick, S; Zhang, Y; Verploegen, E; Hart, A

    2009-01-01

    We study synthesis of vertically aligned carbon nanotube (CNT) 'forests' by a decoupled method that facilitates control of the mean diameter and structural quality of the CNTs and enables tuning of the kinetics for efficient growth to forest heights of several millimeters. The growth substrate temperature (Ts) primarily determines the CNT diameter, whereas independent and rapid thermal treatment (Tp) of the C2H4/H2 reactant mixture significantly changes the growth rate and terminal forest height but does not change the CNT diameter. Synchrotron X-ray scattering is utilized for precise, nondestructive measurement of CNT diameter in large numbers of samples. CNT structural quality monotonically increases with Ts yet decreases with Tp, and forests grown by this decoupled method have significantly higher quality than those grown using a conventional single-zone tube furnace. Chemical analysis reveals that the thermal treatment generates a broad population of hydrocarbon species, and a nonmonotonic relationship between catalyst lifetime and Tp suggests that certain carbon species either enhance or inhibit CNT growth. However, the forest height kinetics, as measured in real-time during growth, are self-similar, thereby indicating that a common mechanism of growth termination may be present over a wide range of process conditions.

  18. Pt-Sn/C catalysts prepared by sodium borohydride reduction for alcohol oxidation in fuel cells: Effect of the precursor addition order

    NASA Astrophysics Data System (ADS)

    López-Suárez, F. E.; Bueno-López, A.; Eguiluz, K. I. B.; Salazar-Banda, G. R.

    2014-12-01

    A series of Pt-Sn/C catalysts used as anodes during ethanol oxidation are synthesized by a deposition process using NaBH4 as the reducing agent. The order in which the precursors are added affects the electrocatalytic activity and physical-chemical characteristics of the bimetallic catalysts, where the Pt-Sn catalyst prepared by co-precipitation of both metals functions best below a potential of 0.5 V and the catalyst prepared by sequential deposition of Sn and Pt (drying after Sn addition) is most active above a potential of 0.5 V. The electrochemical behavior of catalysts during ethanol oxidation in an acidic medium are characterized and monitored in a half-cell test at room temperature by cyclic voltammetry, chronoamperometry and anode potentiostatic polarization. Catalyst structure and chemical composition are investigated by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). This behavior presented for best Pt-Sn catalyst can be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and Sn.

  19. Water-soluble Pd nanoparticles synthesized from ω-carboxyl-S-alkanethiosulfate ligand precursors as unimolecular micelle catalysts.

    PubMed

    Gavia, Diego J; Maung, May S; Shon, Young-Seok

    2013-12-11

    This report describes a two-phase synthesis of water-soluble carboxylate-functionalized alkanethiolate-capped Pd nanoparticles from ω-carboxyl-S-alkanethiosulfate sodium salts. The two-phase methodology using the thiosulfate ligand passivation protocol allowed a highly specific control over the surface ligand coverage of these nanoparticles, which are lost in a one-phase aqueous system because of the base-catalyzed hydrolysis of thiosulfate to thiolate. Systematic synthetic variations investigated in this study included the concentration of ω-carboxyl-S-alkanethiosulfate ligand precursors and reducing agent, NaBH4, and the overall ligand chain length. The resulting water-soluble Pd nanoparticles were isolated and characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), (1)H NMR, UV-vis, and FT-IR spectroscopy. Among different variations, a decrease in the molar equivalent of NaBH4 resulted in a reduction in the surface ligand density while maintaining a similar particle core size. Additionally, reducing the chain length of the thiosulfate ligand precursor also led to the formation of stable nanoparticles with a lower surface coverage. Since the metal core size of these Pd nanoparticle variations remained quite consistent, direct correlation studies between ligand properties and catalytic activities against hydrogenation/isomerization of allyl alcohol could be performed. Briefly, Pd nanoparticles dissolved in water favored the hydrogenation of allyl alcohol to 1-propanol whereas Pd nanoparticles heterogeneously dispersed in chloroform exhibited a rather high selectivity towards the isomerization product (propanal). The results suggested that the surrounding ligand environments, such as the ligand structure, conformation, and surface coverage, were crucial in determining the overall activity and selectivity of the Pd nanoparticle catalysts. PMID:24246150

  20. Water-Soluble Pd Nanoparticles Synthesized from ω-Carboxyl-S-Alkanethiosulfate Ligand Precursors as Unimolecular Micelle Catalysts

    PubMed Central

    Gavia, Diego J.; Maung, May S.; Shon, Young-Seok

    2014-01-01

    This report describes a two-phase synthesis of water-soluble carboxylate-functionalized alkanethiolate-capped Pd nanoparticles from ω-carboxyl-S-alkanethiosulfate sodium salts. The two-phase methodology using the thiosulfate ligand passivation protocol allowed a highly specific control over the surface ligand coverage of these nanoparticles, which are lost in a one-phase aqueous system because of the base-catalyzed hydrolysis of thiosulfate to thiolate. Systematic synthetic variations investigated in this study included the concentration of ω-carboxyl-S-alkanethiosulfate ligand precursors and reducing agent, NaBH4, and the overall ligand chain length. The resulting water-soluble Pd nanoparticles were isolated and characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), 1H NMR, UV–vis, and FT-IR spectroscopy. Among different variations, a decrease in the molar equivalent of NaBH4 resulted in a reduction in the surface ligand density while maintaining a similar particle core size. Additionally, reducing the chain length of the thiosulfate ligand precursor also led to the formation of stable nanoparticles with a lower surface coverage. Since the metal core size of these Pd nanoparticle variations remained quite consistent, direct correlation studies between ligand properties and catalytic activities against hydrogenation/isomerization of allyl alcohol could be performed. Briefly, Pd nanoparticles dissolved in water favored the hydrogenation of allyl alcohol to 1-propanol whereas Pd nanoparticles heterogeneously dispersed in chloroform exhibited a rather high selectivity towards the isomerization product (propanal). The results suggested that the surrounding ligand environments, such as the ligand structure, conformation, and surface coverage, were crucial in determining the overall activity and selectivity of the Pd nanoparticle catalysts. PMID:24246150

  1. Microcalorimetric Studies of Surface Acid/Base Properties of Magnesium Iron Catalysts Prepared from Hydrotalcite-Type Precursors

    NASA Astrophysics Data System (ADS)

    Tu, Mai; Shen, Jianyi; Chen, Yi

    1997-01-01

    Magnesium-iron mixed oxides with Mg/Fe molar ratios 1,3, and 6 were prepared from hydrotalcite-type precursors. Microcalorimetric adsorption of NH 3and CO 2showed that the surface acidity and basicity of the mixed oxides after calcination at 673 K are similar despite the different Mg/Fe ratios. Increasing calcination temperature from 673 to 773 K significantly decreased the surface area of the 3 Mg/Fe oxide, but the densities of both the acid and base sites were not changed. Mössbauer spectroscopy revealed that the reduction of the 3 Mg/Fe oxide (Fe 2O 3/MgO) in H 2at 673 K converted all Fe 3+to Fe 2+. The resulted FeO/MgO exhibited the same acidity as that of the Fe 2O 3/MgO, but the basicity of the FeO/MgO was greatly enhanced. Reduction at 773 K resulted in the formation of 76% Fe 2+and 24% Fe 0as detected by Mössbauer spectroscopy. The Fe/FeO/MgO sample formed exhibited very low heat for the adsorption of NH 3(40 kJ/mol) indicating that all iron atoms on the surface are Fe 0. However, a substantial basicity remained on the surface of this sample that may account for its high olefin selectivity compared with pure iron catalyst in the Fischer-Tropsch synthesis.

  2. Dry reforming of methane on Ni-Mg-Al nano-spheroid oxide catalysts prepared by the sol-gel method from hydrotalcite-like precursors

    NASA Astrophysics Data System (ADS)

    González, Albert R.; Asencios, Yvan J. O.; Assaf, Elisabete M.; Assaf, José M.

    2013-09-01

    Nanocapsular hydrotalcites (layered double hydroxides - LDHs) were synthesized by the sol-gel method and used as precursors of nano-structured mixed oxides containing various nickel loads (4, 15 and 19 wt%). The best conditions for the preparation of LDHs were analyzed and the structures of the resulting mixed oxides were studied. The optimal nickel load and calcining conditions were optimized. Finally, the resulting catalysts were tested in the dry reforming of methane for 8 h at 800 °C under atmospheric pressure. These materials showed high activity and stability, and the coke deposits were minimal on the catalyst prepared under optimal conditions (19 wt% nickel load and thermal treatment at 650 °C). The best catalyst formed amorphous carbon, which seems not to be prejudicial to the reaction.

  3. New layered vandyl(IV) phosphite as a precursor to vanadyl pyrophosphate catalysts for partial oxidation of n-Butane to maleic anhydride

    SciTech Connect

    Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

    1995-10-01

    The synthesis and characterization of layered vanadyl(IV) phosphonates, VOC{sub n}H{sub 2n+1}PO{sub 3}{center_dot}xH{sub 2}O containing the V{sub 2}O{sub 8} dimers have been recently reported. The authors present here the results of partial oxidation of n-butane on VPO catalysts derived from the simplest of these phosphonates, vanadyl phosphite. The results indicate that vanadyl(IV) phosphite is the precursor to vanadyl pyrophosphate catalysts with high surface area (ca. 45 m{sup 2}/g) and selectivity to maleic anhydride in n-butane partial oxidation comparable to the conventional unpromoted catalyst. 10 refs., 3 figs., 1 tab.

  4. Surface properties of the Ni-silica gel catalyst precursors for the vegetable oil hydrogenation process: N2 sorption and XPS studies

    NASA Astrophysics Data System (ADS)

    Nikolova, D.; Krstić, J.; Spasov, L.; Simeonov, D.; Lončarević, D.; Stefanov, Pl.; Jovanović, D.

    2011-12-01

    The effect of the type of the silica gel pore structure on the surface properties of the Ni-silica gel catalyst precursors for the vegetable oil hydrogenation process has been examined applying N2 sorption and X-ray photoelectron spectroscopy techniques. The nickel catalyst precursors with identical composition (SiO2/Ni = 1.0) has been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the three types of silica gel with different pore structures. It is shown that the usage of the silica gel supports with different texture as source of SiO2 causes different location of Ni-species into the support pores and on the external surface area. The XPS data confirm the formation of surface species with different strength of interaction and different dispersion. These surface characteristics of the precursors will predetermine the formation of the active nickel metallic phase as well as the mass transfer of the reactants and products to and from the catalytic sites.

  5. [Catalyst research]. Final Report

    SciTech Connect

    Ian P Rothwell; David R McMillin

    2005-03-14

    Research results are the areas of catalyst precursor synthesis, catalyst fluxionality, catalyst stability, polymerization of {alpha}-olefins as well as the chemistry of Group IV and Group V metal centers with aryloxide and arylsulfide ligands.

  6. Anions in Cometary Comae

    NASA Technical Reports Server (NTRS)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  7. A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells.

    PubMed

    Miller, Hamish A; Lavacchi, Alessandro; Vizza, Francesco; Marelli, Marcello; Di Benedetto, Francesco; D'Acapito, Francesco; Paska, Yair; Page, Miles; Dekel, Dario R

    2016-05-10

    One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM-FCs). The anion exchange membrane fuel cell (AEM-FC) has long been proposed as a solution as non-Pt metals may be employed. Despite this, few examples of Pt-free AEM-FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt-free AEM-FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt-free AEM-FC that employs a mixed carbon-CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM-FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm(-2) . PMID:27062251

  8. Anion-directed self-assembly of two half-sandwich ruthenium-based metallamacrocycles as catalysts for water oxidation.

    PubMed

    Yu, Wei-Bin; He, Qing-Ya; Shi, Hua-Tian; Yuan, Guozan; Wei, Xianwen

    2015-01-01

    The binuclear [η(6) -(cymene)Ru(L)]2 (OTf)2 (TfO(-) =trifluoromethanesulfonate) and tetranuclear [η(6) -(cymene)Ru(L)]4 (NO3 )4 metallacycles were prepared by treating the pyridyl-substituted 8-hydroxyquinoline ligand (E)-2-[2-(pyridin-3-yl)vinyl]quinolin-8-ol (HL) with [(p-cymene)Ru(μ-Cl)Cl]2 in the presence of AgOTf or AgNO3 . The molecular structures of these complexes were confirmed by single-crystal X-ray diffraction, which revealed that both complexes have macrocycle frameworks induced by the TfO(-) and NO3 (-) counteranions, respectively. The electrochemical properties of the two metallacycles were investigated by cyclic voltammetry, which showed that they have great potential as catalysts for water oxidation. Good efficiency was obtained by utilizing the nitrate complex as a water oxidation catalyst in the presence of a Ce(IV) salt as an oxidant at high pH values. PMID:25303729

  9. Anion-π Enzymes

    PubMed Central

    2016-01-01

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anioncatalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anioncatalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pKa of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pKa of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  10. Anion-π Enzymes.

    PubMed

    Cotelle, Yoann; Lebrun, Vincent; Sakai, Naomi; Ward, Thomas R; Matile, Stefan

    2016-06-22

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anioncatalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anioncatalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pK a of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pK a of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  11. In situ construction of three anion-dependent cu(i) coordination networks as promising heterogeneous catalysts for azide-alkyne "click" reactions.

    PubMed

    Xu, Zhenghu; Han, Lu Lu; Zhuang, Gui Lin; Bai, Jing; Sun, Di

    2015-05-18

    Three Cu(I) coordination networks, namely, {[Cu2(bpz)2(CN)X]·CH3CN}n, (X = Cl, 1; I, 3), {[Cu6(bpz)6(CH3CN)3(CN)3Br]·2OH·14CH3CN}n, (2, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazole), were prepared by using solvothermal method. The cyanide ligands in these networks were generated in situ by cleavage of C-C bond of MeCN under solvothermal condition. The structures of these networks are dependent on halogen anions. Complex 1 is a ladderlike structure with μ2-CN(-) as rung and μ2-bpz as armrest. The Cl(-) in 1 is at terminal position but does not extend the one-dimensional (1D) ladder to higher dimensionalities. Complex 2 is a three-dimensional (3D) framework comprised of novel planar [Cu3Br] triangle and single Cu nodes, which are extended by μ2-bpz and μ2-CN(-) to form a novel (3,9)-connected gfy network. Density functional theory calculations showed that single-electron delocalization of Br atom induces the plane structure of [Cu3Br]. Complex 3 also possesses a similar ladderlike subunit as in 1, but the I(-) acts as bidentate bridge to extend the ladder to 3D framework with a four-connected sra topology. The three networks show notable catalytic activity on the click reaction. The compared catalytic results demonstrate that complex 2 possesses the best catalysis performance among three complexes, which is ascribed to the largest solvent-accessible void (porosity: 2 (29.4%) > 1 (25.7%) > 3 (17.6%)) and the more Cu(I) active sites in 2. The present combined structure-property studies provide not only a new synthetic route to obtain a new kind of catalyst for click reaction but also the new insights on catalyst structure-function relationships. PMID:25941881

  12. ESR study of the interaction of O/sub 2//sup -/ radical anions with aromatic molecules on V/SiO/sub 2/, V/ZrO/sub 2/, and V/MgO catalysts

    SciTech Connect

    Gasymov, A.M.; Shvets, V.A.; Kazanskii, V.B.

    1983-02-01

    The reactivity of O/sub 2//sup -/ radical anions adsorbed on supported V/SiO/sub 2/, V/ZrO/sub 2/, and V/MgO catalysts in reactions with benzene, toluene, and o-xylene molecules has been studied quantitatively with the aid of ESR by comparing the rate constants of the elementary steps. It has been found that the reactivity of O/sub 2//sup -/ interacting with benzene, toluene, and o-xylene molecules increases along the series C/sub 6/H/sub 6/ less than or equal to C/sub 6/H/sub 5/CH/sub 3/ less than or equal to C/sub 6/H/sub 4/ (CH/sub 3/)/sub 2/ and that the activity of the radical anions on the catalysts investigated increases along the series V/MgO less than or equal to V/ZrO/sub 2/ less than or equal to V/SiO/sub 2/. The main products of the reaction of O/sub 2//sup -/ radical anions adsorbed on V/SiO/sub 2/ and V/ZrO/sub 2/ catalysts with benzene and o-xylene molecules at 150-250/sup 0/C were the products of thorough oxidation.

  13. Characterization and reactivity of nanoscale La(Co,Cu)O 3 perovskite catalyst precursors for CO hydrogenation

    NASA Astrophysics Data System (ADS)

    Tien-Thao, Nguyen; Alamdari, Houshang; Kaliaguine, Serge

    2008-08-01

    The characterization of La(Co,Cu)O 3 perovskites has been performed by several techniques including XRD, BET, H 2-TPR, O 2-TPO, TPRS, and the solids tested as catalysts for the hydrogenation of CO. The reducibility of the perovskites is strongly affected by the preparation route, calcination temperature, catalyst morphology, and the amount of remnant alkali. Compared with the citrate-derived perovskite, LaCoO 3 sample prepared by mechano-synthesis has various distinct Co 3+ ions in perovskite lattice, which are reduced at different temperatures. Under typical conditions, the reduction of cobalt ions occurs in two consecutive steps: Co 3+/Co 2+ and Co 2+/Co 0, while the intra-lattice copper ions are directly reduced from Cu 2+ to Cu 0. The reducibility of cobalt ions is promoted by the presence of metallic copper, which is formed at a lower reduction temperature. The re-oxidation of the reduced lanthanum cobaltite perovskite could regenerate the original structure, whereas that of the reduced Co-Cu-based samples is less reversible under the same experimental conditions. The cobalt atom in the reduced perovskites plays an important role in the dissociation of CO, but the presence of a neighboring copper along with remnant sodium ions on the catalyst surface has remarkably affected the reactivity of cobalt for CO hydrogenation. The addition of copper into the perovskite framework leads to a change in the product distribution of CO hydrogenation and a decrease in reaction temperature. An increased copper content leads to a substantial decline in the rate of methanation and an increase in the formation of higher alcohols. A close proximity between cobalt and copper sites on the Na +-modified catalyst surface of the reduced nanocrystalline Co-Cu-based perovskites plays a crucial role in the synthesis of higher alcohols from syngas.

  14. Development of a simple method for the preparation of novel egg-shell type Pt catalysts using hollow silica nanostructures as supporting precursors

    SciTech Connect

    Wang Jiexin; Chen Jianfeng

    2008-04-01

    A simple method for the preparation of novel egg-shell type platinum catalysts was developed and achieved by utilizing unique hollow silica nanostructures, i.e., hollow silica nanospheres and nanotubes, as supports. The observation by transmission electron microscopy indicated that the well-dispersed hollow silica supported Pt catalysts with a Pt particle diameter of 8-14 nm can be successfully prepared by wet impregnation process and heat treatment. The Pt-loaded hollow silica nanostructures were also characterized by inductively coupled plasma, X-ray diffraction, specific surface area, Fourier transformation infrared spectroscopy, X-ray photoelectron spectroscopy and energy dispersive spectroscopy. It was thus demonstrated that a higher Pt loading amount (0.392%) could be obtained under the same conditions except the addition of ammonia, which was found to be more effective than that (0.061%) with the addition of HCl in the immobilization of Pt. In addition, the effect of soaking time, Pt precursor concentration and calcination temperature on the loading of Pt in hollow silica nanostructures were investigated as well.

  15. Effect of the support and the reduction temperature on the formation of metallic nickel phase in Ni/silica gel precursors of vegetable oil hydrogenation catalysts

    NASA Astrophysics Data System (ADS)

    Gabrovska, M.; Krstić, J.; Tzvetkov, P.; Tenchev, K.; Shopska, M.; Vukelić, N.; Jovanović, D.

    2011-12-01

    Ni/SiO2 materials with identical composition (SiO2/Ni = 1.0) have been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the silica gel, obtained at three different pH values. The present investigation was undertaken in an endeavor to study the effects of the silica gel support type and the reduction temperature on the formation and dispersion of the metallic nickel phase in the reduced Ni/SiO2 precursors of the vegetable oil hydrogenation catalyst. The physicochemical characterization of the unreduced and reduced precursors has been accomplished appropriately by powder X-ray diffraction, infrared spectroscopy, temperature programmed reduction and H2-chemisorption techniques. It can be stated that the texture peculiarities of the silica gels used as supports influence on the crystalline state and distribution of the deposited Ni-containing phases during the preparation of the precursors, on the reduction temperature of the investigated solids as well as on the bulk size and surface dispersion of the arising metallic nickel particles. It was shown that two types of Ni2+-species are formed during the synthesis procedure, namely basic nickel carbonate-like and Ni-phyllosilicate with different extent of presence, location and strength of interaction. The different location of these species is supposed to result in various strength of Ni-O and Ni-O-Si interaction, thus determining the overall reducibility of the precursors. It was specified that the Ni2+-species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions. It was established that the precursor, derivates from the silica gel obtained at alkaline conditions, demonstrates both significant reduction of the Ni2+ ions at 430°C and finely dispersed metallic nickel particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of

  16. Kinetics of NiO and NiCl2 hydrogen reduction as precursors and properties of produced Ni/Al2O3 and Ni-Pd/Al2O3 catalysts.

    PubMed

    Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

    2015-01-01

    The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623-923 K) and time intervals (1-5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

  17. Kinetics of NiO and NiCl2 Hydrogen Reduction as Precursors and Properties of Produced Ni/Al2O3 and Ni-Pd/Al2O3 Catalysts

    PubMed Central

    Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

    2015-01-01

    The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623–923 K) and time intervals (1–5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

  18. Three-way catalytic performance of Pd/Ce0.67Zr0.33O2-Al2O3 catalysts: Role of the different Pd precursors

    NASA Astrophysics Data System (ADS)

    Lin, Siyu; Yang, Xue; Yang, Linyan; Zhou, Renxian

    2015-02-01

    Catalytic performance of Pd/Ce0.67Zr0.33O2-Al2O3 catalysts for CO, HC and NOx elimination is greatly influenced by Pd precursors. Pd/CZA(Cl) catalyst prepared with H2PdCl4 as precursor exhibits a good catalytic performance for HC and NO conversion. PdOx species are mainly dispersed on Al2O3 surface with larger PdOx particle size and higher electron density. Residual Cl species in the catalyst could be removed and PdOx species would migrate to (Ce,Zr)xO2-rich gain surface after aging treatment, promoting catalyst thermal stability. While Pd/CZA(NO) and Pd/CZA(NH) catalysts prepared with Pd(NO3)2 or Pd(NH3)4(NO3)2 as precursor promote CO oxidation at low temperature. PdOx species are mainly dispersed on (Ce,Zr)xO2-rich gain surface with smaller Pd particle size and strong Pd-support interaction. Surface chemistry under reaction conditions is revealed by in situ DRIFTS studies. PdOx species dispersed on Al2O3 surface in Pd/CZA(Cl) could be partly reduced during reaction, promoting NO adsorption and dissociation. CO is more easily adsorbed than NO on metallic Pd sites dispersed in (Ce,Zr)xO2-rich gain surface, inhibiting NO conversion for Pd/CZA(NO) and Pd/CZA(NH).

  19. Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

    NASA Astrophysics Data System (ADS)

    Wellons, Matthew S.

    The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

  20. Synthesis and structural characterization of double metal cyanides of iron and zinc: catalyst precursors for the copolymerization of carbon dioxide and epoxides.

    PubMed

    Darensbourg, Donald J; Adams, M Jason; Yarbrough, Jason C; Phelps, Andrea L

    2003-12-01

    Several synthetic approaches for the preparation of double metal cyanide (DMC) derivatives of iron(II) and zinc(II) are described. These include (1) metathesis reactions of ZnCl(2) or ZnI(2) with KCpFe(CN)(2)CO in aqueous solution, (2) reactions of KCpFe(CN)(2)CO and its phosphine-substituted analogues with Zn(CH(3)CN)(4)(BF(4))(2) and subsequent displacement of acetonitrile at the zinc centers by the addition of a neutral (phosphine) or anionic (phenoxide) ligand, and (3) reactions of the protonated HCpFe(CN)(2)(phosphine) complexes with Zn(N(SiMe(3))(2))(2), followed by the addition of phenols. All structures are based on a diamond-shaped planar arrangement of the Fe(2)(CN)(4)Zn(2) core with various appended ligands at the metal sites. Although attempts to replace the iodide ligands in [CpFe(mu-CN)(2)PPh(3)ZnI(THF)](2) with acetate using silver acetate failed, two novel cationic mixed-metal cyanide salts based on the [CpFe(PPh(3))(mu-CN)(2)Zn(NC(5)H(5))](2)(2+) framework were isolated from pyridine solution and their structures were defined by X-ray crystallography. The anionic ligand bound to zinc in these derivatives, which serve as an anionic polymerization initiator, was shown to be central to the catalytic copolymerization reaction of CO(2)/epoxide to provide polycarbonates and cyclic carbonates. The structurally stabilized phosphine-strapped complexes [CpFe(mu-CN)(2)Zn(X)THF](2)(mu-dppp), where X = I or phenolate, were shown to be thermally stable under the conditions (80 degrees C) of the copolymerization reaction by in situ infrared spectroscopy. Both of these derivatives were proposed to serve as mimics for the heterogeneous DMC catalysts in the patent literature, with the derivative where the initiator is a phenolate being more active for the production of polycarbonates. PMID:14632496

  1. Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

    PubMed

    Yin, Li-Chang; Wang, Ping; Kang, Xiang-Dong; Sun, Cheng-Hua; Cheng, Hui-Ming

    2007-03-28

    Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate. PMID:17356758

  2. Anion-π catalysis.

    PubMed

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-01

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  3. Effects of precursor and support variation in the genesis of uranium oxide catalysts for CO oxidation and selective reduction of NO: Synthesis and characterization.

    PubMed

    Campbell, Tom; Newton, Mark A; Boyd, Vicky; Lee, Darren F; Evans, John

    2005-02-24

    A range of uranium oxide-based catalysts, derived from UO2(NO3)2.6H2O and UCl4 precursors, and supported on gamma-Al2O3, SiO2 and mesoporous H1SiO2, have been synthesized and then characterized using the following methods: isothermal nitrogen adsorption/desorption measurements, diffuse reflectance infrared spectroscopy (DRIFTS), gas titration of surface hydroxyl groups using Grignard reagents, U L(III) extended X-ray absorption fine structure (EXAFS), powder X-ray diffraction (PXRD), and thermogravimetric and differential thermal analysis. Brij76-templated H1SiO2 mesoporous silicas are found to be essentially stable under flowing oxygen after 16 h at 1073 K. At temperatures above this, however, extensive structural collapse, together with extensive dehydroxylation, ensues. Titration of the accessible hydroxyl group concentrations shows that in these materials the density of OH groups is considerably lower than in their amorphous counterparts. The adsorption of uranyl nitrate onto these dispersants results in a supported, and partially dehydrated, phase of the parent molecule with little obvious structural distortion; however, the adsorption of UCl4 leads to a complex adstructure which may best be described as U(O)2Cl2. The subsequent formation of the uranium oxide phase, nominally active for the oxidation of CO and selective reduction of NO (generally accepted to be U3O8), is found to be a considerable function of both the precursor and support system employed. Calcination of such systems to 1073 K results in extensive extrusion of the supported uranium phase from mesoporous supports, resulting in the formation of very large orthorhombic U3O8 domains. PXRD, however, shows that on amorphous SiO2 and gamma-Al2O3 similar treatment results in the formation of a hexagonal phase of U3O8. The formation of U3O8 is found to be promoted in mesoporous systems and by the presence of Cl in the catalyst make up. Some evidence is also found that suggests that a persistence of Cl

  4. Supported chromium-molybdenum and tungsten sulfide catalysts

    SciTech Connect

    Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

    1988-05-31

    This patent describes the process for preparing a supported hydroprocessing catalyst. The process comprising compositing a quantity of a particulate, porous catalyst support material comprising one or more refactory oxides with one or more catalyst precursor salts and heating the composite at elevated temperature of at least about 200/sup 0/C up to about 600/sup 0/, in the presence of a sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur-bearing compound in an amount whereby sulfur in the form of the sulfur bearing compound is present in excess of that contained in the catalyst precursor and under oxygen-free conditions for a time sufficient to form the catalyst. The catalyst precursor salt contains a tetrathiometallate anion of Mo, W or mixture therof and a cation comprising trivalent chromium or a mixture of trivalent chromium with one or more divalent promoter metals selected from the group consisting of Fe, Ni, Co, Mn, Cu and a mixture thereof wherein the trivalent chromium and divalent promoter metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L.

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

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

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

    PubMed

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

    2014-01-01

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

  8. Hydrotreating catalysts comprising supported mixtures of a sulfide of trivalent chromium and molybdenum or tungsten

    SciTech Connect

    Young, A.R.; Ho, T.C.; Jacobson, A.J.; Chianelli, R.R.

    1986-11-11

    This patent describes a hydrocracking process comprising contacting a hydrocarbon feed at a temperature of at least about 100/sup 0/C. and in the presence of hydrogen, with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material and a hydrated oxide of trivalent chromium with one or more precursor salts and heating the composite at elevated temperature of at least about 150/sup 0/C. The composite is heated in the presence of sulfur or sulfur bearing compound and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising the conjugate acid of one or more neutral, nitrogen-containing ligands, L, at least one of which is a chelating polydentate ligand. The feed contacts the catalyst for a time sufficient to hydrocrack at least a portion of the feed.

  9. Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: reaction intermediates determination.

    PubMed

    Ovejero, G; Rodríguez, A; Vallet, A; García, J

    2013-01-01

    In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed. PMID:22960061

  10. [Ru(η5-C5H5)(η6-C10H8)]PF6 as a catalyst precursor for the one-pot direct C-H alkenylation of nitrogen heterocycles.

    PubMed

    Lynam, Jason M; Milner, Lucy M; Mistry, Neetisha S; Slattery, John M; Warrington, Sally R; Whitwood, Adrian C

    2014-03-21

    The ruthenium naphthalene complex [Ru(η(5)-C5H5)(η(6)-C10H8)](+) is a catalyst precursor for the direct C-H alkenylation of pyridine and related nitrogen heterocycles by terminal alkynes. Stoichiometric studies have demonstrated that the naphthalene ligand may be displaced by either pyridine, 4-methylpyridine or dimethylaminopyridine (DMAP) to give species [Ru(η(5)-C5H5)L3](+) (L = nitrogen-based ligand). Reaction of in situ-generated [Ru(η(5)-C5H5)(py)3](+) (py = pyridine) with PPh3 results in the formation of [Ru(η(5)-C5H5)(PPh3)(py)2](+), the active catalyst for direct alkenylation, some [Ru(η(5)-C5H5)(PPh3)2(py)](+) is also formed in this reaction. A one-pot procedure is reported which has allowed for the nature of the nitrogen heterocycle and phosphine ligand to be evaluated. The sterically demanding phosphine PCy3 inhibits catalysis, and only trace amounts of product are formed when precursors containing a pentamethylcyclopentadienyl group were used. The greatest conversion was observed with PMe3 when used as co-ligand with [Ru(η(5)-C5H5)(η(6)-C10H8)](+). PMID:24481140

  11. Chemical Modeling of Cometary Anions

    NASA Astrophysics Data System (ADS)

    Cordiner, Martin; Charnley, S. B.

    2009-09-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of 1P/Halley. The anions O-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not previously been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydrodynamical model of Rodgers & Charnley (2002), we investigate the role of the hydrocarbon and nitrile anions Cn-, CnH- and CnN- in the coma. We calculate the effects of these anions on the charge balance and examine their impact on cometary coma chemistry. References: Chaizy, P. et al. 1991, Nature, 349, 393 Rodgers, S.D. & Charnley, S.B. 2002, MNRAS, 330, 660

  12. Properties of Cu(thd)2 as a precursor to prepare Cu/SiO2 catalyst using the atomic layer epitaxy technique.

    PubMed

    Chen, Ching S; Lin, Jarrn H; You, Jainn H; Chen, Chi R

    2006-12-20

    The new Cu/SiO2 catalyst is developed by the atomic layer epitaxy (ALE) method. The ALE-Cu/SiO2 catalyst with high dispersion and nanoscale Cu particles appears to have very different catalytic properties from those of the typical Cu-based catalysts, which have satisfactory thermal stability to resist the sintering of Cu particles at 773 K. Due to the formation of small Cu particles, the ALE-Cu/SiO2 can strongly bind CO and give high catalytic activity for CO2 converted to CO in the reverse water-gas-shift reaction. The catalytic activity decreases in the order of 2.4% ALE-Cu/SiO2 =... 2% Pt/SiO2 > 2% Pd/SiO2 > 10.3% IM-Cu/SiO2. PMID:17165704

  13. Relation between hydrodesulfurization activity and the state of promoters in precursor calcined Ni-Co-Mo/Al/sub 2/O/sub 3/ catalysts

    SciTech Connect

    Caceres, C.; Fierro, J.L.G.; Agudo, A.L.; Severino, F.; Laine, J.

    1986-01-01

    Two series of NiCo-Mo/Al/sub 2/O/sub 3/ hydrodesulfurization (HDS) catalysts prepared by different procedures were investigated. In each series the Mo loading and the total content of promoters (Co + Ni) were kept constant but the Co/(Co + Ni) atomic ratio was varied from 0 to 1. The two series of catalysts were prepared by a sequential wet impregnation technique. In series I, the impregnations of both Mo and promoters were carried out at the pH of the impregnating aqueous solutions, employing an intermediate calcination; in series II, Mo was impregnated at pH 10, while the promoters were added in aqueous ethanol solutions without intermediate calcination. Catalysts in their calcined state were characterized by reduction in H/sub 2/ at 500/sup 0/C, O/sub 2/ chemisorption, and infrared spectroscopy of adsorbed NO. The HDS activity and the optimum Co/(Co + Ni) atomic ratio were different for the two series, in agreement with the previous studies, HDS activity being generally higher for series II than for series I. Dispersion of Mo (as estimated from O/sub 2/ chemisorption) and NO adsorption on Mo in reduced catalysts (as judged from the intensity of the band at about 1705 cm/sup -1/) were not substantially different for the two series of catalysts and did not correlate with HDS activity. However, adsorbed NO on promoters in oxidized catalysts (bands at about 1880 and 1800 cm/sup -1/) followed roughly the same trend as HDS activity, suggesting that the active sites may be related to the Co and Ni atoms adsorbing NO. Possible reasons for the differences between HDS activity of the two series are considered.

  14. Electron-Withdrawing Trifluoromethyl Groups in Combination with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond Catalysts, and Anion Receptors

    SciTech Connect

    Shokri, Alireza; Wang, Xue B.; Kass, Steven R.

    2013-06-26

    Electron withdrawing trifluoromethyl groups were characterized in combination with hydrogen bond interactions in three polyols (i.e., CF3CH(OH)CH2CH(OH)CF3, 1; (CF3)2C(OH)C(OH)(CF3)2, 2; ((CF3)2C(OH)CH2)2CHOH, 3) by pKa measurements in DMSO and H2O, negative ion photoelectron spectroscopy and binding constant determinations with Cl–. Their catalytic behavior in several reactions were also examined and compared to a BrØnsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF3)3C6H3NH)2CS). The combination of inductive stabilization and hydrogen bonds was found to afford potent acids which are effective catalysts. It also appears that hydrogen bonds can transmit the inductive effect over distance even in an aqueous environment, and this has far reaching implications.

  15. Amorphous alloy catalysis: VII. Activation and surface characterization of an amorphous Cu-Ti alloy catalyst precursor in the dehydrogenation of 2-propanol and comparison with Cu-Zr

    SciTech Connect

    Katona, T.; Molnar, A.

    1995-05-01

    The activation and catalytic properties of Cu-Ti and Cu-Zr metallic glass precursors in the dehydrogenation of 2-propanol differ substantially. In contrast with Cu-Zr, Cu-Ti can only be activated with HF solution. The pretreatment of Cu-Ti results in catalysts with BET and copper surface areas one order of magnitude smaller than those of Cu-Zr under the same conditions. Cu-Ti exhibits decreasing catalytic activity, while Cu-Zr displays stable activity in the course of the reaction. Crystallization of the metallic glasses prior to HF treatment results in a weaker reactivity toward hydrogen fluoride for both alloys. Scanning electron micrographs of the alloys reveal that HF etching results in surfaces with deep grooves, and copper-rich flakes, a Raney-Cu-like catalyst. Auger electron spectroscopic studies show copper enrichment in the surface region on both alloys after HF treatment. On the surface of Cu-Ti, mostly Cu(II) is detected, whereas Cu(O) and Cu(II) coexist on Cu-Zr. 54 refs., 11 figs., 2 tabs.

  16. A new class of organocatalysts: sulfenate anions.

    PubMed

    Zhang, Mengnan; Jia, Tiezheng; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J

    2014-09-26

    Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst. PMID:25111259

  17. Chelating bis-N-heterocyclic carbene complexes of iron(ii) containing bipyridyl ligands as catalyst precursors for oxidation of alcohols.

    PubMed

    Pinto, Mara F; Cardoso, Bernardo de P; Barroso, Sónia; Martins, Ana M; Royo, Beatriz

    2016-09-14

    Chelating bis-N-heterocyclic carbene (bis-NHC) complexes of iron(ii) containing pyridyl ligands have been prepared by the reaction of [FeCl2L] [L = bipy (1), phen (2)] with [LiN(SiMe3)2] and a bis(imidazolium) salt. The [Fe(bis-NHC)L(I)2] complexes were active pre-catalysts in the oxidation of 1-phenylethanol with tert-butyl hydroperoxide in neat conditions, affording a quantitative yield of acetophenone in 4.5 h. The catalyst could be reused up to six cycles giving a turnover number (TON) of 1500. Various secondary alcohols, both aromatic and aliphatic were selectivity oxidised to the corresponding ketones in excellent yields. Compound 1 is stable in acetonitrile solution for ca. 4 h, although after 16 h, it evolves to a mixture of [Fe(bis-NHC)(bipy)2]I2 (3), [Fe(bipy)3](2+) and bis-imidazolium salt. The molecular structure of 3 has been determined by X-ray diffraction studies. PMID:27506414

  18. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1982-01-01

    The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

  19. Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

    DOEpatents

    Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

    2002-10-29

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  20. Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

    DOEpatents

    Wang. Yong; Peden. Charles H. F.; Choi. Saemin

    2004-11-09

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  1. Development of the local and average structure of a V-Mo-Nb oxide catalyst with Mo5O14-like structure during synthesis from nanostructured precursors

    SciTech Connect

    Kardash, Tatyana Yu; Plyasova, Ludmilla M; Kochubey, Dmitry I; Bondareva, Valentina M; Neder, Reinhard B

    2012-05-29

    A combination of X-ray and neutron PDF measurements with powder diffraction and EXAFS data was used to determine the structures of a V-Mo-Nb-oxide catalyst and its poorly crystallized precursors that exhibit the strongest catalytic activities. The crystalline material belongs to space group P-4 21m, a = 22.8, c = 4.002, and is build up of pentagonal MeO7 bipyramids surrounded by edge sharing Me-octahedrons (Me = Mo, V, Nb). In the average structure all MeO7 units are at the same z-level, while the local structure analysis shows systematic shifts along [001]. Samples synthesized at 300 °C and 400 °C exhibit a nanostructure, whose local structure predates the final crystalline structure. Initial nanoparticles are spherical and grow predominantly along the c-axis. The successful analysis required a reverse analysis that took the crystalline material as starting model for the samples synthesized at lower temperatures.

  2. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    NASA Astrophysics Data System (ADS)

    Chang, Zheng; Zhao, Na; Liu, Junfeng; Li, Feng; Evans, David G.; Duan, Xue; Forano, Claude; de Roy, Marie

    2011-12-01

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N 2 adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide.

  3. Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

    PubMed

    Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

    2009-02-28

    The Ru/Cu system is of historical significance in catalysis. The early development and application of X-ray absorption spectroscopy (XAS) led to the original 'bimetallic cluster" concept for highly-immiscible systems. This work explores alkali leaching of Al-based ternary crystalline and quasicrystalline precursors as a potential route to bulk Ru/Cu alloys. Single-phase ternary alloys at 3 trial compositions; Al(71)Ru(22)Cu(7), Al(70.5)Ru(17)Cu(12.5), and Al(70)Ru(10)Cu(20), were prepared by arc melting of the pure metal components. After leaching, the bimetallic residues were characterized principally by transmission XAS, "as-leached" and after annealing in H(2) (and passivation) in a thermobalance. XRD and BET revealed a nanocrystalline product with a native structure of hexagonal Ru. XPS surface analysis of Ru(22)Cu(7) and Ru(17)Cu(12.5) found only slight enrichment by Cu in the as-leached forms, with little change upon annealing. Ru(10)Cu(20) was highly segregated as-leached. XANES data showed preferential oxidation of Cu in Ru(22)Cu(7), implying that it exists as an encapsulating layer. TG data supports this view since it does not show the distinct two-stage O(2) uptake characteristic of skeletal Ru. Cu K-edge EXAFS data for Ru(22)Cu(7) were unique in showing a high proportion of Ru neighbours. The spacing, d(CuRu) = 2.65 A, was that expected from a hypothetical (ideal) solid solution at this composition, but this is unlikely in such a bulk-immiscible system and Ru K-edge EXAFS failed to confirm bulk alloying. Furthermore its invariance under annealing was more indicative of an interfacial bond between bulk components, although partial alloying with retention of local order cannot entirely be ruled out. The XAS and XPS data were reconciled in a model involving surface and bulk segregation, Cu being present at both the grain exterior and in ultra-fine internal pores. This structure can be considered as the 3-dimensional analogue of the classical type

  4. Anatomy of gold catalysts: facts and myths

    PubMed Central

    Ranieri, Beatrice; Escofet, Imma

    2015-01-01

    This review article covers the main types of gold(i) complexes used as precatalysts under homogeneous conditions in organic synthesis and discusses the different ways of catalyst activation as well as ligand, silver, and anion effects. PMID:26055272

  5. 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.

  6. 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.

  7. Schiff base structured acid-base cooperative dual sites in an ionic solid catalyst lead to efficient heterogeneous knoevenagel condensations.

    PubMed

    Zhang, Mingjue; Zhao, Pingping; Leng, Yan; Chen, Guojian; Wang, Jun; Huang, Jun

    2012-10-01

    An acid-base bifunctional ionic solid catalyst [PySaIm](3)PW was synthesized by the anion exchange of the ionic-liquid (IL) precursor 1-(2-salicylaldimine)pyridinium bromide ([PySaIm]Br) with the Keggin-structured sodium phosphotungstate (Na(3) PW). The catalyst was characterized by FTIR, UV/Vis, XRD, SEM, Brunauer-Emmett-Teller (BET) theory, thermogravimetric analysis, (1)H NMR spectroscopy, ESI-MS, elemental analysis, and melting points. Together with various counterparts, [PySaIm](3)PW was evaluated in Knoevenagel condensation under solvent and solvent-free conditions. The Schiff base structure attached to the IL cation of [PySaIm](3)PW involves acidic salicyl hydroxyl and basic imine, and provides a controlled nearby position for the acid-base dual sites. The high melting and insoluble properties of [PySaIm](3)PW are relative to the large volume and high valence of PW anions, as well as the intermolecular hydrogen-bonding networks among inorganic anions and IL cations. The ionic solid catalyst [PySaIm](3)PW leads to heterogeneous Knoevenagel condensations. In solvent-free condensation of benzaldehyde with ethyl cyanoacetate, it exhibits a conversion of 95.8 % and a selectivity of 100 %; the conversion is even much higher than that (78.2 %) with ethanol as a solvent. The solid catalyst has a convenient recoverability with only a slight decrease in conversion following subsequent recyclings. Furthermore, the new catalyst is highly applicable to many substrates of aromatic aldehydes with activated methylene compounds. On the basis of the characterization and reaction results, a unique acid-base cooperative mechanism within a Schiff base structure is proposed and discussed, which thoroughly explains not only the highly efficient catalytic performance of [PySaIm](3)PW, but also the lower activities of various control catalysts. PMID:22907828

  8. Aryl-triazole foldamers incorporating a pyridinium motif for halide anion binding in aqueous media.

    PubMed

    Shang, Jie; Zhao, Wei; Li, Xichen; Wang, Ying; Jiang, Hua

    2016-03-15

    Aryl-triazole oligomers incorporating a pyridinium motif have been synthesized from their pyridine precursors. Anion binding studies show that methylation of the pyridine units can significantly enhance the halide anion affinities of the folded oligomers so that the foldamers are capable of binding halide anions in aqueous solutions. PMID:26933696

  9. Pressure pyrolysed non-precious oxygen reduction catalysts for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Nallathambi, Vijayadurga

    2011-12-01

    Worldwide energy demand has driven long-term efforts towards developing a clean, hydrogen-based energy economy. Polymer electrolyte membrane fuel cells (PEMFC) are low emissions and high efficiency devices that utilize the power of hydrogen and are a key enabling technology for the hydrogen economy. Carbon supported platinum-black is the state-of the art catalyst for oxygen reduction in a PEMFC because it can withstand the acidic environment. However, the high cost and low abundance of this precious metal has limited large-scale commercialization of PEMFCs. Current efforts focus on developing alternative inexpensive, non-noble metal-based catalysts for oxygen reduction with performance comparable to conventional platinum based electrocatalysts. In this work, inexpensive metal-nitrogen-carbon (MNC) catalysts have been synthesized by pyrolyzing transition metal and nitrogen precursors together with high surface area carbon materials in a closed, constant-volume quartz tube. High pressure generated due to nitrogen precursor evaporation lead to increased surface nitrogen content in the catalysts post-pyrolysis. Electrochemical oxygen reduction activity of MNC catalysts was analyzed using half-cell Rotating Ring Disc Electrode (RRDE) studies. The effect of nitrogen precursor morphology on the generation of active sites has been explored in detail. By increasing the Nitrogen/Carbon ratio of the nitrogen precursor, the accessible active site density increased by reducing carbon deposition in the pores of the carbon support during pyrolysis. The most active catalysts were obtained using melamine, having a N/C ratio of 2. Single PEMFC measurements employing MNC catalysts as cathodes indicated kinetic current density as high as 15 A cm-3 at 0.8 ViR-free and over 100 h of stable current at 0.5 V were observed. Effects of carbon free ammonia generating solid nitrogen precursors such as urea and ammonium carbamate were also studied. These precursors etched the carbon support

  10. Supported chromium-molybdenum and tungsten sulfide catalysts

    SciTech Connect

    Chianelli, R.R.; Ho, T.C.; Jacobson, A.J.; Young, A.R.

    1986-12-02

    A process is described for hydrotreating a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150/sup 0/C. and in the presence of hydrogen with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts. Then the composite is heated at elevated temperature of at least about 150/sup 0/C., in the presence of excess sulfur in the form of one or more sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising trivalent chromium or a mixture of trivalent chromium with one or more divalent promoter metals selected from the group consisting of Fe, Ni, Co, Mn, Zn, and Cu wherein the trivalent chromium and divalent promoter metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L. The contacting occurs for a time sufficient to hydrotreat at least a portion of the feed.

  11. 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.

  12. Transient Anion States of Biomolecules

    NASA Astrophysics Data System (ADS)

    Varella, Marcio

    2012-10-01

    Much of the interest on electron interactions with biomolecules is related to radiation damage [Gohlke and Illenberger, Europhys. News 33, 207 (2002)]. The high energy photons employed in radiology and radiotherapy generate a large number of fast electrons in living cells. These electrons thermalize in a picosecond scale, eventually forming dissociative matestable anions with water and biomolecules. In this work, we employ the parallel version of Schwinger Multichannel Method with Pseudopotentials [Bettega et al., Phys. Rev. A 47, 1111 (1993); Santos et al., J. Phys. Chem. 136, 084307 (2012)] to investigate transient anion states of protein and nucleic acid precursors. We address glycine in both neutral and zwitterionic forms, as well as glycine-water clusters and disulfide bonds. The interest on the two forms of glycine (and other amino acids) relies on the fact that only the neutral form is stable in the gas phase, while the zwitterion is more stable in solution, pointing out limitations of standard gas-phase studies. Electron attachment to disulfide bonds also has potential impact on protein stability. Finally we address transient anion states of substituted uracil molecules in the gas phase. [4pt] In collaboration with M. H. F. Bettega, S. d'A. Sanchez, R. F. da Costa, M. A. P. Lima, J. S. dos Santos, and F. Kossoski.

  13. Sodium citrate-assisted anion exchange strategy for construction of Bi{sub 2}O{sub 2}CO{sub 3}/BiOI photocatalysts

    SciTech Connect

    Song, Peng-Yuan; Xu, Ming; Zhang, Wei-De

    2015-02-15

    Highlights: • Heterostructured Bi{sub 2}O{sub 2}CO{sub 3}/BiOI microspheres were prepared via anion exchange. • Sodium citrate-assisted anion exchange for construction of composite photocatalysts. • Bi{sub 2}O{sub 2}CO{sub 3}/BiOI composites show high visible light photocatalytic activity. - Abstract: Bi{sub 2}O{sub 2}CO{sub 3}/BiOI heterojuncted photocatalysts were constructed through a facile partial anion exchange strategy starting from BiOI microspheres and urea with the assistance of sodium citrate. The content of Bi{sub 2}O{sub 2}CO{sub 3} in the catalysts was regulated by modulating the amount of urea as a precursor, which was decomposed to generate CO{sub 3}{sup 2−} in the hydrothermal process. Citrate anion plays a key role in controlling the morphology and composition of the products. The Bi{sub 2}O{sub 2}CO{sub 3}/BiOI catalysts display much higher photocatalytic activity than pure BiOI and Bi{sub 2}O{sub 2}CO{sub 3} towards the degradation of rhodamine B (RhB) and bisphenol A (BPA). The enhancement of photocatalytic activity of the heterojuncted catalysts is attributed to the formation of p–n junction between p-BiOI and n-Bi{sub 2}O{sub 2}CO{sub 3}, which is favorable for retarding the recombination of photoinduced electron-hole pairs. Moreover, the holes are demonstrated to be the main active species for the degradation of RhB and BPA.

  14. Anion exchange membrane

    DOEpatents

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  15. An anionic surfactant for EOR applications

    NASA Astrophysics Data System (ADS)

    Sagir, Muhammad; Tan, Isa M.; Mushtaq, Muhammad

    2014-10-01

    This work is to investigate the new anionic surfactants for the Enhanced Oil Recovery (EOR) application. Sulfonated anionic surfactant was produced by attaching SO3 to an ethoxylated alcohol to increase the performance of the surfactant. Methallyl chloride and ethoxylated alcohol was reacted followed by the reaction with sodium bisulfite to produce anionic sulfonated surfactant in 80.3 % yield. The sulfonation reaction parameters such as reactants mole ratio, reaction temperature and catalyst amount were optimized. The generation and stability of foam from the synthesized surfactant is also tested and results are reported. The synthesized novel surfactant was further investigated for the effect on the CO2 mobility in porous media and the findings are presented here. This in house developed surfactant has a great potential for CO2- EOR applications.

  16. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    DOEpatents

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2007-01-09

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  17. Cyclopentadienyl-Containing Low-Valent Early Transition Metal Olefin Polymerization Catalysts

    DOEpatents

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2004-06-08

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C-containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  18. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    DOEpatents

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2003-12-30

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, SnR".sub.3, and C.dbd.C containing groups (R".dbd.C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  19. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    DOEpatents

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2003-04-08

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n }.sup.+ {A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 -C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 -C.sub.20 hydrocarbyl, SiR".sub.3, NR".sub.2, OR", SR", GeR".sub.3, and SnR".sub.3 containing groups (R"=C.sub.1 -C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  20. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts

    DOEpatents

    Marks, Tobin J.; Luo, Lubin; Yoon, Sung Cheol

    2006-10-10

    A catalyst system useful to polymerize and co-polymerize polar and non-polar olefin monomers is formed by in situ reduction with a reducing agent of a catalyst precursor comprising {Cp*MRR'.sub.n}.sup.+{A}.sup.- wherein Cp* is a cyclopentadienyl or substituted cyclopentadienyl moiety; M is an early transition metal; R is a C.sub.1 C.sub.20 hydrocarbyl; R' are independently selected from hydride, C.sub.1 C.sub.20 hydrocarbyl, SiR''.sub.3, NR''.sub.2, OR'', SR'', GeR''.sub.3, SnR''.sub.3, and C.dbd.C-containing groups (R''=C.sub.1 C.sub.10 hydrocarbyl); n is an integer selected to balance the oxidation state of M; and A is a suitable non-coordinating anionic cocatalyst or precursor. This catalyst system may form stereoregular olefin polymers including syndiotactic polymers of styrene and methylmethacrylate and isotactic copolymers of polar and nonpolar olefin monomers such as methylmethacrylate and styrene.

  1. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

    1996-01-01

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

  2. Binary ferrihydrite catalysts

    DOEpatents

    Huffman, G.P.; Zhao, J.; Feng, Z.

    1996-12-03

    A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

  3. Formation of Active Catalysts in the System: Chlorocuprates-CCl4-n-C10H22

    NASA Astrophysics Data System (ADS)

    Golubeva, Elena N.; Kharitonov, Dmitry N.; Kochubey, Dmitry I.; Ikorskii, Vladimir N.; Kriventsov, Vladimir V.; Kokorin, Alexander I.; Stoetsner, Julia; Bahnemann, Detlef W.

    2009-08-01

    Transformations of anionic CuII chlorocomplexes have been studied under conditions of catalytic exchange reactions between carbon tetrachloride and n-alkanes. It was shown that chlorocuprates are just precursors and are easily reduced to the genuine catalysts, that is, to the respective CuI complexes. Both the composition and the geometric structure of the precursor (CuCl42-) and, probably, the active site (CuCl32-) have been investigated by several techniques (UV-vis spectroscopy, electron spin resonance (ESR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), and static magnetic measurements). The dependence of the metathesis velocity on the [Cl-]/[Cu] ratio was found to exhibit a maximum most likely corresponding to the highest content of trichlorocuprite CuCl32-.

  4. Anion solvation in alcohols

    SciTech Connect

    Jonah, C.D.; Xujia, Zhang; Lin, Yi

    1996-03-01

    Anion solvation is measured in alcohols using pump-probe pulse radiolysis and the activation energy of solvation is determined. Solvation of an anion appears to be different than excited state solvation. The continuum dielectric model does not appear to explain the results.

  5. Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol.

    PubMed

    Zhang, Jie; Zhang, Changbin; He, Hong

    2015-09-01

    OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO4 (OMS-2-SO4) and Mn(CH3COO)2 (OMS-2-AC) as precursors. SO4(2-)-doped OMS-2-AC catalysts with different SO4(2-) concentrations were prepared next by adding (NH4)2SO4 solution into OMS-2-AC samples to investigate the effect of the anion SO4(2-) on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4(2-) doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4(2-) (SO4/catalyst=0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4(2-) species in the OMS-2-AC catalyst could decrease the Mn-O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4(2-) species in OMS-2-SO4 samples. PMID:26354694

  6. Tuning the Synthesis of Ternary Lead Chalcogenide Quantum Dots by Balancing Precursor Reactivity

    SciTech Connect

    Smith, Danielle K.; Luther, Joseph M; Semonin, Octavi Escala; Nozik, Arthur J; Beard, Matthew C

    2011-01-25

    We report the synthesis and characterization of composition-tunable ternary lead chalcogenide alloys PbSe{sub x}Te{sub 1-x}, PbS{sub x}Te{sub 1-x}, and PbS{sub x}Se{sub 1-x}. This work explores the relative reaction rates of chalcogenide precursors to produce alloyed quantum dots (QDs), and we find the highly reactive bis(trimethylsilyl) (TMS{sub 2})-based precursors allow for the homogeneous incorporation of anions. By varying the Pb to oleic acid ratio, we demonstrate size control of similar composition alloys. We find the resulting QDs are Pb-rich but the Pb/anion ratio is size- and composition-dependent in all alloyed QD as well as in PbSe, PbTe, and PbS QDs and is consistent with the reaction rates of the anion precursors. A more reactive anion precursor results in a lower Pb/anion ratio.

  7. SURFACE-MODIFIED COALS FOR ENHANCED CATALYST DISPERSION AND LIQUEFACTION

    SciTech Connect

    Dr. Yaw D. Yeboah

    1999-09-01

    This is the final report of the Department of Energy Sponsored project DE-FGF22-95PC95229 entitled, surface modified coals for enhanced catalyst dispersion and liquefaction. The aims of the study were to enhance catalyst loading and dispersion in coal for improved liquefaction by preadsorption of surfactants and catalysts on the coal and to train and educate minority scientists in catalysts and separation science. Illinois No. 6 Coal (DEC-24) was selected for the study. The surfactants investigated included dodecyl dimethyl ethyl ammonium bromide (DDAB), a cationic surfactant, sodium dodecyl sulfate, an anionic surfactant, and Triton x-100, a neutral surfactant. Ammonium molybdate tetrahydrate was used as the molybdenum catalyst precursor. Zeta potential, BET, FTIR, AFM, UV-Vis and luminescence intensity measurements were undertaken to assess the surface properties and the liquefaction activities of the coal. The parent coal had a net negative surface charge over the pH range 2-12. However, in the presence of DDAB the negativity of the surface charge decreased. At higher concentrations of DDAB, a positive surface charge resulted. In contrast to the effect of DDAB, the zeta potential of the coal became more negative than the parent coal in the presence of SDS. Adsorption of Triton reduced the net negative charge density of the coal samples. The measured surface area of the coal surface was about 30 m{sup 2}/g compared to 77m{sup 2}/g after being washed with deionized water. Addition of the surfactants decreased the surface area of the samples. Adsorption of the molybdenum catalyst increased the surface area of the coal sample. The adsorption of molybdenum on the coal was significantly promoted by preadsorption of DDAB and SDS. Molybdenum adsorption showed that, over a wide range of concentrations and pH values, the DDAB treated coal adsorbed a higher amount of molybdenum than the samples treated with SDS. The infrared spectroscopy (FTIR) and the atomic force

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

    SciTech Connect

    Branko N. Popov

    2009-03-03

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

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

    SciTech Connect

    Branko N. Popov

    2009-02-20

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

  10. Intrinsic anion oxidation potentials.

    PubMed

    Johansson, Patrik

    2006-11-01

    Anions of lithium battery salts have been investigated by electronic structure calculations with the objective to find a computational measure to correlate with the observed (in)stability of nonaqueous lithium battery electrolytes vs oxidation often encountered in practice. Accurate prediction of intrinsic anion oxidation potentials is here made possible by computing the vertical free energy difference between anion and neutral radical (Delta Gv) and further strengthened by an empirical correction using only the anion volume as a parameter. The 6-311+G(2df,p) basis set, the VSXC functional, and the C-PCM SCRF algorithm were used. The Delta Gv calculations can be performed using any standard computational chemistry software. PMID:17078600

  11. Anion exchange polymer electrolytes

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik

    2015-06-02

    Anion exchange polymer electrolytes that include guanidinium functionalized polymers may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  12. Immobilized catalysts for iridium-catalyzed allylic amination: rate enhancement by immobilization.

    PubMed

    Malakar, Chandi C; Helmchen, Günter

    2015-05-01

    The first immobilized catalyst for Ir-catalyzed asymmetric allylic aminations is described. The catalyst is a cationic (π-allyl)Ir complex bound by cation exchange to an anionic silica gel support. Preparation of the catalyst is facile, and the supported catalyst displayed considerably enhanced activity compared with the parent homogeneous catalyst. Up to 43 consecutive amination runs were possible in recycling experiments. PMID:25787122

  13. Hydrocracking and hydroisomerization of long-chain alkanes and polyolefins over metal-promoted anion-modified transition metal oxides

    DOEpatents

    Venkatesh, Koppampatti R.; Hu, Jianli; Tierney, John W.; Wender, Irving

    2001-01-01

    A method of cracking a feedstock by contacting the feedstock with a metal-promoted anion-modified metal oxide catalyst in the presence of hydrogen gas. The metal oxide of the catalyst is one or more of ZrO.sub.2, HfO.sub.2, TiO.sub.2 and SnO.sub.2, and the feedstock is principally chains of at least 20 carbon atoms. The metal-promoted anion-modified metal oxide catalyst contains one or more of Pt, Ni, Pd, Rh, Ir, Ru, (Mn & Fe) or mixtures of them present between about 0.2% to about 15% by weight of the catalyst. The metal-promoted anion-modified metal oxide catalyst contains one or more of SO.sub.4, WO.sub.3, or mixtures of them present between about 0.5% to about 20% by weight of the catalyst.

  14. Bimetallic complexes and polymerization catalysts therefrom

    DOEpatents

    Patton, Jasson T.; Marks, Tobin J.; Li, Liting

    2000-11-28

    Group 3-6 or Lanthanide metal complexes possessing two metal centers, catalysts derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions and the use of such catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers are disclosed.

  15. Hydrocarbon synthesis catalyst and method of preparation

    DOEpatents

    Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

    1983-08-02

    A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint. 9 figs.

  16. Hydrocarbon synthesis catalyst and method of preparation

    DOEpatents

    Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

    1983-08-02

    A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

  17. Hydrotreating process employing catalysts comprising a supported mixture of a sulfide of a promoter metal, trivalent chromium and molybdenum or tungsten

    SciTech Connect

    Ho, T.C.; Young, A.R. II; Chianelli, R.R.; Jacobson, A.J.

    1986-05-27

    A process is described for improving the oxidation stability of a nitrogen and sulfur containing lube oil feed which comprises contacting the feed at an elevated temperature of at least about 150/sup 0/C and in the presence of hydrogen with a catalyst comprising a support mixture of a sulfide of (i) trivalent chromium, (ii) Mo, W or mixture thereof and (iii) at least one promoter metal selected from the group consisting of Ni, Co, Mn, Cu, Zn and mixture thereof and mixture thereof with Fe. The catalyst has been prepared by compositing a pre-selected quantity of inorganic refractory oxide support material with (a) a hydrated oxide of trivalent chromium and (b) one or more catalyst precursor salts containing a thiometalate anion of Mo, W or mixture thereof and a cation containing at least one of the promoter metals wherein the promoter metal in the cation is divalent and is chelated by at least one neutral, nitrogen-containing polydenate ligand and heating the composite at elevated temperature, in the presence of sulfur or sulfur bearing compound and under oxygen-free conditions for a time sufficient to form the catalyst, the contacting of the feed with the catalyst occurring for a time sufficient to improve the oxidation stability of the oil.

  18. Highly dispersed catalysts for coal liquefaction

    SciTech Connect

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

    1992-06-08

    Iron and molybdenum complexes were studied as precursors to high dispersion catalysts for coal liquefaction. The precursors were either organometallic complexes or water soluble salts and were impregnated into coals of various ranks. The molybdenum catalysts were found to be very effective for conversion of an Illinois {number sign}6 bituminous coal whereas the iron catalysts were not. In contrast, the iron catalysts were found to be very effective for lignite conversions. A H-donor and a non-donor conversion system were compared, using tetralin and n-hexadecane, respectively. In each case the organometallic precursor gave greater yields of toluene soluble material, with differences being most dramatic in the hexadecane system. The yields using the organometallic molybdenum precursors in hexadecane were found to be almost as great as those in the tetralin system, indicating that good catalyst precursors do not require donor solvents. The impregnation techniques were evaluated by comparing conversion yields and analyzing the products using Field Ionization Mass Spectroscopy (f.i.m.s) and FT-IR.

  19. Halogen bonding anion recognition.

    PubMed

    Brown, Asha; Beer, Paul D

    2016-07-01

    A halogen bond is an attractive non-covalent interaction between an electrophilic region in a covalently bonded halogen atom and a Lewis base. While these interactions have long been exploited as a tool in crystal engineering their powerful ability to direct supramolecular self-assembly and molecular recognition processes in solution has, until recently, been overlooked. During the last decade however an ever-increasing number of studies on solution-phase halogen-bond-mediated anion recognition processes has emerged. This Feature Article summarises advancements which have been made thus far in this rapidly developing research area. We survey the use of iodoperfluoroarene, haloimidazolium and halotriazole/triazolium halogen-bond-donor motifs in anion receptor design, before providing an account of our research into the application of mechanically interlocked rotaxane and catenane frameworks as halogen bonding anion host systems. PMID:27273600

  20. Unexpected anion effect in the alkoxylation of alkynes catalyzed by N-heterocyclic carbene (NHC) cationic gold complexes.

    PubMed

    Biasiolo, Luca; Trinchillo, Marina; Belanzoni, Paola; Belpassi, Leonardo; Busico, Vincenzo; Ciancaleoni, Gianluca; D'Amora, Angela; Macchioni, Alceo; Tarantelli, Francesco; Zuccaccia, Daniele

    2014-11-01

    The intermolecular alkoxylation of alkynes is the oldest application of cationic gold(I) catalysts; however, no systematic experimental data about the role of the anion are available. In this contribution, the role of the anion in this catalytic reaction as promoted by a N-heterocyclic carbene-based gold catalyst, [(NHC)AuX] (X=BARF(-) , BF4 (-) , OTf(-) , OTs(-) , TFA(-) , or OAc(-) ) is analyzed, through a combined experimental (NMR spectroscopy) and theoretical (DFT calculation) approach. The most important factor seems to be the ability to abstract the proton from the methanol during the nucleophilic attack, and such ability is related to the anion basicity. On the other hand, too high coordination power or basicity of the anion worsens the catalytic performance by preventing alkyne coordination or by forming too much free methoxide in solution, which poisons the catalyst. The intermediate coordinating power and basicity of the OTs(-) anion provides the best compromise to achieve efficient catalysis. PMID:25263571

  1. Vanadogermanate cluster anions.

    PubMed

    Whitfield, T; Wang, X; Jacobson, A J

    2003-06-16

    Three novel vanadogermanate cluster anions have been synthesized by hydrothermal reactions. The cluster anions are derived from the (V(18)O(42)) Keggin cluster shell by substitution of V=O(2+) "caps" by Ge(2)O(OH)(2)(4+) species. In Cs(8)[Ge(4)V(16)O(42)(OH)(4)].4.7H(2)O, 1, (monoclinic, space group C2/c (No. 15), Z = 8, a = 44.513(2) A, b = 12.7632(7) A, c = 22.923(1) A, beta = 101.376(1) degrees ) and (pipH(2))(4)(pipH)(4)[Ge(8)V(14)O(50).(H(2)O)] (pip = C(4)N(2)H(10)), 2 (tetragonal, space group P4(2)/nnm (No. 134), Z = 2, a = 14.9950(7) A, c = 18.408(1) A), two and four VO(2+) caps are replaced, respectively, and each cluster anion encapsulates a water molecule. In K(5)H(8)Ge(8)V(12)SO(52).10H(2)O, 3, (tetragonal, space group I4/m (No. 87), Z = 2, a = 15.573(1) A, c = 10.963(1) A), four VO(2+) caps are replaced by Ge(2)O(OH)(2)(4+) species, and an additional two are omitted. The cluster ion in 3 contains a sulfate anion disordered over two positions. The cluster anions are analogous to the vanadoarsenate anions [V(18)(-)(n)()As(2)(n)()O(42)(X)](m)(-) (X = SO(3), SO(4), Cl; n = 3, 4) previously reported. PMID:12793808

  2. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  3. Alkaline direct alcohol fuel cells using an anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Matsuoka, Koji; Iriyama, Yasutoshi; Abe, Takeshi; Matsuoka, Masao; Ogumi, Zempachi

    Alkaline direct alcohol fuel cells using an OH-form anion exchange membrane and polyhydric alcohols were studied. A high open circuit voltage of ca. 800 mV was obtained for a cell using Pt-Ru/C (anode) and Pt/C (cathode) at 323 K, which was about 100-200 mV higher than that for a DMFC using Nafion ®. The maximum power densities were in the order of ethylene glycol > glycerol > methanol > erythritol > xylitol. Silver catalysts were used as a cathode catalyst to fabricate alkaline fuel cells, since silver catalyst is almost inactive in the oxidation of polyhydric alcohols. Alkaline direct ethylene glycol fuel cells using silver as a cathode catalyst gave excellent performance because higher concentrations of fuel could be supplied to the anode.

  4. Metallocene catalyst containing bulky organic group

    DOEpatents

    Marks, T.J.; Ja, L.; Yang, X.

    1996-03-26

    An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetrafluoro-aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

  5. Metallocene catalyst containing bulky organic group

    DOEpatents

    Marks, Tobin J.; Ja, Li; Yang, Xinmin

    1996-03-26

    An ionic metallocene catalyst for olefin polymerization which comprises: (1) a cyclopentadienyl-type ligand, a Group IVB transition metal, and alkyl, aryl, or hydride substituents, as a cation, and (2) a weakly coordinating anion comprising boron substituted with halogenated, such as tetra fluoro, aryl substituents preferably containing silylalkyl substitution, such as para-silyl t-butyldimethyl.

  6. Low temperature catalysts for methanol production

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

    1986-09-30

    A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1--6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

  7. Bimetallic Catalysts.

    ERIC Educational Resources Information Center

    Sinfelt, John H.

    1985-01-01

    Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

  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. ION CHROMATOGRAPHY OF ANIONS

    EPA Science Inventory

    A Dionex Model 10 Ion Chromatograph was evaluated for the measurement of anionic species in water. The theoretical effect of hydrogen ion activity (pH) on the elution time of phosphate and arsenate was tested and empirical selectivity coefficients were determined for the major pr...

  10. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1987-05-12

    A process is described for polymerizing at least one alpha olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst system which comprises: a supported catalyst prepared under anhydrous conditions by the sequential steps of: preparing a slurry of inert particulate support material; adding to the slurry a solution of an organomagnesium compound; adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; adding to the slurry and reacting a halogenator; adding to the slurry and reacting a tetravalent titanium halide compound; and recovering solid catalyst.

  11. Polymerization catalyst

    SciTech Connect

    Graves, V.

    1986-10-21

    A process is described for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization wherein the polymerization is conducted in the presence of a catalyst comprising: a supported catalyst prepared under anhydrous conditions by the steps of: (1) sequentially; (a) preparing a slurry of inert particulate support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of zirconium compound; and (2) thereafter; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium compound; (f) recovering solid catalyst; and an organoaluminum compound.

  12. 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

  13. The copper-catalysed Suzuki-Miyaura coupling of alkylboron reagents: disproportionation of anionic (alkyl)(alkoxy)borates to anionic dialkylborates prior to transmetalation.

    PubMed

    Basnet, Prakash; Thapa, Surendra; Dickie, Diane A; Giri, Ramesh

    2016-09-25

    We report the first example of Cu(I)-catalysed coupling of alkylboron reagents with aryl and heteroaryl iodides that affords products in good to excellent yields. Preliminary mechanistic studies with alkylborates indicate that the anionic (alkoxy)(alkyl)borates, generated from alkyllithium and alkoxyboron reagents, undergo disproportionation to anionic dialkylborates and that both anionic alkylborates are active for transmetalation to a Cu(I)-catalyst. Results from a radical clock experiment and the Hammett plot imply that the reaction likely proceeds via a non-radical pathway. PMID:27540605

  14. Studies of oxide anions

    NASA Astrophysics Data System (ADS)

    Castleman, A. W., Jr.

    1991-06-01

    Several metal and metal oxide anion sources were used to investigate the formation and reactivity of species of relevance to the AFGL program. A new class of reactions were identified between anions of the form H(x)M(y)O(z) for several metals including M=W, Ta, Ti, Mo, and HCl. The reactions have analogy to acid-base reactions. In another series of experiments, reactions of Al(n)(-), and these clusters bound with V and or Nb, with O2 were investigated. It was found that the Jellium model, though by no means a compendious concept, provides a good guide to the electronic structure of clusters and their general patterns of reactivity.

  15. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  16. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-01-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  17. Anion permselective membrane

    NASA Astrophysics Data System (ADS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-07-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  18. Catalyst containing oxygen transport membrane

    DOEpatents

    Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

    2012-12-04

    A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

  19. Photo-oxidation catalysts

    DOEpatents

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

    2009-07-14

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

  20. Heterogenization of Homogeneous Catalysts: the Effect of the Support

    SciTech Connect

    Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

    1999-06-29

    We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

  1. Cobalt(II) Complex of a Diazoalkane Radical Anion.

    PubMed

    Bonyhady, Simon J; Goldberg, Jonathan M; Wedgwood, Nicole; Dugan, Thomas R; Eklund, Andrew G; Brennessel, William W; Holland, Patrick L

    2015-06-01

    β-Diketiminate cobalt(I) precursors react with diphenyldiazomethane to give a compound that is shown by computational studies to be a diazoalkane radical anion antiferromagnetically coupled to a high-spin cobalt(II) ion. Thermolysis of this complex results in formal N-N cleavage to give a cobalt(II) ketimide complex. Experimental evaluation of the potential steps in the mechanism suggests that free azine is a likely intermediate in this reaction. PMID:25986783

  2. The atomic structural dynamics of γ-Al2O3 supported Ir-Pt nanocluster catalysts prepared from a bimetallic molecular precursor: a study using aberration-corrected electron microscopy and X-ray absorption spectroscopy.

    PubMed

    Small, Matthew W; Sanchez, Sergio I; Menard, Laurent D; Kang, Joo H; Frenkel, Anatoly I; Nuzzo, Ralph G

    2011-03-16

    This study describes a prototypical, bimetallic heterogeneous catalyst: compositionally well-defined Ir-Pt nanoclusters with sizes in the range of 1-2 nm supported on γ-Al(2)O(3). Deposition of the molecular bimetallic cluster [Ir(3)Pt(3)(μ-CO)(3)(CO)(3)(η-C(5)Me(5))(3)] on γ-Al(2)O(3), and its subsequent reduction with hydrogen, provides highly dispersed supported bimetallic Ir-Pt nanoparticles. Using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM) and theoretical modeling of synchrotron-based X-ray absorption spectroscopy (XAS) measurements, our studies provide unambiguous structural assignments for this model catalytic system. The atomic resolution C(s)-STEM images reveal strong and specific lattice-directed strains in the clusters that follow local bonding configurations of the γ-Al(2)O(3) support. Combined nanobeam diffraction (NBD) and high-resolution transmission electron microscopy (HRTEM) data suggest the polycrystalline γ-Al(2)O(3) support material predominantly exposes (001) and (011) surface planes (ones commensurate with the zone axis orientations frequently exhibited by the bimetallic clusters). The data reveal that the supported bimetallic clusters exhibit complex patterns of structural dynamics, ones evidencing perturbations of an underlying oblate/hemispherical cuboctahedral cluster-core geometry with cores that are enriched in Ir (a result consistent with models based on surface energetics, which favor an ambient cluster termination by Pt) due to the dynamical responses of the M-M bonding to the specifics of the adsorbate and metal-support interactions. Taken together, the data demonstrate that strong temperature-dependent charge-transfer effects occur that are likely mediated variably by the cluster-support, cluster-adsorbate, and intermetallic bonding interactions. PMID:21341654

  3. Attrition resistant bulk iron catalysts and processes for preparing and using same

    DOEpatents

    Jothimurugesan, Kandaswamy; Goodwin, Jr., James G.; Gangwal, Santosh K.

    2007-08-21

    An attrition resistant precipitated bulk iron catalyst is prepared from iron oxide precursor and a binder by spray drying. The catalysts are preferably used in carbon monoxide hydrogenation processes such as Fischer-Tropsch synthesis. These catalysts are suitable for use in fluidized-bed reactors, transport reactors and, especially, slurry bubble column reactors.

  4. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1980-01-01

    The efforts on the synthesis of polymer anion redox membranes were mainly concentrated in two areas, membrane development and membrane fabrication. Membrane development covered the preparation and evaluation of experimental membranes systems with improved resistance stability and/or lower permeability. Membrane fabrication covered the laboratory scale production of prime candidate membranes in quantities of up to two hundred and sizes up to 18 inches x 18 inches (46 cm x 46 cm). These small (10 in x 11 in) and medium sized membranes were mainly for assembly into multicell units. Improvements in processing procedures and techniques for preparing such membrane sets lifted yields to over 90 percent.

  5. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: Controllable preparation and catalytic performance

    SciTech Connect

    Chang Zheng; Zhao Na; Liu Junfeng; Li Feng; Evans, David G.; Duan Xue; Forano, Claude; Roy, Marie de

    2011-12-15

    Cu/Zn/Al layered double hydroxide (LDH) precursors have been synthesized using an anion exchange method with anionic Ce complexes containing the dipicolinate (pyridine-2,6-dicarboxylate) ligand. Cu-Ce-O mixed oxides were obtained by calcination of the Ce-containing LDHs. The materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, and low temperature N{sub 2} adsorption/desorption measurements. The results reveal that the inclusion of Ce has a significant effect on the specific surface area, pore structure, and chemical state of Cu in the resulting Cu-Ce-O mixed metal oxides. The resulting changes in composition and structure, particularly the interactions between Cu and Ce centers, significantly enhance the activity of the Ce-containing materials as catalysts for the oxidation of phenol by hydrogen peroxide. - Graphical Abstract: Cu-Ce-O mixed oxides calcined from [Ce(dipic){sub 3}]{sup 3-}- intercalated Cu/Zn/Al layered double hydroxides were synthesized and displayed good catalytic performances in phenol oxidation due to the Cu-Ce interactions. Highlights: Black-Right-Pointing-Pointer [Ce(dipic){sub 3}]{sup 3-}-intercalated Cu/Zn/Al layered double hydroxides were synthesized. Black-Right-Pointing-Pointer Cu-Ce-O mixed oxides derivated from the LDHs were characterized as catalysts. Black-Right-Pointing-Pointer Presence of Ce influenced physicochemical property and catalytic performance. Black-Right-Pointing-Pointer Cu-Ce interaction was largely responsible for enhanced catalytic ability.

  6. Pseudorotation in fullerene anions

    NASA Astrophysics Data System (ADS)

    Dunn, Janette L.; Hands, Ian D.; Bates, Colin A.

    2007-07-01

    Jahn-Teller (JT) problems are often characterised by an adiabatic potential energy surface (APES) containing either a set of isoenergetic wells or a trough of equivalent-energy points, which may be warped by higher-order coupling terms or anisotropic effects. In all three cases, the JT effect will be dynamic. Either tunnelling between the wells or rotation (of a distortion) around the trough will restore the original symmetry of the system. This motion is referred to as pseudorotation. It should be possible to observe a JT system in a distorted geometry if measurements are made on a sufficiently short timescale. In various cubic systems, this timescale has been calculated to be the order of picoseconds. Such timescales are accessible using modern methods of ultrafast spectroscopy. Measurements of pseudorotation rates can lead to important information on the strength and nature of the JT coupling present. We will present analytical calculations that allow the rate of pseudorotation to be determined in terms of the vibronic coupling parameters. We will show how these results can be applied to E ⊗ e systems and then to the more complicated system applicable to C60- anions. This is of particular interest because of the high icosahedral symmetry of fullerene ions and also because of the many potential uses of materials containing these ions. We conclude by outlining experiments that should be capable of measuring pseudorotation in C 60 anions.

  7. Dynamic chemistry of anion recognition

    SciTech Connect

    Custelcean, Radu

    2012-01-01

    In the past 40 years, anion recognition by synthetic receptors has grown into a rich and vibrant research topic, developing into a distinct branch of Supramolecular Chemistry. Traditional anion receptors comprise organic scaffolds functionalized with complementary binding groups that are assembled by multistep organic synthesis. Recently, a new approach to anion receptors has emerged, in which the host is dynamically self-assembled in the presence of the anionic guest, via reversible bond formation between functional building units. While coordination bonds were initially employed for the self-assembly of the anion hosts, more recent studies demonstrated that reversible covalent bonds can serve the same purpose. In both cases, due to their labile connections, the molecular constituents have the ability to assemble, dissociate, and recombine continuously, thereby creating a dynamic combinatorial library (DCL) of receptors. The anionic guests, through specific molecular recognition, may then amplify (express) the formation of a particular structure among all possible combinations (real or virtual) by shifting the equilibria involved towards the most optimal receptor. This approach is not limited to solution self-assembly, but is equally applicable to crystallization, where the fittest anion-binding crystal may be selected. Finally, the pros and cons of employing dynamic combinatorial chemistry (DCC) vs molecular design for developing anion receptors, and the implications of both approaches to selective anion separations, will be discussed.

  8. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  9. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction

    SciTech Connect

    Chunshan, Song; Kirby, S.; Schmidt, E.

    1995-12-31

    The objective of this project is to explore bimetallic dispersed catalysts for more efficient coal liquefaction. Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting various aromatic units and the reactions of various oxygen functional groups. This paper describes recent results on (1) hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors; and (2) activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-naphthylmethyl) bibenzyl. The results showed that some iron containing catalysts have higher activity in the sulfur-free form, contrary to conventional wisdom. Adding sulfur to Fe precursors with Cp-ligands decreased the activity of the resulting catalyst. This is in distinct contrast to the cases with iron pentacarbonyl and superfine Fe{sub 2}O{sub 3}, where S addition increased their catalytic activity substantially. A positive correlation between sulfur addition and increased activity can be seen, but a reversed trend between Fe cluster size and hydrocracking conversion could be observed, for carbonyl-type Fe precursors. It is apparent that the activity and selectivity of Fe catalysts for NMBB conversion depends strongly on both the type of ligand environment, the oxidation state and the number of intermetal bonds in the molecular precursor.

  10. Polyimide Precursor Solid Residuum

    NASA Technical Reports Server (NTRS)

    Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

    2001-01-01

    A polyimide precursor solid residuum is an admixture of an aromatic dianhydride or derivative thereof and an aromatic diamine or derivative thereof plus a complexing agent, which is complexed with the admixture by hydrogen bonding. The polyimide precursor solid residuum is effectively employed in the preparation of polyimide foam and the fabrication of polyimide foam structures.

  11. 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.

  12. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Alexander, S.; Hodgdon, R. B.

    1977-01-01

    The objective of NAS 3-20108 was the development and evaluation of improved anion selective membranes useful as efficient separators in a redox power storage cell system being constructed. The program was divided into three parts, (a) optimization of the selected candidate membrane systems, (b) investigation of alternative membrane/polymer systems, and (c) characterization of candidate membranes. The major synthesis effort was aimed at improving and optimizing as far as possible each candidate system with respect to three critical membrane properties essential for good redox cell performance. Substantial improvements were made in 5 candidate membrane systems. The critical synthesis variables of cross-link density, monomer ratio, and solvent composition were examined over a wide range. In addition, eight alternative polymer systems were investigated, two of which attained candidate status. Three other alternatives showed potential but required further research and development. Each candidate system was optimized for selectivity.

  13. Organic Anion Transporting Polypeptides

    PubMed Central

    Stieger, Bruno; Hagenbuch, Bruno

    2013-01-01

    Organic anion transporting polypeptides or OATPs are central transporters in the disposition of drugs and other xenobiotics. In addition, they mediate transport of a wide variety of endogenous substrates. The critical role of OATPs in drug disposition has spurred research both in academia and in the pharmaceutical industry. Translational aspects with clinical questions are the focus in academia, while the pharmaceutical industry tries to define and understand the role these transporters play in pharmacotherapy. The present overview summarizes our knowledge on the interaction of food constituents with OATPs, and on the OATP transport mechanisms. Further, it gives an update on the available information on the structure-function relationship of the OATPs, and finally, covers the transcriptional and posttranscriptional regulation of OATPs. PMID:24745984

  14. Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

    NASA Astrophysics Data System (ADS)

    Rannulu, Nalaka S.; Cole, Richard B.

    2012-09-01

    The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

  15. Liquefaction Of Coal With Surfactant And Disposable Catalyst

    NASA Technical Reports Server (NTRS)

    Hickey, Gregory S.; Sharma, Pramod K.

    1996-01-01

    Fuels derived from coal more competitive with petroleum products. Improved coal-liquefaction process exploits synergistic effects of disposable iron oxide catalyst and cheap anionic surfactant. Efficiency of conversion achieved in significantly higher than efficiencies obtained with addition of either surfactant or catalyst alone. No costly pretreatment necessary, and increase in conversion achieved under processing conditions milder than those used heretofore in liquefaction of coal. Quality of distillates obtained after liquefaction in process expected superior to distillates obtained after liquefaction by older techniques.

  16. Mössbauer investigations of the Fe-Cu-Mn catalysts for Fischer-Tropsch synthesis

    NASA Astrophysics Data System (ADS)

    Spânu, Viorica; Filoti, G.; Ilie, Ioana; Zamfirescu, Elena

    1990-07-01

    In the selective process of the syngas conversion to synthetic gasoline a bifunctional catalytic system has to be used. It was obtained by combination a Fischer-Tropsch catalyst with the HZSM-5 zeolite. The phase compositions of the precursor and the fresh catalyst were established as well as the optimum thermal treatment. The catalyst was reduced in pure H2 or in a H2+CO mixture. The influence of the reduction and reaction conditions on the catalyst structure was investigated.

  17. 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.

  18. Earthquakes: hydrogeochemical precursors

    USGS Publications Warehouse

    Ingebritsen, Steven E.; Manga, Michael

    2014-01-01

    Earthquake prediction is a long-sought goal. Changes in groundwater chemistry before earthquakes in Iceland highlight a potential hydrogeochemical precursor, but such signals must be evaluated in the context of long-term, multiparametric data sets.

  19. Enantioselective acylation of silyl ketene acetals through fluoride anion-binding catalysis.

    PubMed

    Birrell, James A; Desrosiers, Jean-Nicolas; Jacobsen, Eric N

    2011-09-01

    A highly enantioselective acylation of silyl ketene acetals with acyl fluorides has been developed to generate useful α,α-disubstituted butyrolactone products. This transformation is promoted by a new thiourea catalyst and 4-pyrrolidinopyridine and represents the first example of enantioselective thiourea anion-binding catalysis with fluoride. PMID:21800916

  20. Combinatorial Optimization of Heterogeneous Catalysts Used in the Growth of Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Cassell, Alan M.; Verma, Sunita; Delzeit, Lance; Meyyappan, M.; Han, Jie

    2000-01-01

    Libraries of liquid-phase catalyst precursor solutions were printed onto iridium-coated silicon substrates and evaluated for their effectiveness in catalyzing the growth of multi-walled carbon nanotubes (MWNTs) by chemical vapor deposition (CVD). The catalyst precursor solutions were composed of inorganic salts and a removable tri-block copolymer (EO)20(PO)70(EO)20 (EO = ethylene oxide, PO = propylene oxide) structure-directing agent (SDA), dissolved in ethanol/methanol mixtures. Sample libraries were quickly assayed using scanning electron microscopy after CVD growth to identify active catalysts and CVD conditions. Composition libraries and focus libraries were then constructed around the active spots identified in the discovery libraries to understand how catalyst precursor composition affects the yield, density, and quality of the nanotubes. Successful implementation of combinatorial optimization methods in the development of highly active, carbon nanotube catalysts is demonstrated, as well as the identification of catalyst formulations that lead to varying densities and shapes of aligned nanotube towers.

  1. Hydrocracking catalyst

    SciTech Connect

    Hilfman, L.; O'Hara, M.

    1980-07-01

    A description is given of a process for the conversion of heavy hydrocarbon oil boiling above about 650/sup 0/F into lower boiling hydrocarbons, which comprises hydrocracking the heavy oil in admixture with hydrogen and in contact with a catalyst with comprising a ra re earth exchange metal component and a platinum group metal component supported on a mixture of ziegler alumina and a zeolite.

  2. New catalysts for coal liquefaction and new nanocrystalline catalysts synthesis methods

    SciTech Connect

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

    1994-09-01

    The use of coal as a source of transportation fuel is currently economically unfavorable due to an abundant world petroleum supply and the relatively high cost of coal liquefaction. Consequently, a reduction in the cost of coal liquefaction, for example by using less and/or less costly catalysts or lower liquefaction temperatures, must be accomplished if coal is to play an significant role as a source of liquid feedstock for the petrochemical industry. The authors and others have investigated the applicability of using inexpensive iron-based catalysts in place of more costly and environmentally hazardous metal catalysts for direct coal liquefaction. Iron-based catalysts can be effective in liquefying coal and in promoting carbon-carbon bond cleavage in model compounds. The authors have been involved in an ongoing effort to develop and optimize iron-based powders for use in coal liquefaction and related petrochemical applications. Research efforts in this area have been directed at three general areas. The authors have explored ways to optimize the effectiveness of catalyst precursor species through use of nanocrystalline materials and/or finely divided powders. In this effort, the authors have developed two new nanophase material production techniques, Modified Reverse Micelle (MRM) and the Rapid Thermal Decomposition of precursors in Solution (RTDS). A second effort has been aimed at optimizing the effectiveness of catalysts by variations in other factors. To this, the authors have investigated the effect that the crystalline phase has on the capacity of iron-based oxide and oxyhydroxide powders to be effectively converted to an active catalyst phase under liquefaction conditions. And finally, the authors have developed methods to produce active catalyst precursor powders in quantities sufficient for pilot-scale testing. Major results in these three areas are summarized.

  3. Ceramic catalyst materials

    SciTech Connect

    Sault, A.G.; Gardner, T.J.; Hanprasopwattanna, A.; Reardon, J.; Datye, A.K.

    1995-08-01

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

  4. New nanophase iron-based catalysts for hydrocracking applications

    SciTech Connect

    Matson, D.W.; Linehan, J.C.; Darab, J.G.; Camaioni, D.M.; Autrey, S.T.; Lui, E.

    1994-11-01

    Development of highly efficient iron-based materials for processes involving carbon-carbon bond cleavage, including petroleum hydrocracking and coal liquefaction, offers the potential for decreasing catalyst costs as well as reducing the need for expensive catalyst recovery and recycling steps. Carbon-carbon bond cleavage catalysts produced in situ at reaction conditions from nanocrystalline hydrated iron oxides, show high activity and selectivity in model compound studies. Two highly active catalyst precursors, ferric oxyhydroxysulfate (OHS) and 6-line ferrihydrite, can be produced by a flow-through hydrothermal powder synthesis method, the Rapid Thermal Decomposition of precursors in Solution (RTDS) process. Model compound studies indicate that both catalyst precursors are active at a 400 C reaction temperature, but that there are significant differences in their catalytic characteristics. The activity of 6-line ferrihydrite is highly dependent on the particle (aggregate) size whereas the activity of the OHS is essentially independent of particle size. These differences are attributed to variations in the crystallite aggregation and particle surface characteristics of the two catalyst precursor materials. Catalytic activity is retained to lower reaction temperatures in tests using OHS than in similar tests using 6-line ferrihydrite.

  5. Composite catalysts supported on modified carbon substrates and methods of making the same

    DOEpatents

    Popov, Branko N.; Subramanian, Nalini; Colon-Mercado, Hector R.

    2009-11-17

    A method of producing a composite carbon catalyst is generally disclosed. The method includes oxidizing a carbon precursor (e.g., carbon black). Optionally, nitrogen functional groups can be added to the oxidized carbon precursor. Then, the oxidized carbon precursor is refluxed with a non-platinum transitional metal precursor in a solution. Finally, the solution is pyrolyzed at a temperature of at least about 500.degree. C.

  6. Attrition resistant fluidizable reforming catalyst

    DOEpatents

    Parent, Yves O.; Magrini, Kim; Landin, Steven M.; Ritland, Marcus A.

    2011-03-29

    A method of preparing a steam reforming catalyst characterized by improved resistance to attrition loss when used for cracking, reforming, water gas shift and gasification reactions on feedstock in a fluidized bed reactor, comprising: fabricating the ceramic support particle, coating a ceramic support by adding an aqueous solution of a precursor salt of a metal selected from the group consisting of Ni, Pt, Pd, Ru, Rh, Cr, Co, Mn, Mg, K, La and Fe and mixtures thereof to the ceramic support and calcining the coated ceramic in air to convert the metal salts to metal oxides.

  7. Can Ni phosphides become viable hydroprocessing catalysts?

    SciTech Connect

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

    2015-05-15

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

  8. Simple cerium-triethanolamine complex: Synthesis, characterization, thermal decomposition and its application to prepare ceria support for platinum catalysts used in methane steam reforming

    NASA Astrophysics Data System (ADS)

    Wattanathana, Worawat; Nootsuwan, Nollapan; Veranitisagul, Chatchai; Koonsaeng, Nattamon; Laosiripojana, Navadol; Laobuthee, Apirat

    2015-06-01

    Cerium-triethanolamine complex was synthesized by simple complexation method in 1-propanol solvent using cerium(III) chloride as a metal source and triethanolamine as a ligand. The structures of the prepared complex were proposed based on FT-IR, FT-Raman and ESI-MS results as equimolar of triethanolamine and cerium chelated complex having monomeric tricyclic structure with and without chloride anion as another coordinating group known as ceratrane. The complex was used as a precursor for ceria material done by thermal decomposition. XRD result revealed that when calcined at 600 °C for 2 h, the cerium complex was totally turned into pure ceria with cubic fluorite structure. The obtained ceria was then employed to synthesize platinum doped ceria catalysts for methane steam reforming. Various amounts of platinum i.e. 1, 3, 5 and 10 mol percents were introduced on the ceria support by microwave-assisted wetness impregnation using ammonium tetrachloroplatinate(II). The platinum-impregnated ceria powders were subjected to calcination in 10% hydrogen/helium atmosphere at 500 °C for 3 h to reduce platinum(II) to platinum(0). XRD patterns of the catalysts confirmed that the platinum particles doped on the ceria support were in the form of platinum(0). Catalytic activity test showed that the catalytic activities got higher as the amounts of platinum doped increased. Besides, the portions of coke formation on the surface of catalysts were reduced as the amounts of platinum doped increased.

  9. Anion Transport with Chalcogen Bonds.

    PubMed

    Benz, Sebastian; Macchione, Mariano; Verolet, Quentin; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-07-27

    In this report, we introduce synthetic anion transporters that operate with chalcogen bonds. Electron-deficient dithieno[3,2-b;2',3'-d]thiophenes (DTTs) are identified as ideal to bind anions in the focal point of the σ holes on the cofacial endocyclic sulfur atoms. Anion binding in solution and anion transport across lipid bilayers are found to increase with the depth of the σ holes of the DTT anionophores. These results introduce DTTs and related architectures as a privileged motif to engineer chalcogen bonds into functional systems, complementary in scope to classics such as 2,2'-bipyrroles or 2,2'-bipyridines that operate with hydrogen bonds and lone pairs, respectively. PMID:27433964

  10. Fischer–Tropsch Synthesis: Characterization Rb Promoted Iron Catalyst

    SciTech Connect

    Sarkar,A.; Jacobs, G.; Ji, Y.; Hamdeh, H.; Davis, B.

    2008-01-01

    Rubidium promoted iron Fischer-Tropsch synthesis (FTS) catalysts were prepared with two Rb/Fe atomic ratios (1.44/100 and 5/100) using rubidium nitrate and rubidium carbonate as rubidium precursors. Results of catalytic activity and deactivation studies in a CSTR revealed that rubidium promoted catalysts result in a steady conversion with a lower deactivation rate than that of the corresponding unpromoted catalyst although the initial activity of the promoted catalyst was almost half that of the unpromoted catalyst. Rubidium promotion results in lower methane production, and higher CO2, alkene and 1-alkene fraction in FTS products. M{umlt o}ssbauer spectroscopic measurements of CO activated and working catalyst samples indicated that the composition of the iron carbide phase formed after carbidization was -Fe5 C2 for both promoted and unpromoted catalysts. However, in the case of the rubidium promoted catalyst, '-Fe2.2C became the predominant carbidic phase as FTS continued and the overall catalyst composition remained carbidic in nature. In contrast, the carbide content of the unpromoted catalyst was found to decline very quickly as a function of synthesis time. Results of XANES and EXAFS measurements suggested that rubidium was present in the oxidized state and that the compound most prevalent in the active catalyst samples closely resembled that of rubidium carbonate.

  11. Synthesis of organic-inorganic hybrid mesoporous tin oxophosphate in the presence of anionic surfactant.

    PubMed

    Mal, Nawal Kishor; Fujiwara, Masahiro; Matsukata, Masahiko

    2005-11-01

    Synthesis of novel mesoporous hybrid tin oxophosphate is reported from phenylphosphonic acid as the only precursor of phosphorus in the presence of anionic surfactant (SDS), which possesses a wormhole mesoporous structure and is stable even after calcination at 550 degrees C. PMID:16228034

  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. Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

    SciTech Connect

    Bowker, Richard H.; Smith, Mica C.; Pease, Melissa; Slenkamp, Karla M.; Kovarik, Libor; Bussell, Mark E.

    2011-07-01

    Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

  14. Photocatalytic Anion Oxidation and Applications in Organic Synthesis.

    PubMed

    Hering, Thea; Meyer, Andreas Uwe; König, Burkhard

    2016-08-19

    Ions and radicals of the same kind differ by one electron only. The oxidation of many stable inorganic anions yields their corresponding highly reactive radicals, and visible light excitable photocatalysts can provide the required oxidation potential for this transformation. Air oxygen serves as the terminal oxidant, or cheap sacrificial oxidants are used, providing a very practical approach for generating reactive inorganic radicals for organic synthesis. We discuss in this perspective several recently reported examples: Nitrate radicals are obtained by one-electron photooxidation of nitrate anions and are very reactive toward organic molecules. The photooxidation of sulfinate salts yields the much more stable sulfone radicals, which smoothly add to double bonds. A two-electron oxidation of chloride anions to electrophilic chlorine species reacting with arenes in aromatic substitutions extends the method beyond radical reactions. The chloride anion oxidation proceeds via photocatalytically generated peracidic acid as the oxidation reagent. Although the number of reported examples of photocatalytically generated inorganic radical intermediates for organic synthesis is still small, future extension of the concept to other inorganic ions as radical precursors is a clear perspective. PMID:27355754

  15. The mechanism of inactivation of a 50-pS envelope anion channel during chloroplast protein import.

    PubMed Central

    van den Wijngaard, P W; Dabney-Smith, C; Bruce, B D; Vredenberg, W J

    1999-01-01

    The mechanism of import-competent precursor protein-induced inactivation of a 50-pS anion channel of the chloroplast envelope is investigated using single-channel recordings. The inactivation by precursor protein is the result of the induction of a long-lived closed state of the channel. The mean duration of this state does not depend on precursor concentration. From this it can be concluded that the protein import related anion channel enters the inactive state less frequently when the precursor concentration is lowered, but that the time spent in this state remains the same. Furthermore, it was found that the presence of precursor protein also decreases the mean durations of preexisting open and closed states of the channel. This decrease is found to be dependent on the precursor concentration. From this it is concluded that there is a direct interaction between the precursor protein and a protein complex of which the channel is a constituent. The mean duration of the precursor-induced long-lived closed state does not depend on the length of the translocation-competent precursor. This suggests that the duration of import is independent of precursor length. PMID:10585937

  16. Organic solvent soluble oxide supported hydrogenation catalyst precursors

    DOEpatents

    Edlund, David J.; Finke, Richard G.; Saxton, Robert J.

    1992-01-01

    The present invention discloses two polyoxoanion supported metal complexes found to be useful in olefin hydrogenation. The complexes are novel compositions of matter which are soluble in organic solvents. In particular, the compositions of matter comprise A.sub.x [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.15 M'.sub.3 O.sub.62 ].sup.x- and A.sub.y [L.sub.n Ir.sup.(I) .multidot.X.sub.2 M.sub.9 M'.sub.3 O.sub.40 ].sup.y- where L is a ligand preferably chosen from 1,5-cyclooctadiene (COD), ethylene, cyclooctene, norbornadiene and other olefinic ligands; n=1 or 2 depending upon the number of double bonds present in the ligand L; X is a "hetero" atom chosen from B, Si, Ge, P, As, Se, Te, I, Co, Mn and Cu; M is either W or Mo; M' is preferably Nb or V but Ti, Zr, Ta, Hf are also useful; and A is a countercation preferably selected from tetrabutyl ammonium and alkali metal ions.

  17. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  18. Ambident reactivities of pyridone anions.

    PubMed

    Breugst, Martin; Mayr, Herbert

    2010-11-01

    The kinetics of the reactions of the ambident 2- and 4-pyridone anions with benzhydrylium ions (diarylcarbenium ions) and structurally related Michael acceptors have been studied in DMSO, CH(3)CN, and water. No significant changes of the rate constants were found when the counterion was varied (Li(+), K(+), NBu(4)(+)) or the solvent was changed from DMSO to CH(3)CN, whereas a large decrease of nucleophilicity was observed in aqueous solution. The second-order rate constants (log k(2)) correlated linearly with the electrophilicity parameters E of the electrophiles according to the correlation log k(2) = s(N + E) (Angew. Chem., Int. Ed. Engl. 1994, 33, 938-957), allowing us to determine the nucleophilicity parameters N and s for the pyridone anions. The reactions of the 2- and 4-pyridone anions with stabilized amino-substituted benzhydrylium ions and Michael acceptors are reversible and yield the thermodynamically more stable N-substituted pyridones exclusively. In contrast, highly reactive benzhydrylium ions (4,4'-dimethylbenzhydrylium ion), which react with diffusion control, give mixtures arising from N- and O-attack with the 2-pyridone anion and only O-substituted products with the 4-pyridone anion. For some reactions, rate and equilibrium constants were determined in DMSO, which showed that the 2-pyridone anion is a 2-4 times stronger nucleophile, but a 100 times stronger Lewis base than the 4-pyridone anion. Quantum chemical calculations at MP2/6-311+G(2d,p) level of theory showed that N-attack is thermodynamically favored over O-attack, but the attack at oxygen is intrinsically favored. Marcus theory was employed to develop a consistent scheme which rationalizes the manifold of regioselectivities previously reported for the reactions of these anions with electrophiles. In particular, Kornblum's rationalization of the silver ion effect, one of the main pillars of the hard and soft acid/base concept of ambident reactivity, has been revised. Ag(+) does not

  19. Bound anionic states of adenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H

    2007-03-20

    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  20. Indirect synthesis of Al{sub 2}O{sub 3}via radiation- or photochemical formation of its hydrated precursors

    SciTech Connect

    Barta, Jan Pospisil, Milan; Cuba, Vaclav

    2014-01-01

    Graphical abstract: - Highlights: • Al{sub 2}O{sub 3} precursors were produced by UV/e-beam irradiation of aqueous solutions. • Depending on the aluminium salt (Cl{sup −} or NO{sub 3}{sup −}), either γ-AlOOH or Al(OH){sub 3} is formed. • The mechanism involved strongly depends on the presence of formate anion. • Prepared mesoporous solid phase has high specific surface area (<190 m{sup 2} g{sup −1}). • Calcination of the precursor leads to the formation of γ-/η-, θ- and α-Al{sub 2}O{sub 3}. - Abstract: γ-, θ- and α-modifications of aluminium oxide (alumina) were successfully prepared by calcination of precursor solid phase obtained by irradiation of clear aqueous solutions by UV light or electron beam. For the precipitate to form, formate anion must be present in the solution in sufficient concentration. According to X-ray diffraction, the precipitate was found to consist of γ-AlOOH or a mixture of γ- and α-Al(OH){sub 3}, when aluminium chloride or aluminium nitrate was used, respectively. The addition of hydrogen peroxide as a ·OH radical source and sensitizer markedly improved the efficiency of the preparation. Some hints for the apparently very complex mechanism involved were listed and discussed. Calcination of the dried precipitate at 500–800 °C produced highly porous γ-alumina with high specific surface area (ca. 150 m{sup 2} g{sup −1}). Mixture of γ- and θ-transition aluminas was obtained at 1000 °C and pure, stable corundum α-Al{sub 2}O{sub 3} formed at 1200 °C. Samples were further investigated by means of scanning electron microscopy and specific surface area or porosity measurement. According to N{sub 2} adsorption isotherm, the precipitate contains mostly mesopores with average pore size 7 nm with specific surface area of ca. 100 m{sup 2} g{sup −1}. Possible applications of the material as sorbent or catalyst as well as a pure matrix for thermoluminescence dosimetry were briefly contemplated. Strong light

  1. Hydrogen in anion vacancies of semiconductors

    SciTech Connect

    Du, Mao-Hua; Singh, David J

    2009-01-01

    Density functional calculations show that, depending on the anion size, hydrogen in anion vacancies of various II-VI semiconductors can be either two-fold or four-fold coordinated, and has either amphoteric or shallow donor character. In general, the multi-coordination of hydrogen in an anion vacancy is the indication of an anionic H, H { ion, in the relatively ionic environment. In more covalent semiconductors, H would form a single cation-H bond in the anion vacancy.

  2. OXIDANT-PRECURSOR RELATIONSHIPS

    EPA Science Inventory

    New methods of ambient air analysis were used to define more clearly the relationships between oxidants and their precursors. Non-methane hydrocarbons, NOx, O2, and oxidants were measured at the same time and location (Riverside, California). The ambient air data presented in thi...

  3. Untangling ENSO Precursors

    NASA Astrophysics Data System (ADS)

    Pegion, K.; Alexander, M. A.

    2014-12-01

    There are several proposed precursors to the El Nino-Southern Oscillation (ENSO) that may provide the ability to predict ENSO as much as one year in advance. Some of these precursors are associated with stochastic forcing from extratropical atmospheric variability. Two examples are the seasonal footprinting mechanism (SFM) and the Pacific meridional mode (PMM). Both of these ENSO precursors are thought to be forced by the North Pacific Oscillation (NPO), a north-south sea level pressure dipole in the north Pacific. Additionally, both the PMM and SFM are thought to impact the tropics through wind evaporation SST feedbacks and have a correlation with ENSO up to one year in advance. These two precursors are discussed interchangeably throughout the literature and various indices used to define them co-mingle them. As a result, whether they are independent of each other or are part of the same process has not been investigated. The research presented is focused on untangling the relationship between the PMM, SFM, NPO, and ENSO using observational datasets and model simulations. Observational results demonstrate that these two mechanisms are different, are forced by different atmospheric circulations, and result in different manifestations of ENSO. Modeling results highlight the extent to which climate models can simulate these relationships and their impact on the simulation of ENSO.

  4. Asymmetric Anion-π Catalysis of Iminium/Nitroaldol Cascades To Form Cyclohexane Rings with Five Stereogenic Centers Directly on π-Acidic Surfaces.

    PubMed

    Liu, Le; Cotelle, Yoann; Avestro, Alyssa-Jennifer; Sakai, Naomi; Matile, Stefan

    2016-06-29

    Anion-π interactions have been introduced to catalysis only recently, and evidence for their significance is so far limited to one classical model reaction in enolate and enamine chemistry. In this report, asymmetric anion-π catalysis is achieved for the first time for a more demanding cascade process. The selected example affords six-membered carbocycles with five stereogenic centers in a single step from achiral and acyclic substrates. Rates, yields, turnover, diastereo- and enantioselectivity are comparable with conventional catalysts. Rates and stereoselectivity increase with the π-acidity of the new anioncatalysts. Further support for operational anion-π interactions in catalysis is obtained from inhibition with nitrate. As part of the stereogenic cascade reaction, iminium chemistry and conjugate additions are added to the emerging repertoire of asymmetric anion-π catalysis. PMID:27327089

  5. Unexpected role of anionic ligands in the ruthenium-catalyzed base-free selective hydrogenation of aldehydes.

    PubMed

    Dupau, Philippe; Bonomo, Lucia; Kermorvan, Laurent

    2013-10-18

    Bigger and better: The replacement of anionic chloride ligands in Noyori-type [(diamine)(diphosphine)RuCl2 ] catalysts with bulky carboxylate ligands enabled the efficient selective hydrogenation of a variety of aldehydes under base-free conditions. Turnover numbers of up to 100 000 were reached in the presence of a bulky carboxylic acid co-catalyst. This type of catalytic system probably operates through an inner-sphere mechanism. PMID:24038827

  6. 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

  7. Supported catalysts using nanoparticles as the support material

    DOEpatents

    Wong, Michael S.; Wachs, Israel E.; Knowles, William V.

    2010-11-02

    A process for making a porous catalyst, comprises a) providing an aqueous solution containing a nanoparticle precursor, b) forming a composition containing nanoparticles, c) adding a first catalytic component or precursor thereof and a pore-forming agent to the composition containing nanoparticles and allowing the first catalytic component, the pore-forming agent, and the nanoparticles form an organic-inorganic structure, d) removing water from the organic-inorganic structure; and e) removing the pore-forming agent from the organic-inorganic structure so as to yield a porous catalyst.

  8. Low temperature catalysts for methanol production

    DOEpatents

    Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.; Mahajan, Devinder

    1986-01-01

    A catalyst and process useful at low temperatures (below about 160.degree. C.) and preferably in the range 80.degree.-120.degree. C. used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa--M(OAc).sub.2 where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M=Ni and R=tertiary amyl). Mo(CO).sub.6 is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

  9. Low temperature catalysts for methanol production

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

    1986-10-28

    A catalyst and process useful at low temperatures (below about 160 C) and preferably in the range 80--120 C used in the production of methanol from carbon monoxide and hydrogen are disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa-M(OAc)[sub 2] where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is NiC (where M = Ni and R = tertiary amyl). Mo(CO)[sub 6] is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

  10. Low temperature catalysts for methanol production

    DOEpatents

    Sapienza, R.S.; Slegeir, W.A.; O'Hare, T.E.; Mahajan, D.

    1985-03-12

    A catalyst and process useful at low temperatures (below about 160/sup 0/C) and preferably in the range 80 to 120/sup 0/C used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH-RONa-M(OAc)/sub 2/ where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1 to 6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M = Ni and R = tertiary amyl). Mo(CO)/sub 6/ is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

  11. Pu Anion Exchange Process Intensification

    SciTech Connect

    Taylor-Pashow, K.

    2015-10-08

    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  12. Ionic Block Copolymers for Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    Tsai, Tsung-Han; Herbst, Dan; Giffin, Guinevere A.; di Noto, Vito; Witten, Tom; Coughlin, E. Bryan

    2013-03-01

    Anion exchange membrane (AEM) fuel cells have regained interest because it allows the use of non-noble metal catalysts. Until now, most of the studies on AEM were based on random polyelectrolytes. In this work, Poly(vinylbenzyltrimethylammonium bromide)-b- (methylbutylene) ([PVBTMA][Br]-b-PMB) was studied by SAXS, TEM and dielectric spectroscopy to understand the fundamental structure-conductivity relationship of ion transport mechanisms within well-ordered block copolymers. The ionic conductivity and the formation of order structure were dependent on the casting solvent. Higher ion exchange capacity (IEC) of the membranes showed higher conductivity at as IEC values below 1.8mmol/g, as above this, the ionic conductivity decreases due to more water uptake leading to dilution of charge density. The humidity dependence of morphology exhibited the shifting of d-spacing to higher value and the alteration in higher characteristic peak of SAXS plot as the humidity increase from the dry to wet state. This phenomenon can be further explained by a newly developed polymer brush theory. Three ionic conduction pathways with different conduction mechanism within the membranes can be confirmed by broadband electric spectroscopy. US Army MURI (W911NF1010520)

  13. 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.

  14. 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.

  15. 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.

  16. Long-Life Catalyst

    NASA Technical Reports Server (NTRS)

    1999-01-01

    STC Catalysts, Inc. (SCi) manufactures a noble metal reducible oxide catalyst consisting primarily of platinum and tin dioxide deposited on a ceramic substrate. It is an ambient temperature oxidation catalyst that was developed primarily for Carbon Dioxide Lasers.The catalyst was developed by the NASA Langley Research Center for the Laser Atmospheric Wind Sounder Program (LAWS) which was intended to measure wind velocity on a global basis. There are a number of NASA owned patents covering various aspects of the catalyst.

  17. Hydrogen-bonded pillars of alternating chiral complex cations and anions: 1. Synthesis, characterization, X-ray structure and thermal stability of catena-{[Co(H(2)oxado)(3)][Cr(C(2)O(4))(3)].5H(2)O} and of its precursor (H(3)oxado)[Co(H(2)oxado)(3)](SO(4))(2).2H(2)O.

    PubMed

    Bélombé, M M; Nenwa, J; Mbiangué, Y A; Majoumo-Mbé, F; Lönnecke, P; Hey-Hawkins, E

    2009-06-21

    Compound (H(3)oxado)[Co(H(2)oxado)(3)](SO(4))(2).2H(2)O () (H(3)oxado(+) = oxamide dioximemonoximium) reacted metathetically with Ba(6)(H(2)O)(17)[Cr(C(2)O(4))(3)](4).7H(2)O in water to give the one-dimensional complex salt {[Co(H(2)oxado)(3)][Cr(C(2)O(4))(3)].5H(2)O}(infinity) () (H(2)oxado = oxamide dioxime). Compounds and were characterized by elemental analysis, FTIR, UV-Vis and by single crystal X-ray structure determination. The structure of consists of infinite pillars of alternating chiral complex cations and anions linked together along [100] by electrostatic and longitudinal O-HO interactions, with an average intrachain CoCr separation of 4.94 A. Equatorial N-HO bridges cross-link neighboring pillars (which are of opposite chirality) and consolidate a three-dimensional lattice framework which delineates elliptic nanochannels parallel to the a axis, encapsulating highly disordered water molecules. The thermal stability of both compounds was assessed by TGA, and the effective magnetic moment of , checked at room temperature, revealed considerable spin-orbit coupling. PMID:19488450

  18. Towards the Rational Design of Nanoparticle Catalysts

    NASA Astrophysics Data System (ADS)

    Dash, Priyabrat

    This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts. In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall "greenness" of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle

  19. Oxidation of alkanes by cobalt(II) salts of weakly coordinating anions

    SciTech Connect

    Goldstein, A.S.; Drago, R.S. )

    1991-11-27

    Catalysts which effect the selective oxidation of alkanes under mild reaction conditions are highly desired. Commercial processes exist which involve the oxidation of alkanes by O{sub 2} with cobalt carboxylate catalysts. Elevated temperatures and pressures are required, and the metal ion function is to decompose hydroperoxides formed in a radical-chain process. The authors have demonstrated that a weakly solvated cobalt-acetonitrile complex (Co(NCCH{sub 3}){sub 4})(PF{sub 6}){sub 2}, with a weakly coordinating anion catalyzes the air oxidation of alkanes under mild conditions (75C and 3 atm). Cyclohexane and adamantane are converted to the corresponding alcohol and ketone products. The commercial catalyst for cyclohexane oxidation does not function under these milder conditions. Experiments indicate a mechanism in which the metal ion functions both as an initiator and as a hydroperoxide decomposition catalyst.

  20. Anion release and uptake kinetics: structural changes of layered 2-dimensional ZnNiHN upon uptake of acetate and chlorinated acetate anions.

    PubMed

    Machingauta, Cleopas; Hossenlopp, Jeanne M

    2013-12-01

    X-ray diffraction and UV-vis spectroscopy were used for the investigation of ion exchange reaction kinetics of nitrates with acetate (Ac), chloro acetate (ClAc), dichloro acetate (dClAc) and trichloro acetate (tClAc) anions, using zinc nickel hydroxy nitrate (ZnNiHN) as the exchange precursor. The exchange reactions conducted at 24, 30, 40 and 50°C revealed that rate constants were inversely related to the calculated anion electronic spatial extent (ESE), while a direct relationship between rate constants and the average oxygen charges was observed. Temporal solid phase structural transformations were shown to be affected by the nature of the guest anions. The amount of nitrates released into solution has been shown to decrease as the guest anions became more chlorinated. Use of isoconversional approach revealed that activation energies changed significantly with α during dClAc intercalation than for the other anions. The topotactic intercalation of the guest anions, except dClAc, followed the Avrami-Erofe'ev kinetic model for the entire reaction progress. PMID:24054447

  1. The EM Earthquake Precursor

    NASA Astrophysics Data System (ADS)

    Jones, K. B., II; Saxton, P. T.

    2013-12-01

    Many attempts have been made to determine a sound forecasting method regarding earthquakes and warn the public in turn. Presently, the animal kingdom leads the precursor list alluding to a transmission related source. By applying the animal-based model to an electromagnetic (EM) wave model, various hypotheses were formed, but the most interesting one required the use of a magnetometer with a differing design and geometry. To date, numerous, high-end magnetometers have been in use in close proximity to fault zones for potential earthquake forecasting; however, something is still amiss. The problem still resides with what exactly is forecastable and the investigating direction of EM. After the 1989 Loma Prieta Earthquake, American earthquake investigators predetermined magnetometer use and a minimum earthquake magnitude necessary for EM detection. This action was set in motion, due to the extensive damage incurred and public outrage concerning earthquake forecasting; however, the magnetometers employed, grounded or buried, are completely subject to static and electric fields and have yet to correlate to an identifiable precursor. Secondly, there is neither a networked array for finding any epicentral locations, nor have there been any attempts to find even one. This methodology needs dismissal, because it is overly complicated, subject to continuous change, and provides no response time. As for the minimum magnitude threshold, which was set at M5, this is simply higher than what modern technological advances have gained. Detection can now be achieved at approximately M1, which greatly improves forecasting chances. A propagating precursor has now been detected in both the field and laboratory. Field antenna testing conducted outside the NE Texas town of Timpson in February, 2013, detected three strong EM sources along with numerous weaker signals. The antenna had mobility, and observations were noted for recurrence, duration, and frequency response. Next, two

  2. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

    SciTech Connect

    Chunshan Song; Schobert, H.H.; Parfitt, D.P.

    1997-11-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

  3. 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.

  4. Anion binding in biological systems

    NASA Astrophysics Data System (ADS)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  5. ''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.

  6. Combinatorial synthesis and screening of fuel cell catalysts

    NASA Astrophysics Data System (ADS)

    Jayaraman, Shrisudersan

    Polymer electrolyte membrane fuel cells (PEMFCs) are compact power sources that can operate with high efficiencies and low emission of environmentally harmful gases. One of the major barriers impeding the development of PEMFCs as a competitive energy source is the inability of existing anode catalysts to oxidize fuels other than hydrogen at sufficient levels due to catalyst deactivation by carbon monoxide (CO) and other partial oxidation products. The focus of this research is the development and application of combinatorial strategies to construct and interrogate electrooxidation (anode) catalysts pertaining to PEMFCs to discover catalysts with enhanced performance in catalyst deactivating environments. A novel method (known as the "gel-transfer" method) for synthesizing catalyst composition gradient libraries for combinatorial catalyst discovery was developed. This method involved transferring a spatial concentration gradient of precursor metal salts created within a polymer gel on to a solid conducting substrate by electrochemical reduction. Chemically sensitive surface-imaging techniques, namely, scanning electrochemical microscopy (SECM) and optical screening with a pH-dependent fluorescence probe were used to characterize the combinatorial catalyst samples. The utility of SECM as a screening tool to measure the activity of multicomponent catalyst libraries towards fuel cell electrooxidation reactions was established with simple catalyst libraries including a platinum coverage gradient and platinum-ruthenium and platinum-ruthenium-molybdenum arrays. A platinum-ruthenium surface composition gradient was constructed through the gel-transfer method and its reactivity towards hydrogen oxidation in the presence of a catalyst poison (CO) was mapped using the SECM. Ruthenium composition between 20 and 30% exhibited superior performance than the rest of the binary. The gel-transfer method was extended to construct a ternary platinum-ruthenium-rhodium catalyst library

  7. In-Situ XAFS Characterization for Nitriding Process of Silica Supported Nb Catalysts Under N2-H2 Gas

    SciTech Connect

    Ichikuni, Nobuyuki; Matsumoto, Hiroari; Haneishi, Hidenori; Shimazu, Shogo; Bando, Kyoko K.

    2007-02-02

    Fe-Nb/SiO2 catalyst was prepared from NbCl5 or peroxoniobic acid as Nb precursors. These precursor catalysts were nitrided by the TPR method under N2-H2 passage (without using NH3). Nb K-edge in-situ XAFS measurements were carried out during the nitriding process and revealed that the Nb species was more nitrided in the Fe-Nb/SiO2 catalyst prepared from peroxoniobic acid than in that prepared from NbCl5 as Nb precursor.

  8. In-Situ XAFS Characterization for Nitriding Process of Silica Supported Nb Catalysts Under N2-H2 Gas

    NASA Astrophysics Data System (ADS)

    Ichikuni, Nobuyuki; Matsumoto, Hiroari; Haneishi, Hidenori; Bando, Kyoko K.; Shimazu, Shogo

    2007-02-01

    Fe-Nb/SiO2 catalyst was prepared from NbCl5 or peroxoniobic acid as Nb precursors. These precursor catalysts were nitrided by the TPR method under N2-H2 passage (without using NH3). Nb K-edge in-situ XAFS measurements were carried out during the nitriding process and revealed that the Nb species was more nitrided in the Fe-Nb/SiO2 catalyst prepared from peroxoniobic acid than in that prepared from NbCl5 as Nb precursor.

  9. A non-precious electrocatalyst for oxygen reduction based on simple heat-treated precursors

    SciTech Connect

    Chung, Hoon T; Zelenay, Piotr; Johnston, Christina; Garzon, Fernando

    2008-07-18

    Some active non-precious catalyst was made by simple heat treated novel precursors. The power density obtained in the H{sub 2}/O{sub 2} fed PEM fuel cells is as high as 0.22 W/cm{sup 2}{sub MEA} at 0.65 V. The active site seems to have little relevance with the nitrogen. We are now working on to figure out the active site(s) in this catalyst.

  10. Collaboration between primitive cell membranes and soluble catalysts.

    PubMed

    Adamala, Katarzyna P; Engelhart, Aaron E; Szostak, Jack W

    2016-01-01

    One widely held model of early life suggests primitive cells consisted of simple RNA-based catalysts within lipid compartments. One possible selective advantage conferred by an encapsulated catalyst is stabilization of the compartment, resulting from catalyst-promoted synthesis of key membrane components. Here we show model protocell vesicles containing an encapsulated enzyme that promotes the synthesis of simple fatty acid derivatives become stabilized to Mg(2+), which is required for ribozyme activity and RNA synthesis. Thus, protocells capable of such catalytic transformations would have enjoyed a selective advantage over other protocells in high Mg(2+) environments. The synthetic transformation requires both the catalyst and vesicles that solubilize the water-insoluble precursor lipid. We suggest that similar modified lipids could have played a key role in early life, and that primitive lipid membranes and encapsulated catalysts, such as ribozymes, may have acted in conjunction with each other, enabling otherwise-impossible chemical transformations within primordial cells. PMID:26996603

  11. Collaboration between primitive cell membranes and soluble catalysts

    PubMed Central

    Adamala, Katarzyna P.; Engelhart, Aaron E.; Szostak, Jack W.

    2016-01-01

    One widely held model of early life suggests primitive cells consisted of simple RNA-based catalysts within lipid compartments. One possible selective advantage conferred by an encapsulated catalyst is stabilization of the compartment, resulting from catalyst-promoted synthesis of key membrane components. Here we show model protocell vesicles containing an encapsulated enzyme that promotes the synthesis of simple fatty acid derivatives become stabilized to Mg2+, which is required for ribozyme activity and RNA synthesis. Thus, protocells capable of such catalytic transformations would have enjoyed a selective advantage over other protocells in high Mg2+ environments. The synthetic transformation requires both the catalyst and vesicles that solubilize the water-insoluble precursor lipid. We suggest that similar modified lipids could have played a key role in early life, and that primitive lipid membranes and encapsulated catalysts, such as ribozymes, may have acted in conjunction with each other, enabling otherwise-impossible chemical transformations within primordial cells. PMID:26996603

  12. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1992

    SciTech Connect

    Song, Chunshan; Schobert, H.H.

    1993-02-01

    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on the development of novel bimetallic dispersed catalysts for temperature-programmed liquefaction. The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular that can be used in low precursors concentrations (< 1 %) but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. The major technical approaches are, first, to prepare the desired heteronuclear organometallic molecules as catalyst precursors that contain covalently bound, two different metal atoms and sulfur in a single molecule. Such precursors will generate finely dispersed bimetallic catalysts such as Fe-Mo, Co-Mo and Ni-Mo binary sulfides upon thermal decomposition. The second major technical approach is to perform the liquefaction of coals unpregnated with the organometallic precursors under temperature-programmed conditions, where the programmed heat-up serves as a step for both catalyst activation and coal pretreatment or preconversion. Two to three different complexes for each of the Fe-Mo, Co-Mo, and Ni-Mo combinations will be prepared. Initial catalyst screening tests will be conducted using a subbituminous coal and a bituminous coal. Effects of coal rank and solvents will be examined with the selected bimetallic catalysts which showed much higher activity than the dispersed catalysts from conventional precursors.

  13. Porous polymers bearing functional quaternary ammonium salts as efficient solid catalysts for the fixation of CO2 into cyclic carbonates

    NASA Astrophysics Data System (ADS)

    Cai, Sheng; Zhu, Dongliang; Zou, Yan; Zhao, Jing

    2016-07-01

    A series of porous polymers bearing functional quaternary ammonium salts were solvothermally synthesized through the free radical copolymerization of divinylbenzene (DVB) and functionalized quaternary ammonium salts. The obtained polymers feature highly cross-linked matrices, large surface areas, and abundant halogen anions. These polymers were evaluated as heterogeneous catalysts for the synthesis of cyclic carbonates from epoxides and CO2 in the absence of co-catalysts and solvents. The results revealed that the synergistic effect between the functional hydroxyl groups and the halide anion Br- afforded excellent catalytic activity to cyclic carbonates. In addition, the catalyst can be easily recovered and reused for at least five cycles without significant loss in activity.

  14. Twisted and tubular silica structures by anionic surfactant fibers encapsulation.

    PubMed

    Chekini, Mahshid; Guénée, Laure; Marchionni, Valentina; Sharma, Manish; Bürgi, Thomas

    2016-09-01

    Organic molecules imprinting can be used for introducing specific properties and functionalities such as chirality to mesoporous materials. Particularly organic self-assemblies can work as a scaffold for templating inorganic materials such as silica. During recent years chiral imprinting of anionic surfactant for fabrication of twisted rod-like silica structures assisted by co-structuring directing agent were thoroughly investigated. The organic self-assemblies of anionic surfactants can also be used for introducing other shapes in rod-like silica structures. Here we report the formation of amphiphilic N-miristoyl-l-alanine self-assemblies in aqueous solution upon stirring and at presence of l-arginine. These anionic surfactant self-assemblies form fibers that grow by increasing the stirring duration. The fibers were studied using transmission electron microscopy, infra-red spectroscopy and vibrational circular dichroism. Addition of silica precursor 1,2-bis(triethoxysilyl)ethylene and co-structuring directing agent N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride at different stages of fibers' growth leads to formation of different silica structures. By controlling stirring duration, we obtained twisted tubular silica structures as a result of fibers encapsulation. We decorated these structures with gold nanoparticles by different methods and measured their optical activity. PMID:27267039

  15. Vascular Precursor Cells

    PubMed Central

    Chaudhury, Hera; Goldie, Lauren C.

    2011-01-01

    Understanding the mechanisms that regulate the proliferation and differentiation of human stem and progenitor cells is critically important for the development and optimization of regenerative medicine strategies. For vascular regeneration studies, specifically, a true “vascular stem cell” population has not yet been identified. However, a number of cell types that exist endogenously, or can be generated or propagated ex vivo, function as vascular precursor cells and can participate in and/or promote vascular regeneration. Herein, we provide an overview of what is known about the regulation of their differentiation specifically toward a vascular endothelial cell phenotype. PMID:22866199

  16. New magnetic organic inorganic composites based on hydrotalcite-like anionic clays for drug delivery

    NASA Astrophysics Data System (ADS)

    Carja, Gabriela; Chiriac, Horia; Lupu, Nicoleta

    2007-04-01

    The structural "memory effect" of anionic clays was used to obtain layered double hydroxides (LDHs) with tailored magnetic properties, by loading iron oxides and/or spinel structures on iron partially substituted hydrotalcite-like materials. The obtained magnetic layered structures were further used as precursors for new hybrid nanostructures, such as aspirin-hydrotalcite-like anionic clays. Transmission electron microscopy (TEM) analysis shows that small iron oxide or spinel nanoparticles coexist with the fibrous drug particles on the surface of partially aggregated typical clay-like particles. The specific saturation magnetization of the loaded LDHs can be increased up to 70 emu/g by using specific post-synthesis treatments.

  17. A highly reactive chalcogenide precursor for the synthesis of metal chalcogenide quantum dots

    NASA Astrophysics Data System (ADS)

    Jiang, Peng; Zhu, Dong-Liang; Zhu, Chun-Nan; Zhang, Zhi-Ling; Zhang, Guo-Jun; Pang, Dai-Wen

    2015-11-01

    Metal chalcogenide semiconductor nanocrystals (NCs) are ideal inorganic materials for solar cells and biomedical labeling. In consideration of the hazard and instability of alkylphosphines, the phosphine-free synthetic route has become one of the most important trends in synthesizing selenide QDs. Here we report a novel phase transfer strategy to prepare phosphine-free chalcogenide precursors. The anions in aqueous solution were transferred to toluene via electrostatic interactions between the anions and didodecyldimethylammonium bromide (DDAB). The obtained chalcogenide precursors show high reactivity with metal ions in the organic phase and could be applied to the low-temperature synthesis of various metal chalcogenide NCs based on a simple reaction between metal ions (e.g. Ag+, Pb2+, Cd2+) and chalcogenide anions (e.g. S2-) in toluene. In addition to chalcogenide anions, other anions such as BH4- ions and AuCl4- ions can also be transferred to the organic phase for synthesizing noble metal NCs (such as Ag and Au NCs).Metal chalcogenide semiconductor nanocrystals (NCs) are ideal inorganic materials for solar cells and biomedical labeling. In consideration of the hazard and instability of alkylphosphines, the phosphine-free synthetic route has become one of the most important trends in synthesizing selenide QDs. Here we report a novel phase transfer strategy to prepare phosphine-free chalcogenide precursors. The anions in aqueous solution were transferred to toluene via electrostatic interactions between the anions and didodecyldimethylammonium bromide (DDAB). The obtained chalcogenide precursors show high reactivity with metal ions in the organic phase and could be applied to the low-temperature synthesis of various metal chalcogenide NCs based on a simple reaction between metal ions (e.g. Ag+, Pb2+, Cd2+) and chalcogenide anions (e.g. S2-) in toluene. In addition to chalcogenide anions, other anions such as BH4- ions and AuCl4- ions can also be transferred to

  18. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

    1997-01-01

    Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  19. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

    1997-09-23

    Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  20. Gallium based low-interaction anions

    DOEpatents

    King, Wayne A.; Kubas, Gregory J.

    2000-01-01

    The present invention provides: a composition of the formula M.sup.+x (Ga(Y).sub.4.sup.-).sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R).sub.x Q.sup.+ Ga(Y).sub.4.sup.- where Q is selected from the group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M.sup.+x.sub.y [X(Ga(Y.sub.3).sub.z ].sup.-y.sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.

  1. The progression of chiral anions from concepts to applications in asymmetric catalysis

    NASA Astrophysics Data System (ADS)

    Phipps, Robert J.; Hamilton, Gregory L.; Toste, F. Dean

    2012-08-01

    Despite the tremendous advances of the past four decades, chemists are far from being able to use chiral catalysts to control the stereoselectivity of any desired reaction. New concepts for the construction and mode of operation of chiral catalysts have the potential to open up previously inaccessible reaction space. The recognition and categorization of distinct approaches seems to play a role in triggering rapid exploration of new territory. This Review both reflects on the origins as well as details a selection of the latest examples of an area that has advanced considerably within the past five years or so: the use of chiral anions in asymmetric catalysis. Defining reactions as involving chiral anions is a difficult task owing to uncertainties over the exact catalytic mechanisms. Nevertheless, we attempt to provide an overview of the breadth of reactions that could reasonably fall under this umbrella.

  2. Effects of anions on the kinetics and reactivity of nanoscale Pd/Fe in trichlorobenzene dechlorination.

    PubMed

    Lim, Teik-Thye; Zhu, Bao-Wei

    2008-11-01

    Influences of anionic co-solutes on dechlorination of 1,2,4-trichlorobenzene (124TCB) by the nanoscale Pd/Fe particles were investigated in batch experiments in the presence of an anionic solute such as nitrate, nitrite, perchlorate, phosphate, carbonate, silica, sulfate, sulfite, or sulfide. Based on the extent of inhibitory effects on the 124TCB dechlorination, the anions can be ranked in the order of: control≈sulfate≈silicaanions on the Pd/Fe surface. Silica and sulfate did not show any significant short-term effect on reactivity of the nanoscale Pd/Fe, because the 124TCB dechlorination reaction was only dependent on the reactivity of the Pd site that was apparently not passivated by the anions. However, sulfide and sulfite could immediately terminate the 124TCB dechlorination process. Based on the natures of their inhibitory effects on 124TCB dechlorination by the Pd/Fe, the anions can be classified as: (1) adsorption-precipitation passivating species (e.g., phosphate and carbonate), (2) redox-active species (e.g., nitrate, nitrite, and perchlorate), and (3) catalyst poisons (e.g., sulfide and sulfite). PMID:18760820

  3. Non-coordinating-Anion-Directed Reversal of Activation Site: Selective C-H Bond Activation of N-Aryl Rings.

    PubMed

    Wang, Dawei; Yu, Xiaoli; Xu, Xiang; Ge, Bingyang; Wang, Xiaoli; Zhang, Yaxuan

    2016-06-13

    An Rh-catalyzed selective C-H bond activation of diaryl-substituted anilides is described. In an attempt to achieve C-H activation of C-aryl rings, we unexpectedly obtained an N-aryl ring product under non-coordinating anion conditions, whereas the C-aryl ring product was obtained in the absence of a non-coordinating anion. This methodology has proved to be an excellent means of tuning and adjusting selective C-H bond activation of C-aryl and N-aryl rings. The approach has been rationalized by mechanistic studies and theoretical calculations. In addition, it has been found and verified that the catalytic activity of the rhodium catalyst is obviously improved by non-coordinating anions, which provides an efficient strategy for obtaining a highly chemoselective catalyst. Mechanistic experiments also unequivocally ruled out the possibility of a so-called "silver effect" in this transformation involving silver. PMID:27159169

  4. Model hydrocracking reactions over monometallic and bimetallic dispersed catalysts

    SciTech Connect

    Schmidt, E.; Song, C.

    1994-12-31

    Coal liquefaction involves the cleavage of methylene and dimethylene bridges connecting polycyclic aromatic units. The selected compound for model reactions is 4-(1-naphthylmethyl)bibenzyl (NMBB). This work describes the synthesis and screening of several metallic complex precursors as dispersed catalysts for hydrocracking of NMBB.

  5. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  6. Anion Solvation in Carbonate Electrolytes

    SciTech Connect

    Zhang, Zhengcheng

    2015-11-16

    With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  7. Lewis Base Catalysts 6: Carbene Catalysts

    PubMed Central

    Moore, Jennifer L.

    2013-01-01

    The use of N-heterocyclic carbenes as catalysts for organic transformations has received increased attention in the past 10 years. A discussion of catalyst development and nucleophilic characteristics precedes a description of recent advancements and new reactions using N-heterocyclic carbenes in catalysis. PMID:21494949

  8. Aza compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  9. Aza compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  10. Catalysts based on PdO_ZrO2 in the hydrodechlorination reaction of chlorobenzene

    NASA Astrophysics Data System (ADS)

    Otroshchenko, T. P.; Turakulova, A. O.; Lokteva, E. S.; Golubina, E. V.; Lunin, V. V.

    2015-07-01

    The possibility of using mixed oxides of palladium and zirconium obtained with biotemplates (cellulose and wood pulp) as the precursor of catalysts for the hydrodechlorination of chlorobenzene is analyzed. The properties of the samples are studied by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), the Brunauer-Emmet-Teller (BET) method, and temperature-programmed reduction (TPR). They are then compared to the properties of a supported analogue. The biomorphic precursors are characterized by high porosity and include micropores, mesopores, and macropores; the results from TPR reveal the presence in the precursors of several forms of PdO that differ by reduction temperature. It is shown that the distribution of palladium in the catalysts obtained by reducing the precursors with hydrogen depends on the method used in synthesizing the precursor. It is shown that the studied catalysts ensure 100% conversion of chlorobenzene at temperatures of 100 to 250°C. It is established that cyclohexane is the principal product in the presence of the supported catalyst across the range of temperatures, while cyclohexane and benzene are detected among the products in the presence of biomorphous samples at temperatures above 130°C. The effect the presence of an admixture of alkaline and alkaline-earth metals in the catalyst has on the selectivity of the process is noted. It is established that the catalysts operate in a stable manner for at least 27 h of use under experimental conditions.

  11. Probing neutral atmospheric collision complexes with anion photoelectron imaging

    NASA Astrophysics Data System (ADS)

    Jarrold, Caroline

    Photodetachment of anionic precursors of neutral collision complexes offers a way to probe the effects of symmetry-breaking collision events on the electronic structure of normally transparent molecules. We have measured the anion photoelectron imaging (PEI) spectra of a series of O2- X complexes, where X is a volatile organic molecule with atmospheric relevance, to determine how the electronic properties of various X molecules affect the low-lying electronic structure of neutral O2 undergoing O2 - X collisons. The study was motivated by the catalog of vibrational and electronic absorption lines induced by O2 - O2, O2 - N2, and other collisions. The energies of electronic features observed in the anion PEI spectra of O2- X (X = hexane, hexene, isoprene and benzene) relative to O2- PEI spectroscopic features indicate that photodetachment of the anion does indeed access a repulsive part of the O2 - X potential. In addition, the spectra of the various complexes show an interesting variation in the intensities of transitions to the excited O2(1Δg) . X and O2(1Σg+) . X states relative to the ground O2(3Σg-) . X state. With X = non-polar species such as hexane, the relative intensities of transitions to the triplet and singlet states of O2 . X are very similar to those of isolated O2, while the relative intensity of the singlet band decreases and becomes lower in energy relative to the triplet band for X = polar molecules. A significant enhancement in the intensities of the singlet bands is observed for complexes with X = isoprene and benzene, both of which have low-lying triplet states. The role of the triplet states in isoprene and benzene, and the implications for induced electronic absorption in O2 undergoing collisions with these molecules, are explored. National Science Foundation NSF CHE 1265991.

  12. Quaternized poly (styrene-co-vinylbenzyl chloride) anion exchange membranes for alkaline water electrolysers

    NASA Astrophysics Data System (ADS)

    Vengatesan, S.; Santhi, S.; Jeevanantham, S.; Sozhan, G.

    2015-06-01

    In this study, poly (ST-co-VBC) based anion exchange membranes with different styrene to VBC ratios (1: 0.16, 1: 0.33 and 1: 1) have been prepared via chloromethylation-free synthetic route using aromatic vinyl monomers. The synthesized co-polymers are identified by FTIR and 1H-NMR analysis. Hydroxide (OH-) ion conductivity of the anion exchange membrane with styrene to VBC ratio of 1: 0.33 is as high as 6.8 × 10-3 S cm-1 in de-ionised water at 25 °C. The membrane also acquires the ion-exchange capacity of 2.14 meq. g-1, and the water uptake of 127%. Membrane-electrode-assembly (MEA) using the anion exchange membrane and Ni - foam catalyst demonstrate the current density of 40 mA cm-2 at 2.3 V in a water electrolyser cell.

  13. Method for dispersing catalyst onto particulate material and product thereof

    DOEpatents

    Utz, Bruce R.; Cugini, Anthony V.

    1992-01-01

    A method for dispersing finely divided catalyst precursors onto the surface of coal or other particulate material includes the steps of forming a wet paste mixture of the particulate material and a liquid solution containing a dissolved transition metal salt, for instance a solution of ferric nitrate. The wet paste mixture is in a state of incipient wetness with all of this solution adsorbed onto the surfaces of the particulate material without the presence of free moisture. On adding a precipitating agent such as ammonia, a catalyst precursor such as hydrated iron oxide is deposited on the surfaces of the coal. The catalyst is activated by converting it to the sulfide form for the hydrogenation or direct liquefaction of the coal.

  14. An interstellar precursor mission

    NASA Technical Reports Server (NTRS)

    Jaffe, L. D.; Ivie, C.; Lewis, J. C.; Lipes, R. G.; Norton, H. N.; Stearns, J. W.; Stimpson, L.; Weissman, P.

    1977-01-01

    A mission out of the planetary system, with launch about the year 2000, could provide valuable scientific data as well as test some of the technology for a later mission to another star. Primary scientific objectives for the precursor mission concern characteristics of the heliopause, the interstellar medium, stellar distances (by parallax measurements), low energy cosmic rays, interplanetary gas distribution, and mass of the solar system. Secondary objectives include investigation of Pluto. Candidate science instruments are suggested. Individual spacecraft systems for the mission were considered, technology requirements and problem areas noted, and a number of recommendations made for technology study and advanced development. The most critical technology needs include attainment of 50-yr spacecraft lifetime and development of a long-life NEP system.

  15. Identified EM Earthquake Precursors

    NASA Astrophysics Data System (ADS)

    Jones, Kenneth, II; Saxton, Patrick

    2014-05-01

    Many attempts have been made to determine a sound forecasting method regarding earthquakes and warn the public in turn. Presently, the animal kingdom leads the precursor list alluding to a transmission related source. By applying the animal-based model to an electromagnetic (EM) wave model, various hypotheses were formed, but the most interesting one required the use of a magnetometer with a differing design and geometry. To date, numerous, high-end magnetometers have been in use in close proximity to fault zones for potential earthquake forecasting; however, something is still amiss. The problem still resides with what exactly is forecastable and the investigating direction of EM. After a number of custom rock experiments, two hypotheses were formed which could answer the EM wave model. The first hypothesis concerned a sufficient and continuous electron movement either by surface or penetrative flow, and the second regarded a novel approach to radio transmission. Electron flow along fracture surfaces was determined to be inadequate in creating strong EM fields, because rock has a very high electrical resistance making it a high quality insulator. Penetrative flow could not be corroborated as well, because it was discovered that rock was absorbing and confining electrons to a very thin skin depth. Radio wave transmission and detection worked with every single test administered. This hypothesis was reviewed for propagating, long-wave generation with sufficient amplitude, and the capability of penetrating solid rock. Additionally, fracture spaces, either air or ion-filled, can facilitate this concept from great depths and allow for surficial detection. A few propagating precursor signals have been detected in the field occurring with associated phases using custom-built loop antennae. Field testing was conducted in Southern California from 2006-2011, and outside the NE Texas town of Timpson in February, 2013. The antennae have mobility and observations were noted for

  16. Perlite as a potential support for nickel catalyst in the process of sunflower oil hydrogenation

    NASA Astrophysics Data System (ADS)

    Radonjić, V.; Krstić, J.; Lončarević, D.; Jovanović, D.; Vukelić, N.; Stanković, M.; Nikolova, D.; Gabrovska, M.

    2015-12-01

    Investigation was conducted in order to elucidate the possibility of using perlite as support for preparation of nickel based precursor catalyst, potentially applicable in vegetable oil hydrogenation process. On three differently prepared expanded perlite, nickel catalyst precursors with identical Ni/SiO2 = 1.1 and Ni/Mg = 10/1 ratios were synthesized by precipitation-deposition method. Different techniques, SEM micrography, He-pycnometry, calcimetry, Hg-porosimetry, N2-physisorption, H2-chemisorption and temperature programmed reduction, were used for characterization of obtained samples. Determining the precursor texture, morphology and reducibility shows a successfully deposited nickel phase on perlite support with promising properties for vegetable oil hydrogenation. Chosen precursor was reduced and passivated in paraffin oil and the obtained catalyst showed significant catalytic activity in the test of sunflower oil hydrogenation.

  17. Iridium-catalyst-based autonomous bubble-propelled graphene micromotors with ultralow catalyst loading.

    PubMed

    Wang, Hong; Sofer, Zdeněk; Eng, Alex Yong Sheng; Pumera, Martin

    2014-11-10

    A novel concept of an iridium-based bubble-propelled Janus-particle-type graphene micromotor with very high surface area and with very low catalyst loading is described. The low loading of Ir catalyst (0.54 at %) allows for fast motion of graphene microparticles with high surface area of 316.2 m(2)  g(-1). The micromotor was prepared with a simple and scalable method by thermal exfoliation of iridium-doped graphite oxide precursor composite in hydrogen atmosphere. Oxygen bubbles generated from the decomposition of hydrogen peroxide at the iridium catalytic sites provide robust propulsion thrust for the graphene micromotor. The high surface area and low iridium catalyst loading of the bubble-propelled graphene motors offer great possibilities for dramatically enhanced cargo delivery. PMID:25293511

  18. PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design

    NASA Astrophysics Data System (ADS)

    Stariha, Sarah; Artyushkova, Kateryna; Workman, Michael J.; Serov, Alexey; Mckinney, Sam; Halevi, Barr; Atanassov, Plamen

    2016-09-01

    This work studies the morphology of platinum group metal-free (PGM-free) iron-nitrogen-carbon (Fe-N-C) catalyst layers for the oxygen reduction reaction (ORR) and compares catalytic performance via polarization curves. Three different nitrogen-rich organic precursors are used to prepare the catalysts. Using scanning electron microscopy (SEM) and focused ion beam (FIB) tomography, the porosity, Euler number (pore connectivity), overall roughness, solid phase size and pore size are calculated for catalyst surfaces and volumes. Catalytic activity is determined using membrane electrode assembly (MEA) testing. It is found that the dominant factor in MEA performance is transport limitations. Through the 2D and 3D metrics it is concluded that pore connectivity has the biggest effect on transport performance.

  19. Morphological investigation of nanostructured CoMo catalysts

    NASA Astrophysics Data System (ADS)

    Pawelec, B.; Castaño, P.; Zepeda, T. A.

    2008-04-01

    This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO 3 and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO 4 phase. For all sulfided catalysts, the presence of MoS 2 phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS 2 particles and their sizes) as determined by HRTEM.

  20. Generation of Nonlinear Vortex Precursors.

    PubMed

    Chen, Yue-Yue; Feng, Xun-Li; Liu, Chengpu

    2016-07-01

    We numerically study the propagation of a few-cycle pulse carrying orbital angular momentum (OAM) through a dense atomic system. Nonlinear precursors consisting of high-order vortex harmonics are generated in the transmitted field due to carrier effects associated with ultrafast Bloch oscillation. The nonlinear precursors survive to propagation effects and are well separated with the main pulse, which provides a straightforward way to measure precursors. By virtue of carrying high-order OAM, the obtained vortex precursors as information carriers have potential applications in optical information and communication fields where controllable loss, large information-carrying capacity, and high speed communication are required. PMID:27447507

  1. Generation of Nonlinear Vortex Precursors

    NASA Astrophysics Data System (ADS)

    Chen, Yue-Yue; Feng, Xun-Li; Liu, Chengpu

    2016-07-01

    We numerically study the propagation of a few-cycle pulse carrying orbital angular momentum (OAM) through a dense atomic system. Nonlinear precursors consisting of high-order vortex harmonics are generated in the transmitted field due to carrier effects associated with ultrafast Bloch oscillation. The nonlinear precursors survive to propagation effects and are well separated with the main pulse, which provides a straightforward way to measure precursors. By virtue of carrying high-order OAM, the obtained vortex precursors as information carriers have potential applications in optical information and communication fields where controllable loss, large information-carrying capacity, and high speed communication are required.

  2. Optimization of Single and Bimetallic Noble Metal Catalysts by Strong Electrostatic Adsorption

    NASA Astrophysics Data System (ADS)

    Barnes, Sean E.

    Heterogeneous catalysts are used in over 90% of chemical processes today. These small metal particles maximize the number of active sites present, which leads to cheaper, more effective catalysts. However, the preparation of heterogeneous catalysts is still a "dark art". An alternate to dry impregnation is the method of Strong Electrostatic Adsorption (SEA). In this method the surface hydroxyl groups of the support can either protonate or deprotonate depending on the pH of the contacting solution. These surface groups then can then attract oppositely charged metal precursors. Preparation of catalysts by SEA leads to the anchoring of small, well dispersed, highly active metal particles. The aim of this work is to optimize the preparation via SEA of various supported catalysts systems, particularly Pt/carbon, Au supported on a variety of materials, and Au-Pd/carbon. Carbon supported metal catalysts are becoming increasingly important not just as electro catalyst in fuel cells, but for many aqueous phase biomass conversion reactions.

  3. Three Component Asymmetric Catalytic Ugi Reaction – Concinnity from Diversity via Substrate Mediated Catalyst Assembly

    PubMed Central

    Zhao, Wenjun; Huang, Li; Guan, Yong; Wulff, William D.

    2014-01-01

    The first asymmetric catalyst for the 3-component Ugi reaction was identified as a result of a screen of a large set of different BOROX catalysts. The BOROX catalysts are assembled in-situ from a chiral biaryl ligand, an amine, water, BH3•SMe2 and an alcohol or phenol. The catalyst screen included 13 different ligands, 12 amines and 47 alcohols or phenols. The optimal catalyst (LAP 8-5-47) provides the α-amino amides with excellent asymmetric induction from an aldehyde, 2° amine and an isonitrile. The catalyst is proposed to consist of an ion pair combination of a chiral boroxinate anion and an iminium cation. PMID:24554529

  4. System for reactivating catalysts

    SciTech Connect

    Ginosar, Daniel M.; Thompson, David N.; Anderson, Raymond P.

    2010-03-02

    A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst is provided. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

  5. 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.

  6. 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.

  7. Highly Conductive Anion-Exchange Membranes from Microporous Tröger's Base Polymers.

    PubMed

    Yang, Zhengjin; Guo, Rui; Malpass-Evans, Richard; Carta, Mariolino; McKeown, Neil B; Guiver, Michael D; Wu, Liang; Xu, Tongwen

    2016-09-12

    The development of polymeric anion-exchange membranes (AEMs) combining high ion conductivity and long-term stability is a major challenge for materials chemistry. AEMs with regularly distributed fixed cationic groups, based on the formation of microporous polymers containing the V-shape rigid Tröger's base units, are reported for the first time. Despite their simple preparation, which involves only two synthetic steps using commercially available precursors, the polymers provide AEMs with exceptional hydroxide conductivity at relatively low ion-exchange capacity, as well as a high swelling resistance and chemical stability. An unprecedented hydroxide conductivity of 164.4 mS cm(-1) is obtained at a relatively a low ion-exchange capacity of 0.82 mmol g(-1) under optimal operating conditions. The exceptional anion conductivity appears related to the intrinsic microporosity of the charged polymer matrix, which facilitates rapid anion transport. PMID:27505421

  8. Synthetic ion transporters that work with anion-π interactions, halogen bonds, and anion-macrodipole interactions.

    PubMed

    Vargas Jentzsch, Andreas; Hennig, Andreas; Mareda, Jiri; Matile, Stefan

    2013-12-17

    these elusive interactions in action, we synthesized naphthalenediimide transporters of increasing π-acidity up to an unprecedented quadrupole moment of +39 Buckinghams and characterized these systems in comparison with tandem mass spectrometry and computational simulations. With π-acidic calixarenes and calixpyrroles, we have validated our results on anion-π interactions and initiated our studies of halogen bonds. Halogen bonds originate from the σ-hole that appears on top of electron-deficient iodines, bromines, and chlorines. Halogen-bond donors are ideal for anion transport because they are as strong and at least as directional as hydrogen-bond donors, but also hydrophobic. The discovery of the smallest possible organic anion transporter, trifluoroiodomethane, illustrates the power of halogen-bond donors. This molecule contains a single carbon atom and is a gas with a boiling point of -22 °C. Anion-macrodipole interactions, finally, differ significantly from anion-π interactions and halogen bonds because they are important in nature and cannot be studied with small molecules. We have used anion-transporting peptide/urea nanotubes to examine these interactions in synthetic transport systems. To facilitate the understanding of the described results, we also include an in-depth discussion of the meaning of Hill coefficients. The use of synthetic transport systems to catch less common noncovalent interactions at work is important because it helps to expand the collection of interactions available to create functional systems. Progress in this direction furthers fundamental knowledge and invites many different applications. For illustration, we briefly discuss how this knowledge could apply to the development of new catalysts. PMID:23547885

  9. Catalyst patterning for nanowire devices

    NASA Technical Reports Server (NTRS)

    Li, Jun (Inventor); Cassell, Alan M. (Inventor); Han, Jie (Inventor)

    2004-01-01

    Nanowire devices may be provided that are based on carbon nanotubes or single-crystal semiconductor nanowires. The nanowire devices may be formed on a substrate. Catalyst sites may be formed on the substrate. The catalyst sites may be formed using lithography, thin metal layers that form individual catalyst sites when heated, collapsible porous catalyst-filled microscopic spheres, microscopic spheres that serve as masks for catalyst deposition, electrochemical deposition techniques, and catalyst inks. Nanowires may be grown from the catalyst sites.

  10. Hydrocarbon synthesis catalyst and method of preparation and use thereof. [DOE patent application

    SciTech Connect

    Sapienza, R.S.; Sansone, M.J.; Slegeir, W.A.R.

    1981-08-14

    A catalyst for the synthesis of hydrocarbons from carbon monoxide and hydrogen composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants. The catalyst is preferably used in dilute slurry form, which is desirable from a heat transfer standpoint.

  11. Textured catalysts and methods of making textured catalysts

    DOEpatents

    Werpy, Todd; Frye, Jr., John G.; Wang, Yong; Zacher, Alan H.

    2007-03-06

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

  12. A highly reactive chalcogenide precursor for the synthesis of metal chalcogenide quantum dots.

    PubMed

    Jiang, Peng; Zhu, Dong-Liang; Zhu, Chun-Nan; Zhang, Zhi-Ling; Zhang, Guo-Jun; Pang, Dai-Wen

    2015-12-01

    Metal chalcogenide semiconductor nanocrystals (NCs) are ideal inorganic materials for solar cells and biomedical labeling. In consideration of the hazard and instability of alkylphosphines, the phosphine-free synthetic route has become one of the most important trends in synthesizing selenide QDs. Here we report a novel phase transfer strategy to prepare phosphine-free chalcogenide precursors. The anions in aqueous solution were transferred to toluene via electrostatic interactions between the anions and didodecyldimethylammonium bromide (DDAB). The obtained chalcogenide precursors show high reactivity with metal ions in the organic phase and could be applied to the low-temperature synthesis of various metal chalcogenide NCs based on a simple reaction between metal ions (e.g. Ag(+), Pb(2+), Cd(2+)) and chalcogenide anions (e.g. S(2-)) in toluene. In addition to chalcogenide anions, other anions such as BH4(-) ions and AuCl4(-) ions can also be transferred to the organic phase for synthesizing noble metal NCs (such as Ag and Au NCs). PMID:26531253

  13. An interstellar precursor mission

    NASA Technical Reports Server (NTRS)

    Jaffe, L. D.; Ivie, C.; Lewis, J. C.; Lipes, R.; Norton, H. N.; Stearns, J. W.; Stimpson, L. D.; Weissman, P.

    1980-01-01

    A mission out of the planetary system, launched about the year 2000, could provide valuable scientific data as well as test some of the technology for a later mission to another star. Primary scientific objectives for the precursor mission concern characteristics of the heliopause, the interstellar medium, stellar distances (by parallax measurements), low-energy cosmic rays, interplanetary gas distribution, and the mass of the solar system. Secondary objectives include investigation of Pluto. The mission should extend to 400-1000 AU from the sun. A heliocentric hyperbolic escape velocity of 50-100 km/sec or more is needed to attain this distance within a reasonable mission duration (20-50 years). The trajectory should be toward the incoming interstellar gas. For a year 2000 launch, a Pluto encounter and orbiter can be included. A second mission targeted parallel to the solar axis would also be worthwhile. The mission duration is 20 years, with an extended mission to a total of 50 years. A system using one or two stages of nuclear electric propulsion (NEP) was selected as a possible baseline. The most promising alternatives are ultralight solar sails or laser sailing, with the lasers in earth orbit, for example. The NEP baseline design allows the option of carrying a Pluto orbiter as a daughter spacecraft.

  14. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

    SciTech Connect

    Hawthorne, M. Frederick; Jalisatgi, Satish S.; Safronov, Alexander V.; Lee, Han Beak; Wu, Jianguo

    2010-10-01

    Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum

  15. Investigation of platinum(IV) ions sorption on some anion exchangers by using photoacoustic and DRS methods

    NASA Astrophysics Data System (ADS)

    Wójcik, G.; Pasieczna, S.; Hubicki, Z.; Ryczkowski, J.

    2006-11-01

    The high cost and increasing demand have prompted the recovery of platinum from low-grade ores and spent catalysts. Platinum exist in chloride solutions in the anionic form, therefore anion-exchanging is a better method than cation exchanging for sorption of platinum(IV) ions. Therefore applicability of four anion exchangers Duolite A 30 B, Lewatit MP 62, Lewatit MP 64 and Purolite A 520E were studied. The FT-IR/PAS spectra were recorded by means of a Bio-Rad Excalibur 3000MX spectrometer equipped with photoacoustic detector MTEC300. The DRS (diffuse reflectance spectrometry) spectra of three anion exchangers Lewatit MP 62, Lewatit MP 64 and Purolite A 520E are similar but spectra of anion exchangers Duolite A 30B is different. The differences in spectra can be result from skeletons of anion exchangers. Recorded FT-IR/PAS spectra allow to distinguish the differences between applied anion exchangers before and after sorption of platinum(IV) ions. In all spectra the biggest differences could be noticed in the OH and CH{2} stretching region.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  17. Adsorption affinity of anions on metal oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.

    2013-03-01

    The dependences of anion (phosphate, carbonate, sulfate, chromate, oxalate, tartrate, and citrate) adsorption affinity anions from geometric characteristics, acid-base properties, and complex forming ability are generalized. It is shown that adsorption depends on the nature of both the anions and the ionic medium and adsorbent. It is established that anions are generally grouped into the following series of adsorption affinity reduction: PO{4/3-}, CO{3/2-} > C2O{4/2-}, C(OH)(CH2)2(COO){3/3-}, (CHOH)2(COO){2/2-} > CrO{4/2-} ≫ SO{4/2-}.

  18. Methods of making textured catalysts

    DOEpatents

    Werpy, Todd; Frye, Jr., John G.; Wang, Yong; Zacher, Alan H.

    2010-08-17

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

  19. Palladium coupling catalysts for pharmaceutical applications.

    PubMed

    Doucet, Henri; Hierso, Jean-Cyrille

    2007-11-01

    This review discusses recent advances made in the area of palladium-catalyzed coupling reactions and describes a selection of the catalytic systems that are useful in the preparation of valuable compounds for the pharmaceutical industry. Most of these types of syntheses have used either simple palladium salts or palladium precursors associated with electron-rich mono- or bidentate phosphine ligands as catalysts. For some reactions, ligands such as triphenyl phosphine, 1,1'-bis(diphenylphosphino)ferrocene, a carbene or a bipyridine have also been employed. Several new procedures for the Suzuki cross-coupling reaction, the activation of aryl chlorides, the functionalization of aromatics and the synthesis of heteroaromatics are discussed. The C-H activation/ functionalization reactions of aryl and heteroaryl derivatives have emerged as powerful tools for the preparation of biaryl compounds, and the recent procedures and catalysts employed in this promising field are also highlighted herein. PMID:17987520

  20. A Novel Methodology to Synthesize Highly Conductive Anion Exchange Membranes

    NASA Astrophysics Data System (ADS)

    He, Yubin; Pan, Jiefeng; Wu, Liang; Zhu, Yuan; Ge, Xiaolin; Ran, Jin; Yang, Zhengjin; Xu, Tongwen

    2015-08-01

    Alkaline polyelectrolyte fuel cell now receives growing attention as a promising candidate to serve as the next generation energy-generating device by enabling the use of non-precious metal catalysts (silver, cobalt, nickel et al.). However, the development and application of alkaline polyelectrolyte fuel cell is still blocked by the poor hydroxide conductivity of anion exchange membranes. In order to solve this problem, we demonstrate a methodology for the preparation of highly OH- conductive anion exchange polyelectrolytes with good alkaline tolerance and excellent dimensional stability. Polymer backbones were grafted with flexible aliphatic chains containing two or three quaternized ammonium groups. The highly flexible and hydrophilic multi-functionalized side chains prefer to aggregate together to facilitate the formation of well-defined hydrophilic-hydrophobic microphase separation, which is crucial for the superior OH- conductivity of 69 mS/cm at room temperature. Besides, the as-prepared AEMs also exhibit excellent alkaline tolerance as well as improved dimensional stability due to their carefully designed polymer architecture, which provide new directions to pursue high performance AEMs and are promising to serve as a candidate for fuel cell technology.

  1. A Novel Methodology to Synthesize Highly Conductive Anion Exchange Membranes

    PubMed Central

    He, Yubin; Pan, Jiefeng; Wu, Liang; Zhu, Yuan; Ge, Xiaolin; Ran, Jin; Yang, ZhengJin; Xu, Tongwen

    2015-01-01

    Alkaline polyelectrolyte fuel cell now receives growing attention as a promising candidate to serve as the next generation energy-generating device by enabling the use of non-precious metal catalysts (silver, cobalt, nickel et al.). However, the development and application of alkaline polyelectrolyte fuel cell is still blocked by the poor hydroxide conductivity of anion exchange membranes. In order to solve this problem, we demonstrate a methodology for the preparation of highly OH− conductive anion exchange polyelectrolytes with good alkaline tolerance and excellent dimensional stability. Polymer backbones were grafted with flexible aliphatic chains containing two or three quaternized ammonium groups. The highly flexible and hydrophilic multi-functionalized side chains prefer to aggregate together to facilitate the formation of well-defined hydrophilic-hydrophobic microphase separation, which is crucial for the superior OH− conductivity of 69 mS/cm at room temperature. Besides, the as-prepared AEMs also exhibit excellent alkaline tolerance as well as improved dimensional stability due to their carefully designed polymer architecture, which provide new directions to pursue high performance AEMs and are promising to serve as a candidate for fuel cell technology. PMID:26311616

  2. Catalyst Alloys Processing

    NASA Astrophysics Data System (ADS)

    Tan, Xincai

    2014-10-01

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

  3. Highly dispersed catalysts for coal liquefaction. Quarterly report No. 3, February 23, 1992--May 22, 1992

    SciTech Connect

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

    1992-06-08

    Iron and molybdenum complexes were studied as precursors to high dispersion catalysts for coal liquefaction. The precursors were either organometallic complexes or water soluble salts and were impregnated into coals of various ranks. The molybdenum catalysts were found to be very effective for conversion of an Illinois {number_sign}6 bituminous coal whereas the iron catalysts were not. In contrast, the iron catalysts were found to be very effective for lignite conversions. A H-donor and a non-donor conversion system were compared, using tetralin and n-hexadecane, respectively. In each case the organometallic precursor gave greater yields of toluene soluble material, with differences being most dramatic in the hexadecane system. The yields using the organometallic molybdenum precursors in hexadecane were found to be almost as great as those in the tetralin system, indicating that good catalyst precursors do not require donor solvents. The impregnation techniques were evaluated by comparing conversion yields and analyzing the products using Field Ionization Mass Spectroscopy (f.i.m.s) and FT-IR.

  4. 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.

  5. METHOD OF PURIFYING CATALYSTS

    DOEpatents

    Joris, G.G.

    1958-09-01

    It has been fuund that the presence of chlorine as an impurity adversely affects the performance of finely divided platinum catalysts such as are used in the isotopic exchange process for the production of beavy water. This chlorine impurity may be removed from these catalysts by treating the catalyst at an elevated temperature with dry hydrogen and then with wet hydrogen, having a hydrogen-water vapor volume of about 8: 1. This alternate treatment by dry hydrogen and wet hydrogen is continued until the chlorine is largely removed from the catalyst.

  6. Polyolefin catalyst manufacturing

    SciTech Connect

    Inkrott, K.E.; Scinta, J.; Smith, P.D. )

    1989-10-16

    Statistical process control (SPC) procedures are absolutely essential for making new-generation polyolefin catalysts with the consistent high quality required by modern polyolefin processes. Stringent quality assurance is critical to the production of today's high-performance catalysts. Research and development efforts during the last 20 years have led to major technological improvements in the polyolefin industry. New generation catalysts, which once were laboratory curiosities, must now be produced commercially on a regular and consistent basis to meet the increasing requirements of the plastics manufacturing industry. To illustrate the more stringent requirements for producing the new generation polyolefin catalysts, the authors compare the relatively simple, first-generation polypropylene catalyst production requirements with some of the basic requirements of manufacturing a more complex new-generation catalyst, such as Catalyst Resources Inc.'s LYNX 900. The principles which hold true for the new-generation catalysts such as LYNX 900 are shown to apply equally to the scale-up of other advanced technology polyolefin catalysts.

  7. Liquefaction with microencapsulated catalysts

    DOEpatents

    Weller, Sol W.

    1985-01-01

    A method of dispersing a liquefaction catalyst within coal or other carbonaceous solids involves providing a suspension in oil of microcapsules containing the catalyst. An aqueous solution of a catalytic metal salt is emulsified in the water-immiscible oil and the resulting minute droplets microencapsulated in polymeric shells by interfacial polycondensation. The catalyst is subsequently blended and dispersed throughout the powdered carbonaceous material to be liquefied. At liquefaction temperatures the polymeric microcapsules are destroyed and the catalyst converted to minute crystallites in intimate contact with the carbonaceous material.

  8. Polymerization of 1,3-Conjugated Dienes with Rare-Earth Metal Precursors

    NASA Astrophysics Data System (ADS)

    Zhang, Zhichao; Cui, Dongmei; Wang, Baoli; Liu, Bo; Yang, Yi

    This chapter surveys the publications except patents related to cis-1,4-, trans-1,4-, 3,4-regio-, and stereoselective polymerizations of 1,3-conjugated dienes with rare-earth metal-based catalytic systems during the past decade from 1999 to 2009. The concerned catalyst systems are classified into the conventional Ziegler-Natta catalysts, the modified Ziegler-Natta catalysts, and the single-site cationic systems composed of lanthanocene and noncyclopentadienyl precursors, respectively. For the conventional Ziegler-Natta catalysts of the most promising industry applicable recipe, the multicomponents based on lanthanide carboxylate or phosphate or alkoxide precursors, research works concern mainly about optimizing the catalyst preparation and polymerization techniques. Special emphases are put on the factors that influence the catalyst homogeneority, catalytic activity and efficiency, as well as cis-1,4-selectivity. Meanwhile, tailor-made lanthanide aryloxide and amide complexes are designed and fully characterized to mimic the conventional Ziegler-Natta catalysts, anticipated to elucidate the key processes, alkylation and cationization, for generating the active species. Regarding to the single-site catalytic systems generally comprising well-defined complexes containing lanthanide-carbon bonds, investigations cover their versatile catalytic activity and efficiency, and the distinguished regio- and stereoselectivity for both polymerization of dienes and copolymerization of dienes with alkenes. The correlation between the sterics and electronics of ligands and the molecular structures of the complexes and their catalytic performances are highlighted. The isolation of the probable active species in these polymerization processes from the stoichiometric reactions of the precursors with activators will be presented.

  9. Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

    DOEpatents

    Ramprasad, Dorai; Waller, Francis Joseph

    1998-01-01

    This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

  10. Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

    DOEpatents

    Ramprasad, D.; Waller, F.J.

    1998-06-16

    This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

  11. Catalysts for the selective oxidation of hydrogen sulfide to sulfur

    SciTech Connect

    Srinivas, Girish; Bai, Chuansheng

    2000-08-08

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

  12. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    SciTech Connect

    Thompson, Robert L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid

    2013-06-01

    The triazole core is a highly versatile heterocyclic ring which can be accessed easily with the Cu(I)-catalyzed Huisgen cycloaddition reaction. Herein we present the preparation of ionic liquids that incorporate a 1,2,3-triazolide anion. These ionic liquids were prepared by a facile procedure utilizing a base-labile pivaloylmethyl group at the 1-position, which can act as precursors to 1H- 4-substituted 1,2,3-triazole. These triazoles were then subsequently converted into ionic liquids after deprotonation using an appropriate ionic liquid cation hydroxide. The densities and thermal decompositions of these ionic liquids were measured. These novel ionic liquids have potential applications in gas separations and in metal-free catalysis.

  13. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

    DOEpatents

    Feder, Harold M.; Rathke, Jerome W.

    1979-01-01

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

  14. Energy and Entropy Effects in Dissociation of Peptide Radical Anions

    SciTech Connect

    Laskin, Julia; Yang, Zhibo; Lam, Corey; Chu, Ivan K.

    2012-04-15

    Time- and collision energy-resolved surface-induced dissociation (SID) of peptide radical anions was studied for the first time using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for SID experiments. Peptide radical cations and anions were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes. The effect of the charge, radical, and the presence of a basic residue on the energetics and dynamics of dissociation of peptide ions was examined using RVYIHPF (1) and HVYIHPF (2) as model systems. Comparison of the survival curves for of [M+H]{sup +}, [M-H]{sup -}, M{sup +{sm_bullet}}, and [M-2H]{sup -{sm_bullet}} ions of these precursors demonstrated that even-electron ions are more stable towards fragmentation than their odd-electron counterparts. RRKM modeling of the experimental data demonstrated that the lower stability of the positive radicals is mainly attributed to lower dissociation thresholds while entropy effects are responsible the relative instability of the negative radicals. Substitution of arginine with less basic histidine residue has a strong destabilizing effect on the [M+H]{sup +} ions and a measurable stabilizing effect on the odd-electron ions. Lower threshold energies for dissociation of both positive and negative radicals of 1 are attributed to the presence of lower-energy dissociation pathways that are most likely promoted by the presence of the basic residue.

  15. Chemistry of nitrile anions in the interstellar medium

    SciTech Connect

    Carles, S.; Le Garrec, J.-L.; Biennier, L.; Guillemin, J.-C.

    2015-12-31

    Despite the extreme conditions of temperature (down to 10K) and density (down to 100 molecules/cm{sup 3}), the giant molecular clouds and the circumstellar envelopes present a rich and complex chemistry. To date, more than 180 molecules have been detected in the InterStellar Medium (ISM) with a large abundance of nitriles (RC≡N). In addition, several anions have been recently observed in this medium: C{sub 4}H{sup ¯}, C{sub 6}H{sup ¯}, C{sub 8}H{sup ¯}, CN{sup ¯}, C{sub 3}N{sup ¯} and C{sub 5}N{sup ¯}. These last species should play a key role in the molecular growth towards complexity. To explore this hypothesis, their reactivity must be studied in the laboratory. The FALP-MS and the CRESU experimental apparatuses of the Rennes University are able to measure absolute rate coefficient of various chemical reactions, including the ion – molecule reactions, in gas phase at low temperature (from 300K for the FALP-MS down to 15K for the CRESU). Therefore, these experimental tools are particularly adapted to the kinetic studies of reactions potentially involved in the Interstellar Medium. One of the difficulties encountered in experiments with anions is their generation. We describe here the formation of the CN{sup ¯} and C{sub 3}N{sup ¯} anions by dissociative electron attachment on the molecular precursors BrCN and BrC{sub 3}N.

  16. Effect of cationic/anionic organic surfactants on evaporation induced self assembled tin oxide nanostructured films

    NASA Astrophysics Data System (ADS)

    Khun Khun, Kamalpreet; Mahajan, Aman; Bedi, R. K.

    2011-01-01

    Tin oxide nanostructures with well defined morphologies have been obtained through an evaporation induced self assembly process. The technique has been employed using an ultrasonic nebulizer for production of aersol and its subsequent deposition onto a heated glass substrate. The precursor used for aersol production was modified by introducing cationic and anionic surfactants namely cetyl trimethyl ammonium bromide and sodium dodecyl sulphate respectively. The effect of surfactants on the structural, electrical and optical properties of self assembled tin oxide nanostructures were investigated by using X-ray diffraction, field emission scanning electroscope microscopy, two probe technique and photoluminiscence studies. The results reveal that high concentration of surfactants in the precursor solution leads to reduction in crystallite size with significant changes in the morphology of tin oxide nanostructures. Photoluminiscence studies of the nanostructures show emissions in the visible region which exhibit marked changes in the intensities upon variation of surfactants in the precursor solutions.

  17. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

    Kuswandi, Bambang; Nuriman; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  18. Enantioselective Selenocyclization via Dynamic Kinetic Resolution of Seleniranium Ions by Hydrogen-Bond Donor Catalysts

    PubMed Central

    2015-01-01

    Highly enantioselective selenocyclization reactions are promoted by the combination of a new chiral squaramide catalyst, a mineral acid, and an achiral Lewis base. Mechanistic studies reveal that the enantioselectivity originates from the dynamic kinetic resolution of seleniranium ions through anion-binding catalysis. PMID:25380129

  19. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, Raghunath

    1998-01-01

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

  20. Vapor-phase synthesis of a solid precursor for {alpha}-alumina through a catalytic decomposition of aluminum triisopropoxide

    SciTech Connect

    Nguyen, Tu Quang; Park, Kyun Young; Jung, Kyeong Youl; Cho, Sung Baek

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer A new solid precursor for {alpha}-alumina was prepared at about 200 Degree-Sign C from aluminum tri-isopropoxide vapor. Black-Right-Pointing-Pointer The obtained precursor was calcined at 1200 Degree-Sign C to form {alpha}-alumina particles, 75 nm in surface area equivalent diameter. Black-Right-Pointing-Pointer The weight loss of the precursor upon calcination was 24%, lower than that of Al(OH){sub 3}, a conventional alumina precursor. -- Abstract: A new solid precursor, hydrous aluminum oxide, for {alpha}-alumina nanoparticles was prepared by thermal decomposition of aluminum triisopropoxide (ATI) vapor in a 500 mL batch reactor at 170-250 Degree-Sign C with HCl as catalyst. The conversion of ATI increased with increasing temperature and catalyst content; it was nearly complete at 250 Degree-Sign C with the catalyst at 10 mol% of the ATI. The obtained precursor particles were amorphous, spherical and loosely agglomerated. The primary particle size is in the range 50-150 nm. The ignition loss of the precursor was 24%, considerably lower than 35% of Al(OH){sub 3}, the popular precursor for alumina particles. Upon calcination of the precursor at 1200 Degree-Sign C in the air with a heating rate of 10 Degree-Sign C/min and a holding time of 2 h, the phase was completely transformed into {alpha}. The spherical particles composing the precursor turned worm-like by the calcination probably due to sintering between neighboring particles. The surface area equivalent diameter of the resulting {alpha}-alumina was 75 nm.

  1. 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.

  2. A broadly applicable and practical oligomeric (salen) Co catalyst for enantioselective epoxide ring-opening reactions

    PubMed Central

    White, David E.; Tadross, Pamela M.; Lu, Zhe

    2014-01-01

    The (salen) Co catalyst (4a) can be prepared as a mixture of cyclic oligomers in a short, chromatography-free synthesis from inexpensive, commercially available precursors. This catalyst displays remarkable enhancements in reactivity and enantioselectivity relative to monomeric and other multimeric (salen) Co catalysts in a wide variety of enantioselective epoxide ring-opening reactions. The application of catalyst 4a is illustrated in the kinetic resolution of terminal epoxides by nucleophilic ring-opening with water, phenols, and primary alcohols; the desymmetrization of meso epoxides by addition of water and carbamates; and the desymmetrization of oxetanes by intramolecular ring opening with alcohols and phenols. The favorable solubility properties of complex 4a under the catalytic conditions facilitated mechanistic studies, allowing elucidation of the basis for the beneficial effect of oligomerization. Finally, a catalyst selection guide is provided to delineate the specific advantages of oligomeric catalyst 4a relative to (salen) Co monomer 1 for each reaction class. PMID:25045188

  3. Gels based on anion recognition between triurea receptor and phosphate anion.

    PubMed

    Yang, Cuiling; Wu, Biao; Chen, Yongming; Zhang, Ke

    2015-04-01

    Anion recognition between the triurea receptor and phosphate anion is demonstrated as the cross-linkage to build supramolecular polymer gels for the first time. A novel multi-block copolymer (3) is designed to have functional triurea groups as cross-linking units along the polymer main chain. By virtue of anion coordination between the triurea receptor and phosphate anion with a binding mode of 2:1, supramolecular polymer gels are then prepared based on anion recognition using 3 as the building block. PMID:25694389

  4. Counterintuitive interaction of anions with benzene derivatives

    NASA Astrophysics Data System (ADS)

    Quiñonero, David; Garau, Carolina; Frontera, Antonio; Ballester, Pau; Costa, Antonio; Deyà, Pere M.

    2002-06-01

    Ab initio calculations were carried out on complexes between 1,3,5-trinitrobenzene (TNB) and anions, where the anion is positioned over the ring along the C3 axis. This study combines crystallographic and computational evidences to demonstrate an attractive interaction between the anion and the π-cloud of TNB. This interaction is rationalized based on the important role of the quadrupole moment of TNB and the anion-induced polarization. In addition, this study has been extended to 1,3,5-trifluorobenzene (TFB), which possesses a very small quadrupole moment. As a result, minimum energy complexes have been found between TFB and both anions and cations due to the stabilization obtained from the ion-induced polarization.

  5. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    PubMed Central

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    2010-01-01

    This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions. PMID:20871791

  6. Creating molecular macrocycles for anion recognition

    PubMed Central

    2016-01-01

    Summary The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures. PMID:27340452

  7. Picosecond dynamics of benzophenone anion solvation

    SciTech Connect

    Lin, Y.; Jonah, C.D. )

    1993-01-14

    The dynamics of benzophenone anion solvation in alcohols are studied by pulse-radiolysis techniques. The solvation process is characterized by the blue shift of the transient absorption spectrum of the anion and is faster for the smaller alcohols. The anion is solvated more slowly than the electron in the same solvent, but the solvation times of both are similar to [tau][sub 2], the solvent dielectric relaxation time. The familiar phenomenological two-state model of solvation was found to be inappropriate for describing the anion solvation process. A multistate process appears to be a more appropriate description. The authors modeled the kinetics of the spectral relaxation. In most cases, nearly quantitative agreement between the calculated and observed spectra is achieved. The characteristic relaxation times for the alcohol solvents around the anions were also reproduced. 50 refs., 8 figs., 3 tabs.

  8. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2015-09-29

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  9. Nanostructured catalyst supports

    DOEpatents

    Zhu, Yimin; Goldman, Jay L.; Qian, Baixin; Stefan, Ionel C.

    2012-10-02

    The present invention relates to SiC nanostructures, including SiC nanopowder, SiC nanowires, and composites of SiC nanopowder and nanowires, which can be used as catalyst supports in membrane electrode assemblies and in fuel cells. The present invention also relates to composite catalyst supports comprising nanopowder and one or more inorganic nanowires for a membrane electrode assembly.

  10. Reducible oxide based catalysts

    DOEpatents

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  11. 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.

  12. Improved zeolitic isocracking catalysts

    SciTech Connect

    Dahlberg, A.J.; Habib, M.M.; Moore, R.O.; Law, D.V.; Convery, L.J.

    1995-09-01

    Chevron Research Company introduced the first low pressure, low temperature catalytic hydrocracking process--ISOCRACKING--in 1959. Within the last four years, Chevron has developed and commercialized three new zeolitic ISOCRACKING catalysts. ICR 209 is Chevron`s latest noble metal ISOCRACKING catalyst. It offers improved liquid yield stability, longer life, and superior polynuclear aromatics control compared to its predecessor. ICR 209`s high hydrogenation activity generates the highest yields of superior quality jet fuel of any zeolitic ISOCRACKING catalyst. The second new ISOCRACKING catalyst, ICR 208, is a base metal catalyst which combines high liquid selectivity and high light naphtha octane in hydrocrackers operating for maximum naphtha production. ICR 210 is another new base metal catalyst which offers higher liquid yields and longer life than ICR 208 by virtue of a higher hydrogenation-to-acidity ratio. Both ICR 208 and ICR 210 have been formulated to provide higher liquid yield throughout the cycle and longer cycle length than conventional base metal/zeolite catalysts. This paper will discuss the pilot plant and commercial performances of these new ISOCRACKING catalysts.

  13. Anion Effects in Oxidative Aliphatic Carbon-Carbon Bond Cleavage Reactions of Cu(II) Chlorodiketonate Complexes.

    PubMed

    Saraf, Sushma L; Miłaczewska, Anna; Borowski, Tomasz; James, Christopher D; Tierney, David L; Popova, Marina; Arif, Atta M; Berreau, Lisa M

    2016-07-18

    Aliphatic oxidative carbon-carbon bond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products. Kinetic studies of this reaction revealed a slow induction phase followed by a rapid decay of the absorption features of 1. Notably, the induction phase is not present when the reaction is performed in the presence of a catalytic amount of chloride anion. In the studies presented herein, a combination of spectroscopic (UV-vis, EPR) and density functional theory (DFT) methods have been used to examine the chloride and benzoate ion binding properties of 1 under anaerobic conditions. These studies provide evidence that each anion coordinates in an axial position of the Cu(II) center. DFT studies reveal that the presence of the anion in the Cu(II) coordination sphere decreases the barrier for O2 activation and the formation of a Cu(II)-peroxo species. Notably, the chloride anion more effectively lowers the barrier associated with O-O bond cleavage. Thus, the nature of the anion plays an important role in determining the rate of reaction of the diketonate complex with O2. The same type of anion effects were observed in the O2 reactivity of the simple Cu(II)-bipyridine complex [(bpy)Cu(PhC(O)C(Cl)C(O)Ph)ClO4] (3). PMID:27377103

  14. Improved catalysts and method

    SciTech Connect

    Taylor, C.E.; Noceti, R.P.

    1990-12-31

    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. 8 figs., 3 tabs.

  15. Metal-catalyst-free carbohydrazide fuel cells with three-dimensional graphene anodes.

    PubMed

    Qi, Ji; Benipal, Neeva; Wang, Hui; Chadderdon, David J; Jiang, Yibo; Wei, Wei; Hu, Yun Hang; Li, Wenzhen

    2015-04-13

    As a potential solution to concerns on sustainable energy, the wide spread commercialization of fuel cell has long been hindered by limited reserves and relatively high costs of metal catalysts. 3D graphene, a carbon-only catalyst prepared by reduction of carbon monoxide with lithium oxide, is found to electrochemically catalyze carbohydrazide oxidation reaction efficiently. A prototype of a completely metal-catalyst-free anion exchange membrane fuel cell (AEMFC) with a 3D graphene anode catalyst and an N-doped CNT (N-CNT) cathode catalyst generate a peak power density of 24.9 mW cm(-2) . The average number of electrons electrochemically extracted from one carbohydrazide molecule is 4.9, indicating the existence of CN bond activation, which is a key factor contributing to high fuel utilization efficiency. PMID:25469500

  16. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.

    PubMed

    Tong, Lianpeng; Inge, A Ken; Duan, Lele; Wang, Lei; Zou, Xiaodong; Sun, Licheng

    2013-03-01

    Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra. PMID:23409776

  17. Progress in the development and production of nanoscale iron-coating catalysts

    SciTech Connect

    Matson, D.W.; Linehan, J.C.; Darab, J.G.; Watrob, H.M.; Lui, E.G.; Phelps, M.R.; Hogan, M.O.

    1995-04-01

    At the Pacific Northwest Laboratory (PNL) we have undertaken a program to investigate nanocrystalline ion-based powders as catalytic precursors in a variety of hydrocracking reactions, including coal liquefaction. One ultrafine powder synthesis method developed at PNL, the Rapid of precursors in Solution (RTDS) process, appears to be particularly large scale production of nanocrystalline powders. Using model compounds we have demonstrated that iron-based RTDS powders can be used to produce highly active carbon-carbon bond scission catalysts under reaction conditions relevant to coal liquefaction processes. In this paper we present recent results of attempts at modifying the activity of RTDS-generated iron-based catalyst powders by doping with other metals and the results of scaleup efforts to produce kilogram quantities of active catalyst precursor by this process.

  18. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, April--June 1993

    SciTech Connect

    Song, Chunshan; Parfitt, D.P.; Schobert, H.H.

    1993-08-01

    The ultimate goal of the present research is to develop novel catalytic hydroliquefaction process using highly active dispersed catalysts. The primary objective of this research is to develop novel bimetallic dispersed catalysts from organometallic molecular precursors, that can be used in low concentrations (precursors of bimetallic dispersed catalysts for liquefaction of a Montana subbituminous coal (DECS-9) at the loading level of 0.5 wt% Mo on dmmf coal. It was found that the structure of the precursors, in particular the ligands to the metal species, affect the activity of the resulting catalyst significantly. Among the M-M` type precursors tested, Mo-Co thiocubane, Mo{sub 2}Co{sub 2}S{sub 4}(Cp){sub 2}(CO){sub 2} [Cp = cyclopentadiene], designated as MoCo-TC2, produced in-situ the best catalyst The performance of the Mo-Co bimetallic catalyst was further enhanced by using temperature programmed (TPL) conditions consisting of a low temperature soaking at 200{degrees}C, programmed heat-up to 400 or 425{degrees}C followed by a 30 minutes hold. The pro ed heat-up serves as an in-situ activation of catalyst and coal pretreatment, which contributes to more effective hydrogenation of reactive fragments at high temperature.

  19. Cl-capped CdSe nanocrystals via in situ generation of chloride anions

    NASA Astrophysics Data System (ADS)

    Palencia, Cristina; Lauwaet, Koen; de La Cueva, Leonor; Acebrón, María; Conde, Julio J.; Meyns, Michaela; Klinke, Christian; Gallego, José M.; Otero, Roberto; Juárez, Beatriz H.

    2014-05-01

    Halide ions cap and stabilize colloidal semiconductor nanocrystal (NC) surfaces allowing for NCs surface interactions that may improve the performance of NC thin film devices such as photo-detectors and/or solar cells. Current ways to introduce halide anions as ligands on surfaces of NCs produced by the hot injection method are based on post-synthetic treatments. In this work we explore the possibility to introduce Cl in the NC ligand shell in situ during the NCs synthesis. With this aim, the effect of 1,2-dichloroethane (DCE) in the synthesis of CdSe rod-like NCs produced under different Cd/Se precursor molar ratios has been studied. We report a double role of DCE depending on the Cd/Se precursor molar ratio (either under excess of cadmium or selenium precursor). According to mass spectrometry (ESI-TOF) and nuclear magnetic resonance (1H NMR), under excess of Se precursor (Se dissolved in trioctylphosphine, TOP) conditions at 265 °C ethane-1,2-diylbis(trioctylphosphonium)dichloride is released as a product of the reaction between DCE and TOP. According to XPS studies chlorine gets incorporated into the CdSe ligand shell, promoting re-shaping of rod-like NCs into pyramidal ones. In contrast, under excess Cd precursor (CdO) conditions, DCE reacts with the Cd complex releasing chlorine-containing non-active species which do not trigger NCs re-shaping. The amount of chlorine incorporated into the ligand shell can thus be controlled by properly tuning the Cd/Se precursor molar ratio.Halide ions cap and stabilize colloidal semiconductor nanocrystal (NC) surfaces allowing for NCs surface interactions that may improve the performance of NC thin film devices such as photo-detectors and/or solar cells. Current ways to introduce halide anions as ligands on surfaces of NCs produced by the hot injection method are based on post-synthetic treatments. In this work we explore the possibility to introduce Cl in the NC ligand shell in situ during the NCs synthesis. With this aim

  20. Design, synthesis, and characterization of novel fine-particle, unsupported catalysts for coal liquefaction

    SciTech Connect

    Klein, M.T.

    1991-09-11

    A series of carbonyl-based homogeneous catalyst precursors has been prepared. These species include: Fe(CO){sub 4}PPh{sub 3}, Fe(CO){sub 3}(PPh{sub 3}){sub 2}, Fe(CO){sub 2}(PPh{sub 3}){sub 2}CS{sub 2}, S{sub 2}Fe{sub 2}(CO){sub 6}, S{sub 2}Fe{sub 3}(CO){sub 9}. Fe(CO){sub 4}PPh{sub 3} was prepared by a combined photochemical and thermal route from triphenylphosphine (PPh{sub 3}) in iron pentacarbonyl (Fe(CO){sub 5}). This preparation procedure, which is selective to the monosubstituted product, is outlined herein. Currently these compounds are being tested as catalysts/catalyst precursors with coal or model compounds in the tubing bomb reactors to provide information relating catalytic activity to catalyst structure and properties. (VC)

  1. 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.

  2. Biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst.

    PubMed

    Li, Ji; Fu, Yu-Jie; Qu, Xue-Jin; Wang, Wei; Luo, Meng; Zhao, Chun-Jian; Zu, Yuan-Gang

    2012-03-01

    In this study, biodiesel production from yellow horn (Xanthoceras sorbifolia Bunge.) seed oil using ion exchange resin as heterogeneous catalyst was investigated. After illustration of the mechanisms of transesterification reactions catalyzed by typical ion exchange resins, the factors affecting microwave-assisted transesterification process were studied. A high conversion yield of about 96% was achieved under optimal conditions using high alkaline anion exchange resins as catalyst. Analyzing the FAMEs composition by GC-MS and main physical-chemical properties demonstrated that the biodiesel product prepared from yellow horn seed oil was of high quality. Compared with conventional alkali catalyst, the outstanding characteristics of reusability and operational stability made the resin catalyst more predominant for biodiesel production. In addition, a comprehensive kinetic model was established for analyzing the reaction. The results of present research showed that microwave-assisted transesterification process catalyzed by high alkaline anion exchange resin was a green, effective and economic technology for biodiesel industry. PMID:22284757

  3. Development of Novel Heterogeneous Catalyst Using Inorganic Ion Exchanger and Their Applications for Green Organic Transformation Process

    NASA Astrophysics Data System (ADS)

    Hara, Takayoshi

    In order to achieve green organic transformation of high-valued chemicals, the use of inorganic ion exchanger as a catalyst support is capable of creating precisely controlled catalytically active species responsible for targeted organic reactions. Layered hydroxy double salts (HDSs) have received considerable interest as anion exchangers due to their potential applications as catalysts and catalyst supports. The Ni-Zn mixed basic salt (NiZn) has a typical chemical composition of Ni1-xZn2x(CH3COO)2x(OH)2·nH2O (0.15anion-exchanged NiZn catalyst based on the unique characteristics of NiZn, e.g., a strong electrostatic interaction with guest anion, high anion exchange ability, and dispersion of monomeric metal cation sites in its matrix. The green organic transformations such as aerobic alcohol oxidation, 1,4-addition reaction between boronic acid and α,β-unsaturated ketones, Knoevenagel reaction in water, and chemical fixation of CO2 into epoxide are also demonstrated by use of our catalysts.

  4. Anion conductance selectivity mechanism of the CFTR chloride channel.

    PubMed

    Linsdell, Paul

    2016-04-01

    All ion channels are able to discriminate between substrate ions to some extent, a process that involves specific interactions between permeant anions and the so-called selectivity filter within the channel pore. In the cystic fibrosis transmembrane conductance regulator (CFTR) anion-selective channel, both anion relative permeability and anion relative conductance are dependent on anion free energy of hydration--anions that are relatively easily dehydrated tend to show both high permeability and low conductance. In the present work, patch clamp recording was used to investigate the relative conductance of different anions in CFTR, and the effect of mutations within the channel pore. In constitutively-active E1371Q-CFTR channels, the anion conductance sequence was Cl(-) > NO3(-) > Br(-) > formate > SCN(-) > I(-). A mutation that disrupts anion binding in the inner vestibule of the pore (K95Q) disrupted anion conductance selectivity, such that anions with different permeabilities showed almost indistinguishable conductances. Conversely, a mutation at the putative narrowest pore region that is known to disrupt anion permeability selectivity (F337A) had minimal effects on anion relative conductance. Ion competition experiments confirmed that relatively tight binding of permeant anions resulted in relatively low conductance. These results suggest that the relative affinity of ion binding in the inner vestibule of the pore controls the relative conductance of different permeant anions in CFTR, and that the pore has two physically distinct anion selectivity filters that act in series to control anion conductance selectivity and anion permeability selectivity respectively. PMID:26779604

  5. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    SciTech Connect

    Kamil Klier; Richard G. Herman; James G.C. Shen; Qisheng Ma

    2000-08-31

    A novel 1,2-ethanediol, bis(hydrogen sulfate), disodium salt precursor-based solid acid catalyst with a zirconia substrate was synthesized and demonstrated to have significantly enhanced activity and high selectivity in producing methyl isobutyl ether (MIBE) or isobutene from methanol-isobutanol mixtures. The precursor salt was synthesized and provided by Dr. T. H. Kalantar of the M.E. Pruitt Research Center, Dow Chemical Co., Midland, MI 48674. Molecular modeling of the catalyst synthesis steps and of the alcohol coupling reaction is being carried out. A representation of the methyl transfer from the surface activated methanol molecule (left) to the activated oxygen of the isobutanol molecule (right) to form an ether linkage to yield MIBE is shown.

  6. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  7. Ketoprofen as a photoinitiator for anionic polymerization.

    PubMed

    Wang, Yu-Hsuan; Wan, Peter

    2015-06-01

    A new photoinitiating system for anionic polymerization of acrylates based on the efficient photodecarboxylation of Ketoprofen (1) and the related derivatives 3 and 4 that generate the corresponding carbanion intermediates is presented. Carbanion intermediates are confirmed by deuterium incorporation in the trapped Michael adducts and by spectroscopic detection using laser flash photolysis (LFP). This novel anionic initiating system features excitation in the near UV and visible regions, potential characteristics of photocontrolled living polymerization, and metal-free photoinitiators generated from photoexcitation, different from typical anionic polymerization where the polymerizations are initiated by heat and strong base containing alkali metals. PMID:25917384

  8. 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.

  9. Technology development for iron F-T catalysts. Final report

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-08-01

    The objectives of this work were twofold. The first objective was to design and construct a pilot plant for preparing precipitated iron oxide F-T precursors and demonstrate that the rate of production from this plant is equivalent to 100 lbs/day of dried metal oxide. Secondly, these precipitates were to be used to prepare catalysts capable of achieving 88% CO + H{sub 2} conversion with {le} 5 mole percent selectivity to methane + ethane.

  10. Popping of graphite oxide: application in preparing metal nanoparticle catalysts.

    PubMed

    Gao, Yongjun; Chen, Xi; Zhang, Jiaguang; Asakura, Hiroyuki; Tanaka, Tsunehiro; Teramura, Kentaro; Ma, Ding; Yan, Ning

    2015-08-26

    A popcorn-like transformation of graphite oxide (GO) is reported and used to synthesize metal nanoparticle catalysts. The popping step is unique and essential, not only generating a high-surface-area support but also partially decomposing the metal precursors to form well-separated metal oxide nuclei, which would further evolve into highly dispersed and uniform-sized nanoparticles in the subsequent reduction. PMID:26179983

  11. Lithium salts of [1,12-dialkyl-CB11Me10]- anions.

    PubMed

    Valášek, Michal; Štursa, Jan; Pohl, Radek; Michl, Josef

    2010-11-15

    We report the syntheses of several [1-R-CB(11)-Me(11)](-) and [1-R-12-R'-CB(11)-Me(10)](-) anions (R, R' = alkyl) and the solubilities of their lithium salts in cyclohexane. These solutions are of interest as Lewis acid catalysts. The new anions are not directly accessible by methylation with methyl triflate because of intervening triflyloxy substitution on one or more boron vertices. The difficulty has been circumvented in two ways. Either (i) an iodo substituent is first introduced into position 12, permitting a clean decamethylation, and then replaced with a methyl by reaction with trimethylaluminum or (ii) the offending triflyloxy substituents are replaced with methyls by reaction with trimethylaluminum. PMID:20932023

  12. Open flow hot isostatic pressing assisted synthesis of highly porous materials and catalysts

    NASA Astrophysics Data System (ADS)

    Siadati, Mohammad Hossein

    Open-flow hot isostatic pressing (OFHIP) technique is applied for synthesizing molecular sieves and highly porous catalytic materials. First, the isostatic pressure is applied to the starting material/catalyst precursor, and then heat is applied. Under this condition, as the organic components gradually decompose and leave the material, the voids left behind are immediately filled/replaced by the gas (pressure medium) in flow. This substitution warrants the preservation as well as the uniformity of the voids/pores. The result is a very porous material with very uniform pore size distribution. Another advantage is the production of the catalyst directly from the precursor, in the absence of solvent (neat), rendering the process simpler and less costly than previous processes. The entire process takes place under flow of the gas that is used as medium to develop the isostatic pressure. Consequently, the entire process, as well as the final product produced, is devoid of any undesirable residues. This endeavor also introduces a viable technique for mass-producing porous materials/catalysts. The resulting materials are termed "amorphous sulfide sieves" to reflect their unique properties that include high surface area, narrow pore size distribution and high activity. The catalysts are potentially licensable to all petroleum and petroleum chemical companies for a wide variety of environmental and product improvement purposes. The results obtained on unpromoted samples synthesized at 300°C indicate that as the synthesis pressure is increased, both surface area and catalytic activity of the materials produced increase. The increase in activity k value from 3 to 6 x 10-7 mol/g.s corresponds to increase in pressure from 100 to 800 psi, respectively. The N2 gas used as pressure medium results in highly porous materials but low activity. H 2 seems to be the ideal gas for both pressure medium and reducing agent. Co-promoted catalysts synthesized at 1400 psi and 300°C show

  13. Precursors of Hypertension: A Review

    PubMed Central

    Thomas, John; Neser, William B.; Thomas, Johniene; Semenya, Kofi; Green, Donald R.

    1983-01-01

    Recent advances in hypertension therapy have been remarkable; however, much less is known about those precursors that facilitate preventive and early intervention measures. This review of the literature indicates that relevant precursors are early elevated casual systolic blood pressures, positive family history, and obesity in females. Additional predisposing or enhancing factors point to high sodium ingestion, heavy smoking, and high socioecologic stress. Evidence for a high-risk hypertensive personality is not conclusive. There is a paucity of longitudinal data on hypertension in the black population. PMID:6864814

  14. Kinetics and mechanism of exogenous anion exchange in FeFbpA-NTA: significance of periplasmic anion lability and anion binding activity of ferric binding protein A.

    PubMed

    Heymann, Jared J; Gabricević, Mario; Mietzner, Timothy A; Crumbliss, Alvin L

    2010-02-01

    The bacterial transferrin ferric binding protein A (FbpA) requires an exogenous anion to facilitate iron sequestration, and subsequently to shuttle the metal across the periplasm to the cytoplasmic membrane. In the diverse conditions of the periplasm, numerous anions are known to be present. Prior in vitro experiments have demonstrated the ability of multiple anions to fulfill the synergistic iron-binding requirement, and the identity of the bound anion has been shown to modulate important physicochemical properties of iron-bound FbpA (FeFbpA). Here we address the kinetics and mechanism of anion exchange for the FeFbpA-nitrilotriacetate (NTA) assembly with several biologically relevant anions (citrate, oxalate, phosphate, and pyrophosphate), with nonphysiologic NTA serving as a representative synergistic anion/chelator. The kinetic data are consistent with an anion-exchange process that occurs in multiple steps, dependent on the identity of both the entering anion and the leaving anion. The exchange mechanism may proceed either as a direct substitution or through an intermediate FeFbpA-X* assembly based on anion (X) identity. Our kinetic results further develop an understanding of exogenous anion lability in the periplasm, as well as address the final step of the iron-free FbpA (apo-FbpA)/Fe(3+) sequestration mechanism. Our results highlight the kinetic significance of the FbpA anion binding site, demonstrating a correlation between apo-FbpA/anion affinity and the FeFbpA rate of anion exchange, further supporting the requirement of an exogenous anion to complete tight sequestration of iron by FbpA, and developing a mechanism for anion exchange within FeFbpA that is dependent on the identity of both the entering anion and the leaving anion. PMID:19813031

  15. Molecular physiology of EAAT anion channels.

    PubMed

    Fahlke, Christoph; Kortzak, Daniel; Machtens, Jan-Philipp

    2016-03-01

    Glutamate is the major excitatory neurotransmitter in the mammalian central nervous system. After release from presynaptic nerve terminals, glutamate is quickly removed from the synaptic cleft by a family of five glutamate transporters, the so-called excitatory amino acid transporters (EAAT1-5). EAATs are prototypic members of the growing number of dual-function transport proteins: they are not only glutamate transporters, but also anion channels. Whereas the mechanisms underlying secondary active glutamate transport are well understood at the functional and at the structural level, mechanisms and cellular roles of EAAT anion conduction have remained elusive for many years. Recently, molecular dynamics simulations combined with simulation-guided mutagenesis and experimental analysis identified a novel anion-conducting conformation, which accounts for all experimental data on EAAT anion currents reported so far. We here review recent findings on how EAATs accommodate a transporter and a channel in one single protein. PMID:26687113

  16. Catalyst for microelectromechanical systems microreactors

    DOEpatents

    Morse, Jeffrey D.; Sopchak, David A.; Upadhye, Ravindra S.; Reynolds, John G.; Satcher, Joseph H.; Gash, Alex E.

    2011-11-15

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  17. Catalyst for microelectromechanical systems microreactors

    DOEpatents

    Morse, Jeffrey D.; Sopchak, David A.; Upadhye, Ravindra S.; Reynolds, John G.; Satcher, Joseph H.; Gash, Alex E.

    2010-06-29

    A microreactor comprising a silicon wafer, a multiplicity of microchannels in the silicon wafer, and a catalyst coating the microchannels. In one embodiment the catalyst coating the microchannels comprises a nanostructured material. In another embodiment the catalyst coating the microchannels comprises an aerogel. In another embodiment the catalyst coating the microchannels comprises a solgel. In another embodiment the catalyst coating the microchannels comprises carbon nanotubes.

  18. Catalysts and method

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1991-01-01

    An improved catlayst 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, HC1 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.

  19. Epoxidation catalyst and process

    DOEpatents

    Linic, Suljo; Christopher, Phillip

    2010-10-26

    Disclosed herein is a catalytic method of converting alkenes to epoxides. This method generally includes reacting alkenes with oxygen in the presence of a specific silver catalyst under conditions suitable to produce a yield of the epoxides. The specific silver catalyst is a silver nanocrystal having a plurality of surface planes, a substantial portion of which is defined by Miller indices of (100). The reaction is performed by charging a suitable reactor with this silver catalyst and then feeding the reactants to the reactor under conditions to carry out the reaction. The reaction may be performed in batch, or as a continuous process that employs a recycle of any unreacted alkenes. The specific silver catalyst has unexpectedly high selectivity for epoxide products. Consequently, this general method (and its various embodiments) will result in extraordinarily high epoxide yields heretofore unattainable.

  20. Polymerization catalyst system

    SciTech Connect

    Graves, V.

    1986-03-25

    This patent describes a catalyst system for polymerizing at least one alpha-olefin under conditions characteristic of Ziegler polymerization. This system consists of: 1. a supported polymerization catalyst or mixture of polymerization catalysts prepared under anhydrous conditions by the sequential steps of: (a) preparing a slurry of inert particulate porous support material; (b) adding to the slurry a solution of an organomagnesium compound; (c) adding to the slurry and reacting a solution of a zirconium halide compound, hafnium compound or mixtures thereof; (d) adding to the slurry and reacting a halogenator; (e) adding to the slurry and reacting a tetravalent titanium halide compound; and (f) recovering solid catalyst component; 2. an organoaluminum compound; and 3. a promotor of chlorinated hydrocarbons having one to 20 carbon atoms.

  1. Hydrocracking catalysts and processes

    SciTech Connect

    Dolbear, G.E.

    1995-12-31

    Hydrocracking processes convert aromatic gas oils into high quality gasoline, diesel, and turbine stocks. They operate at high hydrogen pressures, typically greater than 1500 psig. Operating temperatures range from 600-700{degrees}F (315-382{degrees}C). Commercial catalysts vary in activity and selectivity, allowing process designers to emphasize middle distillates, naphtha, or both. Catalysts are quite stable in use, with two year unit run lengths typical. A pretreatment step to remove nitrogen compounds is usually part of the same process unit. These HDN units operate integrally with the hydrocracking. The hydrogenation reactions are strongly exothermic, while the cracking is roughly thermal neutral. This combination can lead to temperature runaways. To avoid this, cold hydrogen is injected at several points in hydrocracking reactors. The mechanics of mixing this hydrogen with the oil and redistributing the mixture over the catalyst bed are very important in controlling process operation and ensuring long catalyst life.

  2. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October--December 1993

    SciTech Connect

    Schmidt, E.; Kirby, S.; Song, Chunshan; Schobert, H.H.

    1994-04-01

    Development of new catalysts is a promising approach to more, efficient coal liquefaction. It has been recognized that dispersed catalysts can be superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires infinite contact between the catalyst and coal. The primary objective of this research is to explore the potential of bimetallic dispersed catalysts from heterometallic molecular precursors in their use in model compound liquefaction reactions. This quarterly report describes the use of three precursors in model compound reactions. The first catalyst is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule. The second is a thiocubane type complex consisting of cobalt, molybdenum and sulfur. The third is a thiocubane type cluster consisting of iron and sulfur and the fourth, the pure inorganic salt ammonium tetrathiomolybdate (ATM). It was found that the structure and the ligands in the model complexes affect the activity of the resulting catalyst significantly. The optimum reaction at a pressure of 6.9 MPa hydrogen gas varied for different catalysts. The bimetallic catalysts generated in situ from the organometallic precursor are more active than monometallic catalysts like ATTM and the thiocubane type cluster Fe{sub 4}. Main products are hydrogenated phenanthrene derivatives, like DBP, THP, sym-OHP, cis- and trans-unsym-OHP with minor isomerization products such as sym-OHA. Our results indicate that other transition metal and ligand combinations in the organometallic precursors and the use of another model compound could result in substantially higher conversion activity.

  3. Role of Surface Cobalt Silicate in Single-Walled Carbon Nanotube Synthesis from Silica-Supported Cobalt Catalysts

    SciTech Connect

    Li, N.; Wang, X; Derrouiche, S; Haller, G; Pfefferle, L

    2010-01-01

    A silica-supported cobalt catalyst has been developed via incipient wetness impregnation for high-yield synthesis of single-walled carbon nanotubes (SWNTs). Co/SiO{sub 2}-impregnated catalysts have not been observed to be efficient for SWNT synthesis. Using an appropriately chosen precursor, we show that effective catalysts can be obtained for SWNT synthesis with yields up to 75 wt %. Detailed characterization indicates that the active sites for SWNT synthesis are small cobalt particles resulting from the reduction of a highly dispersed surface cobalt silicate species. The SWNTs produced by this catalyst are of high quality and easy to purify, and the process is simple and scalable.

  4. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, R.G.; Dosch, R.G.

    1993-01-05

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  5. Plasmatron-catalyst system

    DOEpatents

    Bromberg, Leslie; Cohn, Daniel R.; Rabinovich, Alexander; Alexeev, Nikolai

    2007-10-09

    A plasmatron-catalyst system. The system generates hydrogen-rich gas and comprises a plasmatron and at least one catalyst for receiving an output from the plasmatron to produce hydrogen-rich gas. In a preferred embodiment, the plasmatron receives as an input air, fuel and water/steam for use in the reforming process. The system increases the hydrogen yield and decreases the amount of carbon monoxide.

  6. Catalytic reforming catalyst

    SciTech Connect

    Buss, W.C.; Kluksdahl, H.E.

    1980-12-09

    An improved catalyst, having a reduced fouling rate when used in a catalytic reforming process, said catalyst comprising platinum disposed on an alumina support wherein the alumina support is obtained by removing water from aluminum hydroxide produced as a by-product from a ziegler higher alcohol synthesis reaction, and wherein the alumina is calcined at a temperature of 1100-1400/sup 0/F so as to have a surface area of 165 to 215 square meters per gram.

  7. Crystalline titanate catalyst supports

    SciTech Connect

    Anthony, R.G.; Dosch, R.G.

    1991-12-31

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  8. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  9. 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.

  10. 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.

  11. Gas Transport Resistance in Polymer Electrolyte Thin Films on Oxygen Reduction Reaction Catalysts.

    PubMed

    Liu, Hang; Epting, William K; Litster, Shawn

    2015-09-15

    Significant reductions in expensive platinum catalyst loading for the oxygen reduction reaction are needed for commercially viable fuel cell electric vehicles as well as other important applications. In reducing loading, a resistance at the Pt surface in the presence of thin perfluorosulfonic acid (PFSA) electrolyte film, on the order of 10 nm thick, becomes a significant barrier to adequate performance. However, the resistance mechanism is unresolved and could be due to gas dissolution kinetics, increased diffusion resistance in thin films, or electrolyte anion interactions. A common hypothesis for the origin of the resistance is a highly reduced oxygen permeability in the thin polymer electrolyte films that coat the catalyst relative to bulk permeability that is caused by nanoscale confinement effects. Unfortunately, the prior work has not separated the thin-film gas transport resistance from that associated with PFSA interactions with a polarized catalyst surface. Here, we present the first characterization of the thin-film O2 transport resistance in the absence of a polarized catalyst, using a nanoporous substrate that geometrically mimics the active catalyst particles. Through a parametric study of varying PFSA film thickness, as thin as 50 nm, we observe no enhanced gas transport resistance in thin films as a result of either interfacial effects or structural changes in the PFSA. Our results suggest that other effects, such as anion poisoning at the Pt catalyst, could be the source of the additional resistance observed at low Pt loading. PMID:26299282

  12. Heterocyclic anions of astrobiological interest

    SciTech Connect

    Cole, Callie A.; Demarais, Nicholas J.; Bierbaum, Veronica M.; Yang, Zhibo; Snow, Theodore P. E-mail: Nicholas.Demarais@colorado.edu E-mail: Zhibo.Yang@ou.edu

    2013-12-20

    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N{sub 2}O, O{sub 2}, CO, OCS, CO{sub 2}, and SO{sub 2}) and other reactive species (CS{sub 2}, CH{sub 3}Cl, (CH{sub 3}){sub 3}CCl, and (CH{sub 3}){sub 3}CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  13. Heterocyclic Anions of Astrobiological Interest

    NASA Astrophysics Data System (ADS)

    Cole, Callie A.; Demarais, Nicholas J.; Yang, Zhibo; Snow, Theodore P.; Bierbaum, Veronica M.

    2013-12-01

    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N2O, O2, CO, OCS, CO2, and SO2) and other reactive species (CS2, CH3Cl, (CH3)3CCl, and (CH3)3CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  14. Comprehensive catalyst management

    SciTech Connect

    Pritchard, S.

    2007-05-15

    From January 2009, as SCR season expands from five months to year-round to meet new US Clean Air Interstate Rule standards, new catalyst strategies are increasingly important. Power plants will need a comprehensive management strategy that accounts for a wide range of old and new issues to achieve peak performance. An optimum plan is necessary for catalyst replacement or addition. SCR systems should be inspected and evaluated at least once a year. Levels of deactivation agents, most often arsenic and calcium oxide, need to match the particular coals used. Tools such as Cormetech's FIELD Guide are available to quantify the effect on catalyst life under various fuel-firing scenarios. Tests should be conducted to evaluate the NH{sub 3}/NOx distribution over time to maximise catalyst performance. The article gives a case study of catalyst management at the Tennessee Valley Authority Allen plant. Recent changes have created new variables to be considered in a catalyst management process, notably the expansion of the operating temperature range, mercury oxidation and SO{sub 3} emission limits. Cormetech has researched these areas. 5 figs., 2 photos.

  15. 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.

  16. Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

    DOEpatents

    Shelnutt, J.A.

    1984-11-29

    A method is disclosed improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation. The method comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound ..pi..-..pi.. complexes which can develop.

  17. Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system

    DOEpatents

    Shelnutt, John A.

    1986-01-01

    A method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system for hydrogen generation which comprises forming an aqueous solution comprising an electron donor, methylviologen, and certain metalloporphyrins and metallochlorins, and irradiating said aqueous solution with light in the presence of a catalyst. In the photosynthesis process, solar energy is collected and stored in the form of a gas hydrogen. Ligands attached above and below the metalloporphyrin and metallochlorin plane are capable of sterically blocking photochemically inactive electrostatically bound .pi.--.pi. complexes which can develop.

  18. Alkoxylation using modified calcium-containing bimetallic or polymetallic catalysts

    SciTech Connect

    King, S.W.

    1992-05-19

    This patent describes a method for providing an alkoxylation catalyst. It comprises reacting or solubilizing, at least partially, calcium metal or a calcium-containing compound, by mixing with an activator or solubilizing thereby forming a calcium-containing reacting a divalent or polyvalent metal or a divalent or polyvalent metal-containing compound wherein the divalent or polyvalent metal is selected from the group consisting of beryllium, magnesium, strontium, barium, lanthanum, titanium, zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, iron, cobalt, nickel, copper, zinc, boron, gallium, silicon, germanium tin, phosphorus, antimony, sulfur, selenium, tellurium, cerium and thorium with an organic compound having at least one active hydrogen to produce a divalent or polyvalent metal-containing composition: reacting the calcium-containing composition with the divalent or polyvalent metal-containing composition under effective reaction conditions to produce a catalyst precursor composition; and reacting the catalyst precursor composition with a divalent or polyvalent oxyacid or a divalent or polyvalent metal salt of an oxyacid or mixtures thereof under effective reaction conditions to produce the alkoxylation catalyst.

  19. Preparation of the Cyclopentazole Anion in the Bulk: A Computational Study.

    PubMed

    Geiger, Uzi; Haas, Yehuda

    2016-07-01

    The cyclopentazole anion (cyclo-N5(-)), calculated to be a stable species, was prepared in the gas phase but attempts to synthesize it in the bulk have so far been futile. An aryl pentazole radical anion was suggested as a promising precursor in the gas phase. It is shown computationally that the radical anion (which may be prepared by reduction of the phenyl pentazole neutral) may indeed be used to form the cyclopetazolate anion in the gas phase and in liquid solution, alongside and in competition with the extrusion of N2 to produce the corresponding azide. In the gas phase, the C-N dissociation yields are very low due to much more efficient detachment of an electron. In polar solvents, ionization is suppressed and the primary yields of the two competing reactions are similar. The reaction must be carried out at low temperatures and special measures have to be taken to avoid recombination of the nascent cyclo-N5(-) with the geminate phenyl radical. A possible remedy is to use a solvent that reacts efficiently with the phenyl radical by H atom transfer. PMID:27028051

  20. A New Approach for Removing Anionic Organic Dyes from Wastewater Based on Electrostatically Driven Assembly.

    PubMed

    Sansuk, Sira; Srijaranai, Somkiat; Srijaranai, Supalax

    2016-06-21

    A conceptually new approach for an efficient removal of anionic organic dyes from wastewater using layered double hydroxides (LDHs) through their formation is presented. Acid yellow 25 (AY25) was used as anionic organic dye model molecules. As a result of the electrostatic induction, the removal mechanism involved a concurrent incorporation of AY25 molecules into the interlayer of LDHs during their structural arrangement, where Mg(2+) and Al(3+) ions were utilized to construct the base of LDHs in an alkaline solution. It was found that the molar stoichiometry of all precursors was a key factor affecting the removal efficiency. Within 5 min removal time, this method still maintained high removal efficiency of over 97% and provided a removal capacity of ∼186 mg g(-1), comparable to that of other LDH-based methods. Also, almost complete dye recovery was simply achieved by anionic exchange with common anions (Cl(-), NO3(-), and CO3(2-)). Additionally, the present technique is straightforward, cost-effective, and environmentally friendly since it avoids the synthesis step of sorbents, thus significantly saving time, chemicals, and energy. Hence, this strategy not only exhibits the alternative exploitation of LDHs, but also provides new insights into the removal of contaminants from wastewater. PMID:27231753

  1. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, R.

    1998-08-04

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic and/or reduced particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of all metals in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products. 7 figs.

  2. Preparation of superconductor precursor powders

    DOEpatents

    Bhattacharya, Raghunath; Blaugher, Richard D.

    1995-01-01

    A process for the preparation of a precursor metallic powder composition for use in the subsequent formation of a superconductor. The process comprises the steps of providing an electrodeposition bath comprising an electrolyte medium and a cathode substrate electrode, and providing to the bath one or more soluble salts of one or more respective metals, such as nitrate salts of thallium, barium, calcium, and copper, which are capable of exhibiting superconductor properties upon subsequent appropriate treatment. The bath is continually energized to cause the metallic particles formed at the electrode to drop as a powder from the electrode into the bath, and this powder, which is a precursor powder for superconductor production, is recovered from the bath for subsequent treatment. The process permits direct inclusion of thallium in the preparation of the precursor powder, and yields an amorphous product mixed on an atomic scale to thereby impart inherent high reactivity. Superconductors which can be formed from the precursor powder include pellet and powder-in-tube products.

  3. The direct formate fuel cell with an alkaline anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Bartrom, Amy M.; Haan, John L.

    2012-09-01

    We demonstrate for the first time an operating Direct Formate Fuel Cell employing formate salts as the anode fuel, air or oxygen as the oxidant, a polymer anion exchange membrane, and metal catalysts at the anode and cathode. Operation of the DFFC at 60 °C using 1 M KOOCH and 2 M KOH as the anode fuel and electrolyte and oxygen gas at the cathode produces 144 mW cm-2 of peak power density, 181 mA cm-2 current density at 0.6 V, and an open circuit voltage of 0.931 V. This performance is competitive with alkaline Direct Liquid Fuel Cells (DLFCs) previously reported in the literature and demonstrates that formate fuel is a legitimate contender with alcohol fuels for alkaline DLFCs. A survey of the literature shows that a formate-oxygen fuel cell has a high theoretical potential, and the safe, renewable formate fuel does not poison the anode catalyst.

  4. Easy To Synthesize, Robust Organo‐osmium Asymmetric Transfer Hydrogenation Catalysts

    PubMed Central

    Coverdale, James P. C.; Sanchez‐Cano, Carlos; Clarkson, Guy J.; Soni, Rina

    2015-01-01

    Abstract Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori‐type RuII catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X‐ray crystal structures of the 16‐electron OsII catalysts are almost identical to those of RuII. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The OsII catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones. PMID:25853228

  5. Optimization of Fe/Ni/Mg Trimetallic Catalyst for Carbon Nanotubes Growth by Using Fluidized Floating Catalyst Method

    NASA Astrophysics Data System (ADS)

    Azira, A. A.; Zainal, N. F. A.; Nik, S. F.; Rusop, M.

    2009-06-01

    Fluidized floating catalyst method has been used for preparing carbon nanotubes with average size ˜11 nm which yielded high yield even at low temperature; 650° C. Optimum concentration of the Fe/Ni/Mg metal alloy catalyst has been found to be at 2.133% for producing carbon nanotubes with high yield. Carbon nanotubes are formed by the evaporation of the camphor oil (precursor), which decomposes `in situ' and aggregates on the metal alloy catalyst particles present in the ceramic boat. From the PXRD analyses, graphite layers detected which provide an indication of the degree of graphitic character. However, by using the Scherrer equation is not suitable for carbon nanotubes as the value is slightly different from the average diameter determine from FESEM micrographs. Since the metallic alloy was obtained by calcining the respective nitrates, it is expected to have residual entrapped nitrogen, which may bond with the depositing CNTs as observed from FTIR spectroscopy.

  6. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    SciTech Connect

    Schoeb, A.M.

    1997-02-01

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO{sub 2} catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO{sub 2} system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, {sup 1}H NMR and microcalorimetry. The Pt-Ag/SiO{sub 2} and Pt-Cu/SiO{sub 2} catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO{sub 2} catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO{sub 2} catalysts for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO{sub 2}, Pt-Ag/SiO{sub 2} and Pt-Cu/SiO{sub 2} catalysts produced only butyraldehyde. Initial heats of adsorption ({approximately}90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the {sup 1}H NMR Knight shift.

  7. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    SciTech Connect

    Kamil Klier; Richard G. Herman; Heock-Hoi Kwon; James G. C. Shen; Qisheng Ma; Robert A. Hunsicker; Andrew P. Butler; Scott J. Bollinger

    2003-03-01

    A tungstena-zirconia (WZ) catalyst has been investigated for coupling methanol and isobutanol to unsymmetrical ethers, i.e. methyl isobutyl ether (MIBE) and compared with earlier studied sulfated-zirconia (SZ) and Nafion-H catalysts. In all cases, the ether synthesis mechanism is a dual site S{sub N}2 process involving competitive adsorption of reactants on proximal acid sites. At low reaction temperatures, methylisobutylether (MIBE) is the predominant product. However, at temperatures >135 C the WZ catalyst is very good for dehydration of isobutanol to isobutene. The surface acid sites of the WZ catalyst and a Nafion-H catalyst were diagnosed by high resolution X-ray photoelectron spectroscopy (XPS) of N 1s shifts after adsorption of amines. Using pyridine, ethylenediamine, and triethylamine, it is shown that WZ has heterogeneous strong Broensted acid sites. Theoretical study located the transition state of the alcohol coupling reaction on proximal Broensted acid sites and accounted well for XPS core-level shifts upon surface acid-base interactions. While computations have not been carried out with WZ, it is shown that the SZ catalyst is a slightly stronger acid than CF{sub 3}SO{sub 3}H (a model for Nafion-H) by 1.3-1.4 kcal/mol. A novel sulfated zirconia catalyst having proximal strong Broensted acid sites was synthesized and shown to have significantly enhanced activity and high selectivity in producing MIBE or isobutene from methanol/isobutanol mixtures. The catalyst was prepared by anchoring 1,2-ethanediol bis(hydrogen sulfate) salt precursor onto zirconium hydroxide, followed by calcination to remove the -(CH{sub 2}CH{sub 2})- bridging residues.

  8. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

    PubMed Central

    2015-01-01

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  9. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    PubMed

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  10. Synthesis of 1D Silica Nanostructures with Controllable Sizes Based on Short Anionic Peptide Self-Assembly.

    PubMed

    Wang, Shengjie; Cai, Qingwei; Du, Mingxuan; Xue, Junyi; Xu, Hai

    2015-09-10

    Artificial synthesis of silica under benign conditions is usually achieved by using cationic organic matrices as templates while the anionic analogues have not received enough consideration, albeit they are also functioning in biosilica formation. In this work, we report the design and self-assembly of an anionic peptide amphiphile (I3E) and the use of its self-assemblies as templates to synthesize 1D silica nanostructures with tunable sizes. We show that short I3E readily formed long nanofibrils in aqueous solution via a hierarchical self-assembly process. By using APTES and TEOS as silica precursors, we found that the I3E nanofibrils templated the production of silica nanotubes with a wide size distribution, in which the silica size regulation was achieved by tuning the interactions among the peptide template and silicon species. These results clearly illustrate a facile method for generating silica nanomaterials based on anionic matrices. PMID:26301578

  11. Novel pseudo-delocalized anions for lithium battery electrolytes.

    PubMed

    Jónsson, Erlendur; Armand, Michel; Johansson, Patrik

    2012-05-01

    A novel anion concept of pseudo-delocalized anions, anions with distinct positive and negative charge regions, has been studied by a computer aided synthesis using DFT calculations. With the aim to find safer and better performing lithium salts for lithium battery electrolytes two factors have been evaluated: the cation-anion interaction strength via the dissociation reaction LiAn ⇌ Li(+) + An(-) and the anion oxidative stability via a vertical ionisation from anion to radical. Based on our computational results some of these anions have shown promise to perform well as lithium salts for modern lithium batteries and should be interesting synthetic targets for future research. PMID:22441354

  12. A 1,3-Capped Calix[4] Conjugate Possessing an Amine Moiety as an Anion Receptor: Reversible Anion Sensing Detected by Spectroscopy and Characterization of the Supramolecular Features by Microscopy.

    PubMed

    Nehra, Anita; Yarramala, Deepthi S; Rao, Chebrolu Pulla

    2016-06-20

    A phenylenediamine-capped conjugate of calix[4]arene (Lamino ) was synthesized by reducing its precursor, Limino , with sodium borohydride in methanol. The Lamino sample binds to anions due to the more flexible and bent conformation of the capped aminophenolic binding core, compared to the precursor Limino . The Lamino sample showed selectivity towards H2 PO4 (-) by exhibiting a ratiometric increase in emission by about 11-fold with a detection limit of (1.2±0.2) μm ((116±20) ppb) over 15 anions studied, including other phosphates, such as P2 O7 (4-) , adenosine monophosphate (AMP(2-) ), adenosine diphosphate (ADP(2-) ), and adenosine triphosphate (ATP(2-) ). The Lamino sample shows an increase in the absorbance at λ=315 nm in the presence of H2 PO4 (-) , CO3 (2-) , HCO3 (-) , CH3 CO2 (-) , and F(-) . The (1) H NMR spectroscopic titration of Lamino with H2 PO4 (-) , F(-) , and CH3 CO2 (-) showed major changes in the phenylene-capped and salicyl moieties, and thereby, confirming the aminophenolic region as the binding core. However, the binding strength of these anions followed the trend H2 PO4 (-) >F(-) ≫CH3 CO2 (-) >HSO4 (-) . The heat changes observed by isothermal titration calorimetry support this trend. The Lamino sample showed reversible sensing towards H2 PO4 (-) and F(-) in the presence of Mg(2+) and Ca(2+) , respectively. NOESY studies of Lamino , in comparison with its anionic complexes, revealed that major conformational changes occurred in the capping region to facilitate the binding of anion. ESI-MS and the Job's method revealed 1:1 stoichiometry between Lamino and H2 PO4 (-) or F(-) . In the SEM micrographs of Lamino , the spherical particles are converted into spherical aggregates and further form large agglomerates and even branched sheets in the presence of anions, depending upon their binding strength. PMID:27218408

  13. 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.

  14. Novel Fischer-Tropsch slurry catalysts and process concepts for selective transportation fuel production: Final report

    SciTech Connect

    Withers, H.P. Jr.; Eliezer, K.F.; Mitchell, J.W.

    1987-12-01

    The preparation, characterization and performance of cobalt and ruthenium carbonyl cluster-based catalysts for use in slurry-phase Fischer-Tropsch (FT) technology was investigated. The use of metal carbonyls as active metal precursor allows for the possible control of metal particle size on the support surface and thus offers the potential for better control of activity and selectivity of the FT reaction. Accomplishments included reproducible catalyst preparation, improvements in activity by use of a silica support, understanding diffeences between nitrate and carbonyl precursors, a nd good activity maintenance in the slurry reactor. A CO/sub 2/(CO)/sub 8/Zr(OPr)/sub 4/SiO/sub 2/ catalyst (3.5% CO, 6.6% Zr) was developed as the most active system in the slurry reactor and also gave the best liquid fuel selectivity. Silica support provided the highest catalyst activities. This catalyst was successfully tested in an extended slurry-phase run that achieved 6 months on stream with a 10% loss in activity. Ru catalysts showed the highest activity in the fixed-bed reactor but deactivated rapidly in the slurry reactor. In the analysis of the kinetic data, catalyst deactivation was assumed to proceed linearly between baseline experients at fixed temperture. Causes of the deactivation are not fully understood. 27 refs., 37 figs., 20 tabs.

  15. Characterization of Al2O3 Supported Nickel Catalysts Derived from RFNon-thermal Plasma Technology

    SciTech Connect

    Jang, Ben W; Helleson, Michael J; Shi, Chunkai; Rondinone, Adam Justin; Schwartz, Viviane; Liang, Chengdu; Overbury, Steven {Steve} H

    2008-01-01

    Catalysts derived from non-thermal plasma techniques have previously shown unusual and highly advantageous catalytic properties including room temperature reduction, unusual metal particle structure and metal-support interactions, and enhanced selectivity and stability. This study focuses on the characterization of Al2O3 supported Ni catalysts derived from the RF non-thermal plasma technique with in-situ XRD, TPR-MS and STEM and on relating the results to the enhanced activity and stability of benzene hydrogenation. The results suggest that catalysts with plasma treatments before impregnation are relatively easier to be reduced and result in better activities under mild reduction conditions. These plasma treatments stabilize the nickel particle sizes of air(B) and H2(B) catalysts at 600 C by slowing down the sintering process. Plasma treatments after the impregnation of precursors, on the other hand, tend to delay the growth of nickel particles below 600 C, forming smaller Ni particles, but with a sudden increase in particle size near 600 C. It suggests that the structure of Ni nitrate and the metal-support interaction have been altered by the plasma treatments. The reduction patterns of plasma 1 treated catalysts are, therefore, changed. The catalyst with a combination plasma treatment demonstrates that the effect of a combination plasma treatment is larger than either the plasma treatment before or after the impregnation alone. Both plasma treatments before and after the impregnation of metal precursor play important roles in modifying supported metal catalysts.

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2006-09-30

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

  17. Growth Mechanism Of Carbon Nanotubes Prepared By Fluidized Floating Catalyst Method

    NASA Astrophysics Data System (ADS)

    Azira, A. A.; Zainal, N. F. A.; Nik, S. F.; Rusop, M.

    2009-06-01

    In this paper, carbon nanotubes were synthesized by fluidized floating catalyst method which yielded high yield even at low temperature; 650° C using camphor oil as carbon source and Argon as carrier gas. Optimum concentration for trimetal alloy catalyst; Fe/Ni/Mg has been found to be the suitable catalyst for producing carbon nanotubes at high yield. Carbon nanotubes are formed by the evaporation of the camphor oil (precursor), which decomposes `in situ' and aggregates on the metal alloy catalyst particles present in the ceramic boat. The morphology of carbon nanotubes were characterized by field emission scanning electron microscopy (FESEM). This result demonstrates that fluidized floating catalyst method is suitable for effective formation of CNTs with average size ˜11.5 nm. The morphological studies support `tip growth mechanism' for the growth of the CNT's in our case.

  18. Effect of preparation parameters on the microporous structure of Ni/SiO{sub 2} catalysts

    SciTech Connect

    Castillon, F.F.; Bodganchikova, N.; Fuentes, S.; Avalos, M.

    1996-12-31

    In this work the authors report the synthesis of Ni/SiO{sub 2} catalysts promoted by group 2 (IIA) cations (calcium and barium) which are currently used as hydrogenation catalysts. The effect of the preparation parameters-aging, base agent, and type of cation, on the surface area of catalysts--is evaluated. Catalysts were prepared by precipitation of the precursor silicic acid, along with nickel nitrate and calcium and barium carbonates, with NaOH, NH{sub 4}OH and Na{sub 2}CO{sub 3} as precipitating agents. Catalysts were characterized by diffuse reflectance spectra (DRS) and by BET-surface area measurements. Results are discussed in terms of sol-gel chemistry.

  19. Ru-Containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols.

    PubMed

    Manaenkov, Oleg V; Mann, Joshua J; Kislitza, Olga V; Losovyj, Yaroslav; Stein, Barry D; Morgan, David Gene; Pink, Maren; Lependina, Olga L; Shifrina, Zinaida B; Matveeva, Valentina G; Sulman, Esther M; Bronstein, Lyudmila M

    2016-08-24

    Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter are obtained by thermal decomposition of ruthenium acetylacetonate in the pores. The catalysts showed excellent activities and selectivities at 100% cellulose conversion, exceeding those for the commercial Ru/C. High selectivities as well as activities are attributed to the influence of Fe3O4 on the Ru(0)/Ru(4+) NPs. A facile synthetic protocol, easy magnetic separation, and stability of the catalyst performance after magnetic recovery make these catalysts promising for industrial applications. PMID:27484222

  20. Molecular pharmacology of renal organic anion transporters.

    PubMed

    Van Aubel, R A; Masereeuw, R; Russel, F G

    2000-08-01

    Renal organic anion transport systems play an important role in the elimination of drugs, toxic compounds, and their metabolites, many of which are potentially harmful to the body. The renal proximal tubule is the primary site of carrier-mediated transport from blood to urine of a wide variety of anionic substrates. Recent studies have shown that organic anion secretion in renal proximal tubule is mediated by distinct sodium-dependent and sodium-independent transport systems. Knowledge of the molecular identity of these transporters and their substrate specificity has increased considerably in the past few years by cloning of various carrier proteins. However, a number of fundamental questions still have to be answered to elucidate the participation of the cloned transporters in the overall tubular secretion of anionic xenobiotics. This review summarizes the latest knowledge on molecular and pharmacological properties of renal organic anion transporters and homologs, with special reference to their nephron and plasma membrane localization, transport characteristics, and substrate and inhibitor specificity. A number of the recently cloned transporters, such as the p-aminohippurate/dicarboxylate exchanger OAT1, the anion/sulfate exchanger SAT1, the peptide transporters PEPT1 and PEPT2, and the nucleoside transporters CNT1 and CNT2, are key proteins in organic anion handling that possess the same characteristics as has been predicted from previous physiological studies. The role of other cloned transporters, such as MRP1, MRP2, OATP1, OAT-K1, and OAT-K2, is still poorly characterized, whereas the only information that is available on the homologs OAT2, OAT3, OATP3, and MRP3-6 is that they are expressed in the kidney, but their localization, not to mention their function, remains to be elucidated. PMID:10919840

  1. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. PMID:25002191

  2. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, January--March, 1995

    SciTech Connect

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

    1995-05-01

    Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. The selected compound for model coal liquefaction reactions are 4-(1-naphthylmethyl)bibenzyl (NMBB) and anthrone. This report describes hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors and activity and selectivity of dispersed Fe catalysts from organometallic and inorganic precursors for hydrocracking of 4-(1-Naphthylmethyl) bibenzyl. For hydrodeoxygenation, model compound studies were performed using multi-ring systems, or those of comparable molecular weight, to investigate the capabilities of the dispersed catalysts. The model compounds selected include anthrone (carbonyl); dinaphthyl ether (aryl-aryl ether); xanthene (heterocyclic ether); and 2,6-di-t-butyl-4-methylphenol (hydroxyl). The catalyst precursors used were (NH{sub 4}){sub 2}MoS{sub 4}, [Ph{sub 4}P]{sub 2}[Ni(MoS{sub 4}){sub 2}] and Cp{sub 2}Co{sub 2}Mo{sub 2}(CO){sub 2}S{sub 4}. 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. The authors have examined various precursors, including a thiocubane type cluster Cp{sub 4}Fe{sub 4}S{sub 4}, a cyclopentadienyliron dicarbonyl dimer Cp{sub 2}Fe{sub 2}(CO){sub 4}, ferrocene Cp{sub 2}Fe, a series of carbonyl precursors including Fe(CO){sub 5}, Fe{sub 2}(CO){sub 9}, and Fe{sub 3}(CO){sub 12}, and superfine iron oxide with average particle size of 30 {angstrom}.

  3. Highly efficient platinum group metal free based membrane-electrode assembly for anion exchange membrane water electrolysis.

    PubMed

    Pavel, Claudiu C; Cecconi, Franco; Emiliani, Chiara; Santiccioli, Serena; Scaffidi, Adriana; Catanorchi, Stefano; Comotti, Massimiliano

    2014-01-27

    Low-temperature electricity-driven water splitting is an established technology for hydrogen production. However, the two main types, namely proton exchange membrane (PEM) and liquid alkaline electrolysis, have limitations. For instance, PEM electrolysis requires a high amount of costly platinum-group-metal (PGM) catalysts, and liquid alkaline electrolysis is not well suited for intermittent operation. Herein we report a highly efficient alkaline polymer electrolysis design, which uses a membrane-electrode assembly (MEA) based on low-cost transition-metal catalysts and an anion exchange membrane (AEM). This system exhibited similar performance to the one achievable with PGM catalysts. Moreover, it is very suitable for intermittent power operation, durable, and able to efficiently operate at differential pressure up to 3 MPa. This system combines the benefits of PEM and liquid alkaline technologies allowing the scalable production of low-cost hydrogen from renewable sources. PMID:24339230

  4. Deactivator for olefin polymerization catalyst

    SciTech Connect

    Rekers, L.J.; Speca, A.N.; Mayhew, H.W.

    1987-03-10

    A method is described comprising deactivating an olefin polymerization catalyst selected from the group consisting of Ziegler-Natta transition element catalysts and catalysts based on transition metal oxides by contacting the catalyst with a copolymer. The copolymer consists of an alpha-olefin having from 2 to about 12 carbon atoms and an unsaturated ester of a carboxylic acid. The deactivating copolymer is present in an amount such that the molar ratio of the unsaturated ester thereof to the sum of the transition element component of the polymerization catalyst and a cocatalyst for the transition element catalyst is in the range of between about 0.1 and about 6.

  5. ANNUAL REPORT. SUPRAMOLECULAR CHEMISTRY OF SELECTIVE ANION RECOGNITION FOR ANIONS OF ENVIRONMENTAL RELEVANCE

    EPA Science Inventory

    This project involves the design and synthesis of receptors for anions of environmental importance, including emphasis on high level and low activity waste. Polyammonium macrocycles as receptors and nitrate as target anion were the focus of the first phase of this project. A seco...

  6. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-12-11

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  7. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, Kristen

    2004-12-01

    This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical and structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.

  8. Correction of the anion gap for albumin in order to detect occult tissue anions in shock

    PubMed Central

    Hatherill, M; Waggie, Z; Purves, L; Reynolds, L; Argent, A

    2002-01-01

    Background: It is believed that hypoalbuminaemia confounds interpretation of the anion gap (AG) unless corrected for serum albumin in critically ill children with shock. Aim: To compare the ability of the AG and the albumin corrected anion gap (CAG) to detect the presence of occult tissue anions. Methods: Prospective observational study in children with shock in a 22 bed multidisciplinary paediatric intensive care unit of a university childrenrsquo;s hospital. Blood was sampled at admission and at 24 hours, for acid-base parameters, serum albumin, and electrolytes. Occult tissue anions (lactate + truly "unmeasured" anions) were calculated from the strong ion gap. The anion gap ((Na + K) - (Cl + bicarbonate)) was corrected for serum albumin using the equation of Figge: AG + (0.25 x (44 - albumin)). Occult tissue anions (TA) predicted by the anion gap were calculated by (anion gap - 15 mEq/l). Optimal cut off values of anion gap were compared by means of receiver operating characteristic (ROC) curves. Ninety three sets of data from 55 children (median age 7 months, median weight 4.9 kg) were analysed. Data are expressed as mean (SD), and mean bias (limits of agreement). Results: The incidence of hypoalbuminaemia was 76% (n = 42/55). Mean serum albumin was 25 g/l (SD 8). Mean AG was 15.0 mEq/l (SD 6.1), compared to the CAG of 19.9 mEq/l (SD 6.6). Mean TA was 10.2 mmol/l (SD 6.3). The AG underestimated TA with mean bias 10.2 mmol/l (4.1–16.1), compared to the CAG, mean bias 5.3 mmol/l (0.4–10.2). A clinically significant increase of TA >5 mmol/l was present in 83% (n = 77/93) of samples, of which the AG detected 48% (n = 36/77), and the CAG 87% (n = 67/77). Post hoc ROC analysis revealed optimal cut off values for detection of TA >5 mmol/l to be AG >10 mEq/l, and CAG >15.5 mEq/l. Conclusion: Hypoalbuminaemia is common in critically ill children with shock, and is associated with a low observed anion gap that may fail to detect clinically significant amounts of

  9. Electron impact induced anion production in acetylene.

    PubMed

    Szymańska, Ewelina; Čadež, Iztok; Krishnakumar, E; Mason, Nigel J

    2014-02-28

    A detailed experimental investigation of electron induced anion production in acetylene, C2H2, in the energy range between 1 and 90 eV is presented. The anions are formed by two processes in this energy range: dissociative electron attachment (DEA) and dipolar dissociation (DD). DEA in C2H2 is found to lead to the formation of H(-) and C2(-)/C2H(-) through excitation of resonances in the electron energy range 1-15 eV. These anionic fragments are formed with super thermal kinetic energy and reveal no anisotropy in the angular distributions. DD in C2H2 leads to the formation of H(-), C(-)/CH(-) and C2(-)/C2H(-) with threshold energies of 15.7, 20.0 and 16.5 eV respectively. The measured anion yields have been used to calculate anion production rates for H(-), C(-)/CH(-) and C2(-)/C2H(-) in Titan's ionosphere. PMID:24343432

  10. Infrared spectroscopy of anionic hydrated fluorobenzenes

    SciTech Connect

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-09-21

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C{sub 6}F{sub 6}{sup -}{center_dot}H{sub 2}O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules.

  11. Electroosmotic Flow Hysteresis for Dissimilar Anionic Solutions.

    PubMed

    Lim, An Eng; Lim, Chun Yee; Lam, Yee Cheong

    2016-08-16

    Electroosmotic flow (EOF) with two or more fluids is often encountered in various microfluidic applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during displacement flow of solutions with dissimilar anion species. In this investigation, EOF of dissimilar anionic solutions was studied experimentally through the current monitoring method and numerically through finite element simulations. As opposed to other conventional displacement flows, EOF involving dissimilar anionic solutions exhibits counterintuitive behavior, whereby the current-time curve does not reach the steady-state value of the displacing electrolyte. Two distinct mechanics have been identified as the causes for this observation: (a) ion concentration adjustment when the displacing anions migrate upstream against EOF due to competition between the gradients of electromigrative and convective fluxes and (b) ion concentration readjustment induced by the static diffusive interfacial region between the dissimilar fluids which can only be propagated throughout the entire microchannel with the presence of EOF. The resultant ion distributions lead to the flow rate to be directional-dependent, indicating that the flow conditions are asymmetric between these two different flow directions. The outcomes of this investigation contribute to the in-depth understanding of flow behavior in microfluidic systems involving inhomogeneous fluids, particularly dissimilar anionic solutions. The understanding of EOF hysteresis is fundamentally important for the accurate prediction of analytes transport in microfluidic devices under EOF. PMID:27426052

  12. pH-dependent release of trace elements including platinum group elements (PGEs) from gasoline and diesel catalysts

    NASA Astrophysics Data System (ADS)

    Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav

    2014-05-01

    The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (< 0.5 mg.kg-1, < 0.1 mg.kg-1, respectively). To evaluate leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.

  13. Quality assurance for purchased catalysts

    SciTech Connect

    Puls, F.H. )

    1988-09-01

    Petrochemical industries require many different types of catalysts in process operations. A significantly portion of these requirements is being met through purchases from merchant catalyst suppliers. The importance of catalysts and of catalyst quality to these industries cannot be overstated. It is not surprising that in the quest for quality which has affected much of US industry in the last few years, catalysts were among the first products which were singled out for development of quality assurance. Currently, catalyst supplier auditing and certification procedures are being implemented. Primary emphasis is on the implementation of statistical process control procedures in the manufacture of commercially available catalyst. Thus, a trend exists to move from quality assurance (QA) and quality control (QC) for purchased catalysts to statistical process control (SPC). This development is being supported by audits of the suppliers' manufacturing quality control systems. The keystone of quality management is the concept of customer and supplier working together for their mutual advantage. The focus in this presentation will be on two topics. (1) Fixed bed catalysts: The recognition of lot-to-lot variations led to purchase specifications which then led to quality control procedures for purchased catalysts. (2) Catalyst suppliers: the limitations of quality control for catalysts will be discussed, and the efforts of catalyst suppliers to apply SPC will be mentioned.

  14. Alumina-supported bimetallics of palladium alloyed with germanium, tin, lead, or antimony from organometallic precursors I. Preparation and characterization

    SciTech Connect

    Aduriz, H.R.; Bodnariuk, P. , Bahia Blanca ); Coq, B.; Figueras, F. )

    1989-09-01

    Bimetallic PdSn, PdSb, PdPb, and PdGe on alumina catalysts with a low metal content have been prepared using either chloride or organometallic precursors. For the catalysts obtained from chloride precursors no interaction was observed between the two metals, and the catalysts behaved like pure Pd/Al{sub 2}O{sub 3}. In contrast, the reactions of (C{sub 4}H{sub 9}){sub 4}Sn, (C{sub 4}H{sub 9}){sub 4}Pb, (C{sub 4}H{sub 9}){sub 4}Ge, or (C{sub 4}H{sub 9}){sub 3}Sb in n-heptane solution with reduced Pd/Al{sub 2}O{sub 3} catalyst yielded a supported alloy. The interaction between metallic palladium and the organic modifier is highly selective and leads to the formation of a well-tailored bimetallic catalyst. When these final solids are reduced at 573 or 773 K, the second metal locates preferentially at the outer layer of the bimetallic aggregates. After reduction at 773 K large metallic aggregates are obtained (particle size 15 nm), and the formation of {beta}-palladium hydride, which can be formed with pure palladium catalysts, is suppressed by the addition of a small amount of the second metal. The specific activity of the palladium surface atoms for isoprene hydrogenation is then lowered, and the selectivity increased.

  15. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis.

    PubMed

    Huang, Daria L; Beltrán-Suito, Rodrigo; Thomsen, Julianne M; Hashmi, Sara M; Materna, Kelly L; Sheehan, Stafford W; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H

    2016-03-01

    This paper introduces Ir(I)(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*Ir(III)(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue Ir(IV) species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting Ir(IV) species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By (1)H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3. PMID:26901517

  16. An Innovative Anion Regulation Strategy for Energy Bands of Semiconductors: A Case from Bi2O3 to Bi2O(OH)2SO4

    PubMed Central

    Tian, Hao; Teng, Fei; Xu, Juan; Lou, Sunqi; Li, Na; Zhao, Yunxuan; Chen, Mindong

    2015-01-01

    How to develop a new, efficient photo catalyst is still a big challenge to us. A suitable band gap is the key for light absorption of semiconductor. Herein, an innovative anion intercalation strategy is, for the first time, developed to regulate the energy band of semiconductor. Typically, we introduce a layered sulfate compound (Bi2O(OH)2SO4) as a new photo catalyst, which has not been known before. Both partial density of states (PDOS) and total density of states (TDOS) have demonstrated that compared with Bi2O3 (2.85 eV), the band gap of Bi2O(OH)2SO4 has been widened to 4.18 eV by the intercalation of sulfate anion. Moreover, the band gap width of oxyacid salt compound is mainly predominated by the number of the outmost electrons (NOE) of central atom of anion. This study suggests that new photo catalysts can be developed by grouping anions with the existing oxides or sulfides. PMID:25597769

  17. An innovative anion regulation strategy for energy bands of semiconductors: a case from Bi2O3 to Bi2O(OH)2SO4.

    PubMed

    Tian, Hao; Teng, Fei; Xu, Juan; Lou, Sunqi; Li, Na; Zhao, Yunxuan; Chen, Mindong

    2015-01-01

    How to develop a new, efficient photo catalyst is still a big challenge to us. A suitable band gap is the key for light absorption of semiconductor. Herein, an innovative anion intercalation strategy is, for the first time, developed to regulate the energy band of semiconductor. Typically, we introduce a layered sulfate compound (Bi2O(OH)2SO4) as a new photo catalyst, which has not been known before. Both partial density of states (PDOS) and total density of states (TDOS) have demonstrated that compared with Bi2O3 (2.85 eV), the band gap of Bi2O(OH)2SO4 has been widened to 4.18 eV by the intercalation of sulfate anion. Moreover, the band gap width of oxyacid salt compound is mainly predominated by the number of the outmost electrons (NOE) of central atom of anion. This study suggests that new photo catalysts can be developed by grouping anions with the existing oxides or sulfides. PMID:25597769

  18. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, Dorai; Waller, Francis Joseph

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  19. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  20. Supported organoiridium catalysts for alkane dehydrogenation

    DOEpatents

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  1. The Innate Lymphoid Cell Precursor.

    PubMed

    Ishizuka, Isabel E; Constantinides, Michael G; Gudjonson, Herman; Bendelac, Albert

    2016-05-20

    The discovery of tissue-resident innate lymphoid cell populations effecting different forms of type 1, 2, and 3 immunity; tissue repair; and immune regulation has transformed our understanding of mucosal immunity and allergy. The emerging complexity of these populations along with compounding issues of redundancy and plasticity raise intriguing questions about their precise lineage relationship. Here we review advances in mapping the emergence of these lineages from early lymphoid precursors. We discuss the identification of a common innate lymphoid cell precursor characterized by transient expression of the transcription factor PLZF, and the lineage relationships of innate lymphoid cells with conventional natural killer cells and lymphoid tissue inducer cells. We also review the rapidly growing understanding of the network of transcription factors that direct the development of these lineages. PMID:27168240

  2. Precursor polymer compositions comprising polybenzimidazole

    SciTech Connect

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

    2015-07-14

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  3. Behavior of borate complex anion on the stabilities and the hydrogen evolutions of ZnxCo3-xO4 decorated graphene

    NASA Astrophysics Data System (ADS)

    Hao, Xuqiang; Jin, Zhiliang; Wang, Fang; Xu, Jing; Min, Shixiong; Yuan, Hong; Lu, Gongxuan

    2015-06-01

    The electron oscillation of borate complex anions in the borate solution was a very interesting peculiar phenomenon in the study of Solution Chemistry up to now. By means of borate complex anions addition, reacting system inertion and the electrons addition, based on the peculiar contribution of borate complex anions with an electron oscillation characters, the stabilities and the hydrogen evolutions of ZnxCo3-xO4 decorated graphene were greatly improved. Here, the photocatalytic activity was dependent on the synergetic effects of borate complex anions and graphene. The structure-activity relationships between the borate complex anions and the ZnxCo3-xO4 decorated grapheme were investigated. The borate complex anions can not only contribute to the more efficiently capture electrons from excited Eosin dye but also beneficial to the more efficiently transfer electrons to the decorated catalysts. So the charge separation and the electrons transfer were more efficient in the condition of the borate complex anions addition as supported by fluorescence studies. The synergetic effects between boron and grapheme were due to the double-pathway of synergetic effects for electrons transfer.

  4. A simple method of producing aligned carbon nanotubes from an unconventional precursor Camphor

    NASA Astrophysics Data System (ADS)

    Kumar, Mukul; Ando, Yoshinori

    2003-06-01

    Vertically aligned multi-wall carbon nanotubes of diameter 20-40 nm and length ˜200 μm were grown on quartz substrate by pyrolyzing camphor with ferrocene catalyst at 900 °C in argon atmosphere at ambient pressure. Catalyst requirement with camphor was found to be low by a factor of 10 as compared to available reports of aligned nanotubes from conventional precursors. Because of the low catalyst requirement with camphor, as-grown nanotubes are least contaminated with metal particles, whereas the oxygen atom present in camphor helps in oxidizing amorphous carbon in-situ, eliminating the need of post-deposition purification. Good graphitization of the tube layers was observed by TEM, whereas high purity was confirmed by EDX analysis. The estimated yield of as-grown nanotubes is ˜90%.

  5. An efficient, overall [4+1] cycloaddition of 1,3-dienes and nitrene precursors.

    PubMed

    Wu, Qiong; Hu, Jian; Ren, Xinfeng; Zhou, Jianrong

    2011-10-01

    Intermolecular cycloadditions of conjugated dienes and nitrene precursors usually produce aziridines. A generally useful method was lacking to directly provide the [4+1] cycloadducts, 3-pyrrolines. We have realized this transformation by using an uniquely active catalyst, copper(II) 1,1,1,5,5,5-hexafluoroacetylacetonate ([Cu(hfacac)(2)]). The method is applicable to a wide array of dienes with good yields. When 1,4-disubstituted dienes are used as substrates, good-to-excellent cis or trans selectivity can be obtained. Interestingly, the cis or trans preference depends on the nature of the substituents, rather than diene geometry. Mechanistic studies reveal that the [4+1] cycloaddition proceeds through diene aziridination and subsequent ring expansion. Among common copper catalysts, only [Cu(hfacac)(2)] can efficiently catalyze both steps, which explains the unique efficiency of the catalyst. PMID:21887836

  6. TOPICAL REVIEW: Nanoparticle catalysts

    NASA Astrophysics Data System (ADS)

    Moshfegh, A. Z.

    2009-12-01

    In this review, the importance of nanoparticles (NPs), with emphasis on their general and specific properties, especially the high surface-to-volume ratio (A/V), in many technological and industrial applications is studied. Some physical and chemical preparation methods for growing several metallic and binary alloy NP catalysts are reviewed. The growth and mechanism of catalytic reactions for synthesis of 1D nanostructures such as ZnO nanowires and multiwall carbon nanotubes (MWCNTs) are discussed. Gas-phase production with emphasis on dependence of catalytic activity and selectivity on size, shape and structure of NPs is also investigated. Application of NP catalysts in several technological processes including H2 production and storage as well as antibacterial effect, gas sensors and fuel cells is discussed. The mechanism of H2 production from catalytic photoelectrochemical and photocatalytic degradation reactions of some organic dyes is discussed. Finally, the future outlook of NP catalysts in various disciplines is presented.

  7. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  8. Catalyst, method of making, and reactions using the catalyst

    DOEpatents

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

    2009-03-03

    The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

  9. Catalyst, Method Of Making, And Reactions Using The Catalyst

    DOEpatents

    Tonkovich, Anna Lee Y.; Wang, Yong; Gao, Yufei

    2004-07-13

    The present invention includes a catalyst having a layered structure with, (1) a porous support, (2) a buffer layer, (3) an interfacial layer, and optionally (4) a catalyst layer. The invention also provides a process in which a reactant is converted to a product by passing through a reaction chamber containing the catalyst.

  10. Nucleation precursors in protein crystallization

    PubMed Central

    Vekilov, Peter G.; Vorontsova, Maria A.

    2014-01-01

    Protein crystal nucleation is a central problem in biological crystallography and other areas of science, technology and medicine. Recent studies have demonstrated that protein crystal nuclei form within crucial precursors. Here, methods of detection and characterization of the precursors are reviewed: dynamic light scattering, atomic force microscopy and Brownian microscopy. Data for several proteins provided by these methods have demonstrated that the nucleation precursors are clusters consisting of protein-dense liquid, which are metastable with respect to the host protein solution. The clusters are several hundred nanometres in size, the cluster population occupies from 10−7 to 10−3 of the solution volume, and their properties in solutions supersaturated with respect to crystals are similar to those in homogeneous, i.e. undersaturated, solutions. The clusters exist owing to the conformation flexibility of the protein molecules, leading to exposure of hydrophobic surfaces and enhanced intermolecular binding. These results indicate that protein conformational flexibility might be the mechanism behind the metastable mesoscopic clusters and crystal nucleation. Investigations of the cluster properties are still in their infancy. Results on direct imaging of cluster behaviors and characterization of cluster mechanisms with a variety of proteins will soon lead to major breakthroughs in protein biophysics. PMID:24598910

  11. Pt ∧Ru/C catalysts synthesized by a two-stage polyol reduction process for methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Li, Yuexia; Zheng, Liping; Liao, Shijun; Zeng, Jianhuang

    Highly dispersed Ru/C catalysts are prepared using high viscosity glycerol as a reducing agent and are treated in H 2 atmosphere to ensure stability. A Pt ∧Ru/C catalyst is prepared by an ethylene glycol process based on the pre-formed Ru/C. The catalyst is tested for methanol oxidation reaction at room temperature and is compared with the activity of the as-prepared PtRu/C alloyed catalyst (prepared by co-reduction of Pt and Ru precursors) and commercial PtRu/C from E-TEK. The catalysts are extensively characterized by Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements by cyclic voltammetry (CV) showed consistently high catalytic activities and improved CO resistance for the Pt ∧Ru/C catalyst.

  12. Conversion of C2-C4 alcohols over copper-containing catalysts on carbon and fluorocarbon fibers

    NASA Astrophysics Data System (ADS)

    Tveritinova, E. A.; Zhitnev, Yu. N.; Roshchina, T. M.; Lunin, V. V.

    2011-07-01

    Carbon and fluorocarbon fibers were used as carriers for the preparation of copper catalysts from copper oxalate as precursor. The catalytic properties of catalyst were studied in the reaction of the dehydrogenation of C2-C4 alcohols by the pulsed microcatalytic method. The effect of the copper content in the catalyst, the reaction temperature on the degree of conversion, and the relation of the reaction channels were studied. The electron microphotographs were obtained, specific surfaces were measured, and X-ray pictures and infrared spectra of catalysts were taken. The activity of the catalysts on the carbon and fluorocarbon fibers in the dehydration-dehydrogenation reactions of C2-C4 alcohols was comparatively estimated. It was shown that the selectivity of the products from the dehydrogenation reaction is higher for the Cu-fluorocarbon fiber catalyst.

  13. Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution

    PubMed Central

    Hartwig, John F.; Stanley, Levi M.

    2010-01-01

    Conspectus Enantioselective allylic substitution reactions comprise some of the most versatile methods for preparing enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon–nitrogen, carbon–oxygen, carbon–carbon, and carbon–sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals have revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsymmetrical allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, we describe an iridium precursor and a phosphoramidite ligand that catalyze reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or separately in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prepare intermediates containing allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from our laboratory on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields

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

    PubMed

    Serna, Pedro; Gates, Bruce C

    2014-08-19

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

  15. Infrared Spectroscopy of Hydrated Nitromethane Anions

    NASA Astrophysics Data System (ADS)

    Marcum, Jesse C.; Weber, J. Mathias

    2009-06-01

    The hydration of molecular anions is still not as thoroughly explored as for atomic anions. We present IR spectra and quantum chemical calculations of hydrated nitromethane anions. In the monohydrate, the nitro group of the ion interacts with the water molecule via two hydrogen bonds, one from each O atom. This motif is partially conserved in the dihydrate. Adding the third water molecule results in a ring-like structure of the water ligands, each of which forms one H bond to one of the O atoms of the nitro group and another to a neighboring water ligand, reminiscent of the hydration motif of the heavier halides. Interestingly, while the methyl group is not directly involved in the interaction with the water ligands, its infrared signature is strongly affected by the changes in the intramolecular charge distribution through hydration.

  16. Secret Lives of Catalysts Revealed

    SciTech Connect

    Salmeron, Miquel; Somorjai, Gabor

    2008-01-01

    Miquel Salmeron and Gabor Somorjai of Berkeley Lab's Materials Sciences Division discuss the first-ever glimpse of nanoscale catalysts in action. More information: http://newscenter.lbl.gov/press-releases/2008/10/21/catalysts/

  17. Engelhard expands oxidation catalysts portfolio

    SciTech Connect

    Rotman, D.

    1997-02-26

    Engelhard says its agreement earlier this month to market Amoco Chemical`s proprietary maleic anhydride catalyst reflects an effort to expand its speciality catalysts business (CW, Feb. 19, p.5). In particular, the company says it is looking for additional alliances to bolster its oxidation catalysts portfolio. {open_quotes}There are some areas of oxidation catalysis that are reasonably attractive,{close_quotes} says Paul Lamb, marketing director/chemical catalysts. He says that while Engelhard is not interested in commodity oxidation catalysts, such as those used to make sulfuric acid, it does want to boost offerings for higher-value oxidation catalysts. Engelhard is collaborating with Geon to offer oxychlorination catalysts for making ethylene dichloride. It also markets oxidation catalysts for vinyl acetate production.

  18. Carbon-supported and alumina-supported niobium sulfide catalysts

    SciTech Connect

    Allali, N.; Marie, A.M.; Danot, M.

    1995-10-01

    Few studies deal with the properties of niobium sulfide as a hydrodesulfurization catalyst. In this paper, the preparation of carbon-supported niobium sulfide catalysts was optimized concerning (i) the nature of the soluble precursor, (ii) the drying process, and (iii) the sulfurizing treatment, which was always performed under atmospheric pressure but for different H{sub 2}S-based flows and reaction temperatures. The activities of the best samples prepared with niobium oxalate as the impregnation salt, drying at room temperature, and presulfurization with N{sub 2}/H{sub 2}S at 400{degrees}C are superior to that of a supported MoS{sub 2} reference catalyst. Alumina-supported systems can be sulfurized only under more severe conditions (CS{sub 2} under pressure). After optimization of the sulfurization treatment (400{degrees}C, 10 h) the maximum activity obtained is significantly higher than that of a molybdenum sulfide reference catalyst. The catalytic activities of the various catalysts studied are related to their morphological and chemical characteristics using TPR and EXAFS measurements. The work illustrates the importance of the support and the sulfurization method on the genesis of a niobium sulfide active phase. 37 refs., 7 figs., 4 tabs.

  19. 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.

  20. Microemulsion flame pyrolysis for hopcalite nanoparticle synthesis: a new concept for catalyst preparation.

    PubMed

    Biemelt, T; Wegner, K; Teichert, J; Kaskel, S

    2015-04-01

    A new route to highly active hopcalite catalysts via flame spray pyrolysis of an inverse microemulsion precursor is reported. The nitrate derived nanoparticles are around 15 nm in diameter and show excellent conversion of CO under ambient conditions, outperforming commercial reference hopcalite materials produced by co-precipitation. PMID:25726946

  1. Competitive transesterification of soybean oil with mixed methanol/ethanol over heterogeneous catalysts.

    PubMed

    Kim, M; Yan, S; Salley, S O; Ng, K Y S

    2010-06-01

    Methylesters and ethylesters of fatty acids were synthesized using homogeneous CH(3)ONa and CH(3)CH(2)ONa, anion exchanged resin, and CaO-La(2)O(3) catalysts. Methanol, ethanol, and methanol/ethanol mixtures were used as the alcohol feed for transesterification of soybean oil. With a homogeneous catalyst (CH(3)ONa) there was essentially no difference in conversion rates between methanolysis and ethanolysis in batch reactions. However, with a heterogeneous resin and CaO-La(2)O(3) catalysts, significant differences in the conversion rates between the methanolysis and ethanolysis were observed. The formation rate of methylesters over a CaO-La(2)O(3) catalyst was higher than that of ethylesters, which may be attributable to a steric hindrance effect. Conversely, with a heterogeneous resin catalyst, the conversion rate of ethylester was higher than that of methylesters which may be attributable to the surface hydrophobicity of the anion exchanged resin. When the transesterification of soybean oil was carried out with an equimolar methanol/ethanol mixture, the yield ratio of methylester to ethylester formed within the first 30 min was 2.6 for the homogeneous catalyst (0.3% CH(3)ONa), and 3.4 for the heterogeneous CaO-La(2)O(3)catalyst. These differences in selectivity are likely due to both the higher reactivity of methoxide and to a steric hindrance effect of ethoxide on the catalyst surface. In addition, the transformation of methylester to ethylester was observed when a methanol/ethanol mixture was used. PMID:20153166

  2. Gas-Phase Fragmentation Pathways of Mixed Addenda Keggin Anions: PMo12-nW nO 40 3- (n = 0-12).

    PubMed

    Gunaratne, K Don D; Prabhakaran, Venkateshkumar; Johnson, Grant E; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo(12-n)W(n)O(40)(3-) (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed addenda POMs examined in this study. CID of molybdenum-rich anions, PMo(12-n)W(n)O(40)(3-) (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and 22 oxygen atoms (M(7)O(22)(2-)) and its complementary singly charged PM(5)O(18)(-) ion. In comparison, the doubly charged Lindqvist anion, (M(6)O(19)(2-)) and its complementary singly charged PM(6)O(21)(-) ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo(12-n)W(n)O(40)(3-) (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms in the POM may be attributed to the higher barrier of tungsten-rich anions towards isomerization. We present evidence that the observed distribution of Mo and W atoms in the major M(6)O(19)(2-) and M(7)O(22)(2-) fragment ions is different from that predicted by a random distribution, indicating substantial segregation of the addenda metal atoms in the POMs. Charge reduction of the triply charged precursor anion resulting in formation of doubly charged anions is also observed. This is a dominant pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and charge loss pathways in CID of POM anions. PMID:25832027

  3. Gas-Phase Fragmentation Pathways of Mixed Addenda Keggin Anions: PMo12-nWnO40 3- (n = 0-12)

    NASA Astrophysics Data System (ADS)

    Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo12-nWnO40 3- (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed addenda POMs examined in this study. CID of molybdenum-rich anions, PMo12-nWnO40 3- (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and 22 oxygen atoms (M7O22 2-) and its complementary singly charged PM5O18 - ion. In comparison, the doubly charged Lindqvist anion, (M6O19 2-) and its complementary singly charged PM6O21 - ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo12-nWnO40 3- (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms in the POM may be attributed to the higher barrier of tungsten-rich anions towards isomerization. We present evidence that the observed distribution of Mo and W atoms in the major M6O19 2- and M7O22 2- fragment ions is different from that predicted by a random distribution, indicating substantial segregation of the addenda metal atoms in the POMs. Charge reduction of the triply charged precursor anion resulting in formation of doubly charged anions is also observed. This is a dominant pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and charge loss pathways in CID of POM anions.

  4. Gas-Phase Fragmentation Pathways of Mixed-Addenda Keggin Anions: PMo12-nWnO403- (n = 0-12)

    SciTech Connect

    Gunaratne, Kalupathirannehelage Don D.; Prabhakaran, Venkateshkumar; Johnson, Grant E.; Laskin, Julia

    2015-06-01

    We report a collision-induced dissociation (CID) investigation of the mixed addenda polyoxometalate (POM) anions, PMo12-nWnO403- (n = 0-12). The anions were generated in solution using a straightforward single-step synthesis approach and introduced into the gas phase by electrospray ionization (ESI). Distinct differences in fragmentation patterns were observed for the range of mixed POMs examined in this study. CID of molybdenum-rich anions, PMo12- nWnO403- (n = 0-2), generates an abundant doubly charged fragment containing seven metal atoms (M) and twenty-two oxygen atoms (M7O222-) and its complementary singly charged PM5O18- ion, while the Lindqvist anion, (M6O192-) and its complementary PM6O21- ion are the dominant fragments of Keggin POMs containing more than two tungsten atoms, PMo12-nWnO403- (n = 3-12). The observed transition in the dissociation pathways with an increase in the number of W atoms may be attributed to the higher stability of tungsten-rich anions towards isomerization. We find that the observed distribution of Mo and W atoms in the major M6O192- and M7O222- fragment ions is different from that predicted by a random distribution indicating substantial segregation of the addenda metal atoms in the POMs. Electron detachment from the triply charged precursor anion resulting in formation of doubly charged anions is observed. This is a dominant dissociation pathway for mixed POMs having a majority (8-11) of W atoms and a minor channel for other precursors indicating a close competition between fragmentation and electron detachment pathways of POM anions.

  5. Process of making supported catalyst

    SciTech Connect

    Schwarz, James A.; Subramanian, Somasundaram

    1992-01-01

    Oxide supported metal catalysts have an additional metal present in intimate association with the metal catalyst to enhance catalytic activity. In a preferred mode, iridium or another Group VIII metal catalyst is supported on a titania, alumina, tungsten oxide, silica, or composite oxide support. Aluminum ions are readsorbed onto the support and catalyst, and reduced during calcination. The aluminum can be added as aluminum nitrate to the iridium impregnate solution, e.g. chloroiridic acid.

  6. 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

  7. Identification and characterization of anion binding sites in RNA

    SciTech Connect

    Kieft, Jeffrey S.; Chase, Elaine; Costantino, David A.; Golden, Barbara L.

    2010-05-24

    Although RNA molecules are highly negatively charged, anions have been observed bound to RNA in crystal structures. It has been proposed that anion binding sites found within isolated RNAs represent regions of the molecule that could be involved in intermolecular interactions, indicating potential contact points for negatively charged amino acids from proteins or phosphate groups from an RNA. Several types of anion binding sites have been cataloged based on available structures. However, currently there is no method for unambiguously assigning anions to crystallographic electron density, and this has precluded more detailed analysis of RNA-anion interaction motifs and their significance. We therefore soaked selenate into two different types of RNA crystals and used the anomalous signal from these anions to identify binding sites in these RNA molecules unambiguously. Examination of these sites and comparison with other suspected anion binding sites reveals features of anion binding motifs, and shows that selenate may be a useful tool for studying RNA-anion interactions.

  8. Further analysis of the involvement of the envelope anion channel PIRAC in chloroplast protein import.

    PubMed

    van den Wijngaard, P W; Demmers, J A; Thompson, S J; Wienk, H L; de Kruijff, B; Vredenberg, W J

    2000-06-01

    The ability of preferredoxin to inactivate a 50-pS anion channel of the chloroplast inner membrane in the presence of an energy source was investigated using single-channel recordings. It was found that preferredoxin cannot inactivate the channel when GTP is the only energy source present. From this it is concluded that the precursor has to interact with the, translocon of the inner membrane of chloroplasts (Tic) complex to be able to inactivate the 50-pS anion channel. The ability of two mutants of preferredoxin with deletions in their transit sequence to inactivate the channel was also tested. Both mutants have been shown to have a similar binding affinity for the chloroplast envelope, but only one is able to fully translocate. The mutants were both able to inactivate the channel in a similar manner. From this it is concluded that full translocation is not necessary for the inactivation of the channel. It is also shown that preferredoxin is capable of inactivating the 50-pS anion channel in the chloroplast-attached configuration as was previously found in the inside-out configuration. From this it is concluded that stromal factors do not influence the protein-import-induced inactivation of the 50-pS anion channel of the chloroplast inner membrane. Finally the effect of the anion channel blocker 4, 4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS) on the channel activity and on protein import was investigated. It was found that DIDS blocked the channel. Furthermore the addition of the channel blocker reduces the efficiency of import to 52%. This leads to the conclusion that correct functioning of the channel is important for protein import. PMID:10849000

  9. Electron anions and the glass transition temperature.

    PubMed

    Johnson, Lewis E; Sushko, Peter V; Tomota, Yudai; Hosono, Hideo

    2016-09-01

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32](2+) ⋅ (e(-))2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design. PMID:27559083

  10. Anionic polymerization of azo substituted methacrylates

    SciTech Connect

    Dimov, D.K.; Dalton, L.R.; Hogen-Esch, T.E.

    1993-12-31

    The anionic polymerization of 4-phenylazophenyl methacrylate (PAM) and 6-(4-phenylazophenoxy)-hexyl methacrylate (PAHM) initiated by {open_quotes}living{close_quotes} PMMA with lithium counterion was studied in THF at {minus}78{degrees}C. The polymerization of PAM was prevented by a side termination reaction. The polymerization of PAHM proceeded smoothly to furnish PMMA/azopolymer block copolymers. The process showed features typical of {open_quotes}living{close_quotes} anionic polymerization. No phase transitions could be detected by DSC to prove liquid crystalline mesophase formation by the block copolymers.

  11. Tris-ureas as transmembrane anion transporters.

    PubMed

    Olivari, Martina; Montis, Riccardo; Berry, Stuart N; Karagiannidis, Louise E; Coles, Simon J; Horton, Peter N; Mapp, Lucy K; Gale, Philip A; Caltagirone, Claudia

    2016-08-01

    Nine tris-urea receptors (L(1)-L(9)) have been synthesised and shown to coordinate to a range of anionic guests both by (1)H NMR titration techniques and single crystal X-ray structural analysis. The compounds have been shown to be capable of mediating the exchange of chloride and nitrate and also chloride and bicarbonate across POPC or POPC : cholesterol 7 : 3 vesicle bilayer membranes at low transporter loadings. An interesting dependency of anion transport on the nature of the cation is evidence to suggest that a M(+)/Cl(-) cotransport process may also contribute to the release of chloride from the vesicles. PMID:27383134

  12. Negative Ion Photoelectron Spectra of Halomethyl Anions

    NASA Astrophysics Data System (ADS)

    Vogelhuber, Kristen M.; Wren, Scott W.; McCoy, Anne B.; Ervin, Kent M.; Lineberger, W. Carl

    2009-06-01

    Halomethyl anions undergo a significant geometry change upon electron photodetachment, resulting in multiple extended vibrational progressions in the photoelectron spectra. The normal mode analysis that successfully models photoelectron spectra when geometry changes are modest is unable to reproduce the experimental data using physically reasonable parameters. A three-dimensional anharmonic coupled-mode analysis was employed to accurately reproduce the observed vibrational structure. We present the 364 nm negative ion photoelectron spectra of the halomethyl anions CHX_2^- and CDX_2^- (X = Cl, Br, I) and report electron affinities, vibrational frequencies, and geometries.

  13. Methanol and methyl fuel catalysts. Final technical report, September 1980-August 1983

    SciTech Connect

    Klier, K.; Herman, R.G.; Simmons, G.W.

    1983-12-01

    Copper-based catalysts for alcohol synthesis were prepared, tested for catalytic activity and selectivity, and characterized. These catalysts include Cu/ZnO, Cu/Co/ZnO, Cu/Co/Cr/sub 2/O/sub 3/, Cu/Co/Cr/sub 2/O/sub 3//K/sub 2/O, and Cu/ZnO/KOH. The chromia-containing catalysts exhibited a low activity and selectivity, while the Cu/ZnO catalyst was verified to be a very active and selective methanol synthesis catalyst. Cobalt imparted a methanation function to the catalysts, while potassium suppressed the activity and the selectivity. Over the quaternary catalyst, higher pressure and lower GHSV enhanced the selectivity to higher alcohols. Low concentrations of carbon dioxide in H/sub 2//CO synthesis gas over Cu/ZnO catalysts promote methanol synthesis, while at high concentrations it behaves as a retardant of the synthesis. The water gas shift reaction readily proceeds over the Cu/ZnO catalyst. Analogous to the CO/sub 2/ effect, the presence of water in the synthesis gas has a profound effect on the synthesis of methanol. The Cu/ZnO catalyst is a good hydrogenation catalyst. Olefins, aldehydes, and acids are hydrogenated at a faster rate than CO is hydrogenated to methanol, but aromatics are hydrogenated at slower rates. Chemical trapping of the intermediates on these surface sites with amines demonstrates that a kinetically significant intermediate in methanol synthesis is a surface formyl or hydroxycarbene species. These species can be formed from synthesis gas or by alcohols in the reactant stream, and they readily alkylate amines in the reactant gas stream. Over an Fe/Cu/ZnO catalyst, amines inhibit the production of alcohols by trapping the precursor intermediates, while changing the hydrocarbon selectivity from paraffins to predominantly olefins. 68 references, 9 figures, 25 tables.

  14. PtRu-LiCoO 2—an efficient catalyst for hydrogen generation from sodium borohydride solutions

    NASA Astrophysics Data System (ADS)

    Krishnan, Palanichamy; Yang, Tae-Hyun; Lee, Won-Yong; Kim, Chang-Soo

    Hydrogen generation by the hydrolysis of aqueous sodium borohydride (NaBH 4) solutions is studied using IRA-400 anion resin dispersed Pt, Ru catalysts and lithium cobalt oxide (LiCoO 2) supported Pt, Ru and PtRu catalysts. The performance of the LiCoO 2 supported catalysts is better than that of ion-exchange resin dispersed catalysts. There is a marked concentration dependence on the performance of the LiCoO 2 supported catalysts and the hydrogen generation rate decreases if the borohydride concentration is increased beyond 10 wt.%. The efficiency of PtRu-LiCoO 2 is almost double that of either Ru-LiCoO 2 or Pt-LiCoO 2 for NaBH 4 concentrations up to 10 wt.%.

  15. Use of dispersed catalysts for direct coal liquefaction

    SciTech Connect

    Hirschon, A.S.; Kim, S.; Wilson, R.B.; Ghaly, O.

    1996-12-31

    With dwindling supplies of petroleum products, efforts to utilize alternative energy feedstocks such as coal, is essential. Several areas in coal conversion technology have been identified that, if improved, could make coal liquefaction more cost competitive with petroleum. The objectives of this project are to address possible improvements in the economics by utilizing low-rank coals, new precursors to dispersed catalysts, and processing variations such as using syngas atmospheres. The purpose of the dispersed catalysts is to better control retrogressive reactions and avoid char formation, while the purpose of the carbon monoxide atmosphere is to improve the economics by simplifying or totally eliminating a separate water-gas-shift step, and perhaps help remove oxygen in the product slate. These possible improvements are being examined and evaluated for potential use in a 2-stage liquefaction process with the goal of converting coal to distillable liquids at a cost competitive to petroleum of $25/bbl. To evaluate our catalysts and process conditions, we used three types of laboratory-scale operations. In the first operation, we compared the reaction chemistry of various ranks of coals and catalysts in synthetic solvents such as hexadecane. This method allowed us to better compare our catalysts without the complications of solvent initiated chemistry. Once the catalysts were tested in this manner, they were examined for the conversions of a Black Thunder subbituminous coal using a recycle vehicle derived from the same coal as the solvent. Finally, we upgraded selected first-stage conversion products using a conventional hydrotreating catalyst to compare with recent results in two-stage coal liquefaction development. The results were evaluated for economic feasibility through a subcontract with Bechtel Corp.

  16. Studies of supported hydrodesulfurization catalysts: Progress report for September 1, 1987 to December 31, 1988

    SciTech Connect

    Hercules, D.M.

    1988-10-01

    The objectives of the proposal are: (1) to study the mechanism of adsorption of anions pertinent to HDS catalysts (Mo,W) on Al2O3 (or TiO2) surfaces, (2) to determine the distribution of Mo (or W) oxidation states in Mo (or W)/TiO2 (or Al2O3) catalysts on reduction and to correlate Mo oxidation state to the catalytic activity observed for various probe reactions, (3) to apply the methodology for quantitative analysis of the distribution of supported species by Laser Raman Spectroscopy (LRS) (developed from an early study of Mo/TiO2 catalysts) to other systems relevant to HDS catalysts (e.g., W/TiO2), and finally (4) to correlate the Mo (or W) speciation derived from LRS with HDS activity. The accomplishments of the past year are as follows: We have investigated the nature of the interaction of molybdate and tungstate with alumina by comparing their adsorption behavior with that of perrhenate and permanganate anions; We have monitored by ESCA and gravimetric analysis the changes in Mo oxidation states for Mo/TiO2 catalyst as a function of reduction conditions. The results were correlated with benzene hydrogenation activity. We have extended the methodology for quantitative analysis of the distribution of supported species by LRS to the W/TiO2 system. Finally, we have correlated the Mo speciation in Mo/TiO2 derived from LRS with HDS activity.

  17. Cl-capped CdSe nanocrystals via in situ generation of chloride anions.

    PubMed

    Palencia, Cristina; Lauwaet, Koen; de la Cueva, Leonor; Acebrón, María; Conde, Julio J; Meyns, Michaela; Klinke, Christian; Gallego, José M; Otero, Roberto; Juárez, Beatriz H

    2014-06-21

    Halide ions cap and stabilize colloidal semiconductor nanocrystal (NC) surfaces allowing for NCs surface interactions that may improve the performance of NC thin film devices such as photo-detectors and/or solar cells. Current ways to introduce halide anions as ligands on surfaces of NCs produced by the hot injection method are based on post-synthetic treatments. In this work we explore the possibility to introduce Cl in the NC ligand shell in situ during the NCs synthesis. With this aim, the effect of 1,2-dichloroethane (DCE) in the synthesis of CdSe rod-like NCs produced under different Cd/Se precursor molar ratios has been studied. We report a double role of DCE depending on the Cd/Se precursor molar ratio (either under excess of cadmium or selenium precursor). According to mass spectrometry (ESI-TOF) and nuclear magnetic resonance ((1)H NMR), under excess of Se precursor (Se dissolved in trioctylphosphine, TOP) conditions at 265 °C ethane-1,2-diylbis(trioctylphosphonium)dichloride is released as a product of the reaction between DCE and TOP. According to XPS studies chlorine gets incorporated into the CdSe ligand shell, promoting re-shaping of rod-like NCs into pyramidal ones. In contrast, under excess Cd precursor (CdO) conditions, DCE reacts with the Cd complex releasing chlorine-containing non-active species which do not trigger NCs re-shaping. The amount of chlorine incorporated into the ligand shell can thus be controlled by properly tuning the Cd/Se precursor molar ratio. PMID:24827847

  18. Hydrogen evolution reaction catalyst

    DOEpatents

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

    2016-02-09

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

  19. 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.

  20. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  1. Catalyst, 2000-01.

    ERIC Educational Resources Information Center

    Ryan, Barbara E., Ed.

    2001-01-01

    "Catalyst" is a publication designed to assist higher education in developing alcohol and other drug prevention polices and programs that will foster students' academic and social development and promote campus and community safety. Issue 1 of volume 6 introduces a series of "Presidential Profiles" in which university presidents describe their…

  2. Tight bifunctional hierarchical catalyst.

    PubMed

    Højholt, Karen T; Vennestrøm, Peter N R; Tiruvalam, Ramchandra; Beato, Pablo

    2011-12-28

    A new concept to prepare tight bifunctional catalysts has been developed, by anchoring CoMo(6) clusters on hierarchical ZSM-5 zeolites for simultaneous use in HDS and hydrocracking catalysis. The prepared material displays a significant improved activity in HDS catalysis compared to the impregnated counterpart. PMID:22048337

  3. Salesperson, Catalyst, Manager, Leader.

    ERIC Educational Resources Information Center

    Worth, Michael J.; Asp, James W., II

    1996-01-01

    This article examines four roles of the college or university development officer: salesperson (when direct solicitation is seen as the officer's primary role); catalyst (or sales manager, adviser, expert, facilitator); manager (stressing the importance of the overall office functioning); and leader (who exerts a leadership role in the…

  4. Sabatier Catalyst Poisoning Investigation

    NASA Technical Reports Server (NTRS)

    Nallette, Tim; Perry, Jay; Abney, Morgan; Knox, Jim; Goldblatt, Loel

    2013-01-01

    The Carbon Dioxide Reduction Assembly (CRA) on the International Space Station (ISS) has been operational since 2010. The CRA uses a Sabatier reactor to produce water and methane by reaction of the metabolic CO2 scrubbed from the cabin air and the hydrogen byproduct from the water electrolysis system used for metabolic oxygen generation. Incorporating the CRA into the overall air revitalization system has facilitated life support system loop closure on the ISS reducing resupply logistics and thereby enhancing longer term missions. The CRA utilizes CO2 which has been adsorbed in a 5A molecular sieve within the Carbon Dioxide Removal Assembly, CDRA. There is a potential of compounds with molecular dimensions similar to, or less than CO2 to also be adsorbed. In this fashion trace contaminants may be concentrated within the CDRA and subsequently desorbed with the CO2 to the CRA. Currently, there is no provision to remove contaminants prior to entering the Sabatier catalyst bed. The risk associated with this is potential catalyst degradation due to trace organic contaminants in the CRA carbon dioxide feed acting as catalyst poisons. To better understand this risk, United Technologies Aerospace System (UTAS) has teamed with MSFC to investigate the impact of various trace contaminants on the CRA catalyst performance at relative ISS cabin air concentrations and at about 200/400 times of ISS concentrations, representative of the potential concentrating effect of the CDRA molecular sieve. This paper summarizes our initial assessment results.

  5. Photoelectron spectroscopy and theoretical studies of anion-π interactions: binding strength and anion specificity.

    PubMed

    Zhang, Jian; Zhou, Bin; Sun, Zhen-Rong; Wang, Xue-Bin

    2015-02-01

    Proposed in theory and then their existence confirmed, anion-π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, anion-π interaction strengths that are free from complications of condensed-phase environments have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic, was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl(-), Br(-), I(-), linear thiocyanate SCN(-), trigonal planar nitrate NO3(-), pyramidic iodate IO3(-), and tetrahedral sulfate SO4(2-)). The binding energies of the resultant gaseous 1 : 1 complexes (1·Cl(-), 1·Br(-), 1·I(-), 1·SCN(-), 1·NO3(-), 1·IO3(-) and 1·SO4(2-)) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion-specific effects. The binding strengths of Cl(-), NO3(-), IO3(-) with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal mol(-1), but only about 40% of that between 1 and SO4(2-). Quantum chemical calculations reveal that all the anions reside in the center of the cavity of 1 with an anion-π binding motif in the complexes' optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and charge distribution analyses further support anion-π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work illustrates that size-selective photoelectron

  6. Precursors of Short Gamma-Ray Bursts

    NASA Technical Reports Server (NTRS)

    Troja, E.; Rosswog, S.; Gehrels, N.

    2010-01-01

    We carried out a systematic search of precursors on the sample of short GRBs observed by Swift. We found that approx. 8-10% of short GRBs display such early episode of emission. One burst (GRB 090510) shows two precursor events, the former approx.13 s and the latter approx. 0.5 s before the GRB. We did not find any substantial difference between the precursor and the main GRB emission, and between short GRBs with and without precursors. We discuss possible mechanisms to reproduce the observed precursor emission within the scenario of compact object mergers. The implications of our results on quantum gravity constraints are also discussed.

  7. Characterization of ZrO 2-promoted Cu/ZnO/nano-Al 2O 3 methanol steam reforming catalysts

    NASA Astrophysics Data System (ADS)

    Jones, Samuel D.; Neal, Luke M.; Everett, Michael L.; Hoflund, Gar B.; Hagelin-Weaver, Helena E.

    2010-10-01

    Three Cu/ZnO/ZrO 2/Al 2O 3 methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO 2 from a monoclinic nanoparticle ZrO 2 precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO 2 produced by impregnation using a Zr(NO 3) 2 precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO 2 phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.

  8. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.

    PubMed

    Li, Jiang; Liu, Jun-Ling; Zhou, Hong-Jun; Fu, Yao

    2016-06-01

    Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation. PMID:27144965

  9. 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.

  10. Porous polymers bearing functional quaternary ammonium salts as efficient solid catalysts for the fixation of CO2 into cyclic carbonates.

    PubMed

    Cai, Sheng; Zhu, Dongliang; Zou, Yan; Zhao, Jing

    2016-12-01

    A series of porous polymers bearing functional quaternary ammonium salts were solvothermally synthesized through the free radical copolymerization of divinylbenzene (DVB) and functionalized quaternary ammonium salts. The obtained polymers feature highly cross-linked matrices, large surface areas, and abundant halogen anions. These polymers were evaluated as heterogeneous catalysts for the synthesis of cyclic carbonates from epoxides and CO2 in the absence of co-catalysts and solvents. The results revealed that the synergistic effect between the functional hydroxyl groups and the halide anion Br(-) afforded excellent catalytic activity to cyclic carbonates. In addition, the catalyst can be easily recovered and reused for at least five cycles without significant loss in activity. PMID:27365001

  11. Noble metal ionic catalysts.

    PubMed

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

    2009-06-16

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

  12. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2011-11-22

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  13. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2010-12-07

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  14. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  15. Anion-Conducting Polymer, Composition, and Membrane

    SciTech Connect

    Pivovar, Bryan S.; Thorn, David L.

    2008-10-21

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  16. Sulfur condensation in Claus catalyst

    SciTech Connect

    Schoffs, G.R.

    1985-02-01

    The heterogeneous reactions in which catalyst deactivation by pore plugging occur are listed and include: coke formation in petroleum processing, especially hydrocracking and hydrodesulfurization catalysts; steam reforming and methnation catalysts; ammonia synthesis catalyst; and automobile exhause catalysts. The authors explain how the Claus process converts hydrogen sulfide produced by petroleum desulfurization units and gas treatment processes into elemental sulfur and water. More than 15 million tons of sulfur are recovered annually by this process. Commercial Claus plants appear to operate at thermodynamic equilibrium. Depending on the H2S content of the feed and the number of reactors, total H2S conversion to elemental sulfur can exceed 95%.

  17. Molybdenum sulfide/carbide catalysts

    DOEpatents

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

    2007-05-29

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

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

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-03-31

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

  19. Polymer precursors for ceramic composites

    NASA Technical Reports Server (NTRS)

    Hurwitz, Frances I.

    1986-01-01

    The fiber composite approach to reinforced ceramics provides the possibility of achieving ceramics with high fracture toughness relative to monolithics. Fabrication of ceramic composites, however, demands low processing temperatures to avoid fiber degradation. Formation of complex shapes further requires small diameter fibers as well as techniques for infiltrating the matrix between fibers. Polymers offer low temperature processability, control of rheology not available with ceramic powders, and should serve as precursors to matrix fibers. In recent years, a number of polysilanes and polysilezanes were investigated as potential presursors. A review of candidate polymers is presented, including recent studies of silsesquioxanes.

  20. 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

  1. Preparation, structural characterization and catalytic properties of Co/CeO2 catalysts for the steam reforming of ethanol and hydrogen production

    NASA Astrophysics Data System (ADS)

    Lovón, Adriana S. P.; Lovón-Quintana, Juan J.; Almerindo, Gizelle I.; Valença, Gustavo P.; Bernardi, Maria I. B.; Araújo, Vinícius D.; Rodrigues, Thenner S.; Robles-Dutenhefner, Patrícia A.; Fajardo, Humberto V.

    2012-10-01

    In this paper, Co/CeO2 catalysts, with different cobalt contents were prepared by the polymeric precursor method and were evaluated for the steam reforming of ethanol. The catalysts were characterized by N2 physisorption (BET method), X-ray diffraction (XRD), UV-visible diffuse reflectance, temperature programmed reduction analysis (TPR) and field emission scanning electron microscopy (FEG-SEM). It was observed that the catalytic behavior could be influenced by the experimental conditions and the nature of the catalyst employed. Physical-chemical characterizations revealed that the cobalt content of the catalyst influences the metal-support interaction which results in distinct catalyst performances. The catalyst with the highest cobalt content showed the best performance among the catalysts tested, exhibiting complete ethanol conversion, hydrogen selectivity close to 66% and good stability at a reaction temperature of 600 °C.

  2. Catalytic etherification of glycerol to produce biofuels over novel spherical silica supported Hyflon® catalysts.

    PubMed

    Frusteri, Francesco; Frusteri, Leone; Cannilla, Catia; Bonura, Giuseppe

    2012-08-01

    Etherification of glycerol (GLY) with isobutylene (IB) to produce biofuels was investigated in liquid phase using spherical silica supported Hyflon® catalysts (SSHC). As reference catalyst, Amberlyst® 15 (A-15) acid ion-exchange resin was used. Experiments were carried out in batch mode at a reaction temperature ranging from 323 to 343 K. SSHC were found to be very effective systems in etherification of glycerol with IB, providing cumulative di- and tri-ethers yields higher than that obtained by using A-15 catalyst. Furthermore, such catalysts were stable and easily reusable; no leaching of active phase was observed. The formation of poly-substituted ethers, suitable additives for conventional fuels, was favored by operating at an isobutylene/glycerol molar ratio >3 and low reaction time (<6 h); however, the concentration of mono-ether reached values lower than 3 wt.% only when SSHC catalyst was used. Turnover frequency of glycerol (TOF(GLY)) highlighted that SSHC systems were much more active than A-15 catalyst: the accessibility and nature of active sites and the surface properties of catalysts were indicated as the main factors affecting the catalytic behavior. A lower acid site density of SSHC than that of A-15 catalyst was decisive in preventing the occurrence of oligomerization reaction which leads to the formation of di-isobutylene (DIB), precursors of gummy products. PMID:22705542

  3. Production of biohydrogen by aqueous phase reforming of polyols over platinum catalysts supported on three-dimensionally bimodal mesoporous carbon.

    PubMed

    Park, Hyun Ju; Kim, Ho-Dong; Kim, Tae-Wan; Jeong, Kwang-Eun; Chae, Ho-Jeong; Jeong, Soon-Yong; Chung, Young-Min; Park, Young-Kwon; Kim, Chul-Ung

    2012-04-01

    Now in 3D! Three-dimensionally bimodal carbons (3D-BMC) with mesopores of tunable size (controlled through the polymerization of the carbon precursor) are synthesized. After loading with platinum, the catalysts are used in aqueous phase reforming of polyols, and show superior performance in terms of carbon conversion, hydrogen yield, selectivity, and hydrogen production rate compared to platinum catalysts supported on activated carbon or two-dimensional CMK-3. PMID:22415941

  4. SUPRAMOLECULAR CHEMISTRY OF SELECTIVE ANION RECOGNITION FOR ANIONS OF ENVIRONMENTAL RELEVANCE

    EPA Science Inventory

    The supramolecular chemistry of selective anion recognition by synthetic polyammonium macrocycles will be explored in a comprehensive, long term program designed to provide new solutions to problems critical to the environmental initiative of DOE. Highly shape- and charge selecti...

  5. Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion

    SciTech Connect

    Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J; Lynch, Vincent M.; Hay, Benjamin; Moyer, Bruce A; Sessler, Jonathan L.

    2014-01-01

    Cage-type calix[4]pyrroles 2 and 3 bearing two additional pyrrole groups on the strap have been synthesized. Compared with the parent calix[4]pyrrole (1), they were found to exhibit remarkably enhanced affinities for anions, including the sulfate anion (TBA+ salts), in organic media (CD2Cl2). This increase is ascribed to participation of the bipyrrole units in anion binding. Receptors 2 and 3 extract the hydrophilic sulfate anion (as the methyltrialkyl(C8-10)ammonium (A336+) salt)) from aqueous media into a chloroform phase with significantly improved efficiency (>10-fold relative to calix[4]pyrrole 1). These two receptors also solubilize into chloroform the otherwise insoluble sulfate salt, (TMA)2SO4 (tetramethylammonium sulfate).

  6. Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

    NASA Technical Reports Server (NTRS)

    Moser, Thomas P.

    1990-01-01

    An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

  7. Annealing of aromatic polyimide precursors

    NASA Technical Reports Server (NTRS)

    Wakelyn, N. T.

    1975-01-01

    A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.

  8. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Jonathan L. Sessler

    2007-09-21

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  9. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins.

    PubMed

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S

    2014-07-01

    Ionic organic contaminants (OCs) are a growing concern for water treatment and the environment and are removed inefficiently by many existing technologies. This study examined removal of anionic OCs by anion exchange resins (AXRs) as a promising alternative. Results indicate that two polystyrene AXRs (IRA910 and IRA96) have higher sorption capacities and selectivity than a polyacrylate resin (A860). For the polystyrene resins, selectivity follows: phenolates ≥ aromatic dicarboxylates > aromatic monocarboxylates > benzenesulfonate > aliphatic carboxylates. This trend can be explained based on hydration energy, the number of exchange groups, and aromaticity and hydrophobicity of the nonpolar moiety (NPM) of the anions. For A860, selectivity only varies within a narrow range (0.13-1.64). Despite the importance of the NPM of the anions, neutral solutes were sorbed much less, indicating synergistic combinations of electrostatic and nonelectrostatic interactions in the overall sorption. By conducting multiple linear regression between Abraham's descriptors and nature log of selectivity, induced dipole-related interactions and electrostatic interactions were found to be the most important interaction forces for sorption of the anions, while solute H-bond basicity has a negative effect. A predictive model was then developed for carboxylates and phenolates based on the poly parameter linear free energy relationships established for a diverse range of 16 anions and 5 neutral solutes, and was validated by accurate prediction of sorption of five test solutes within a wide range of equilibrium concentrations and that of benzoate at different pH. PMID:24877792

  10. Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly technical progress report No. 7, April 1993--June 1993

    SciTech Connect

    Curtis, C.W.; Chander, S.; Gutterman, C.

    1994-09-01

    The overall objective of this project is to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The project is being carried out under contract to the United States Department of Energy. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. In addition, a synergistic effect has been demonstrated, in which solvent blends are more effective for coal swelling than the pure solvents alone. Therefore, it will be necessary to use only low levels of swelling agents and yet promote the impregnation of catalyst precursors. The rate of the impregnation of catalyst precursors into swollen coal increases greatly as the effectiveness of the solvent to swell the coal increases. This effect is also demonstrated by improved catalyst precursor impregnation with increased contact temperature. Laboratory- and bench-scale liquefaction experimentation is underway using swelled and catalyst impregnated coal samples. Higher coal conversions were observed for the SO{sub 2}-treated coal than the raw coal, regardless of catalyst type. Conversions of swelled coal were highest when Molyvan-L, molybdenum naphthenate, and nickel octoate, respectively, were added to the liquefaction solvent.

  11. Improved Steroids Detection and Evidence for Their Regiospecific Decompositions Using Anion Attachment Mass Spectrometry.

    PubMed

    Dumont, Quentin; Bárcenas, Mariana; Dossmann, Héloïse; Bailloux, Isabelle; Buisson, Corinne; Mechin, Nathalie; Molina, Adeline; Lasne, Françoise; Rannulu, Nalaka S; Cole, Richard B

    2016-04-01

    Nonpolar anabolic steroids are doping agents that typically do not provide strong signals by electrospray ionization-mass spectrometry (ESI-MS) owing especially to the low polarity of the functional groups present. We have investigated the addition of anions, in ammonium salt form, to anabolic steroid samples as ionization enhancers and have confirmed that lower instrumental limits of detection (as low as 10 ng/mL for fluoxymesterone-M) are obtained by fluoride anion attachment mass spectrometry, as compared to ESI(+)/(-) or atmospheric pressure photoionization (APPI)(+). Moreover, collision-induced decomposition (CID) spectra of precursor fluoride adducts of the bifunctional steroid "reduced pregnenolone" (containing two hydroxyl groups) and its d4-analogue provide evidence of regiospecific decompositions after attachment of fluoride anion to a specific hydroxyl group of the steroid. This type of charting of specific CID reaction pathways can offer value to selected reaction monitoring experiments (SRM) as it may result in a gain in selectivity in detection as well as in improvements in quantification. PMID:26926765

  12. Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor.

    PubMed

    Carrero, Carlos A; Keturakis, Christopher J; Orrego, Andres; Schomäcker, Reinhard; Wachs, Israel E

    2013-09-21

    The oxidative dehydrogenation (ODH) of propane to propylene by supported vanadia catalysts has received much attention in recent years, but different reactivity trends have been reported for this catalytic reaction system. In the present investigation, the origin of these differing trends are investigated with synthesis of supported V/SiO2, V/TiO2, and V/Al2O3 catalysts prepared with three different vanadium oxide precursors (2-propanol/vanadyl triisopropoxide [VO(O-Pri)3] (VTI), oxalic acid/ammonium metavanadate [NH4VO3] (AMV), and toluene/vanadyl acetylacetonate [VO(C5H7O2)2] (VAA)) in order to elucidate the influence of the precursor on supported vanadia phase and propane ODH activity. In situ Raman spectroscopy revealed that the choice of vanadium precursor does not affect the dispersion of the supported vanadium oxide phase below 4 V nm(-2) (0.5 monolayer coverage), where only isolated and oligomeric surface VO4 species are present, and only the AMV precursor favors crystalline V2O5 nanoparticle (NP) formation below monolayer coverage (8 V nm(-2)). The propane ODH specific reactivity trend demonstrated that there is no significant difference in TOF for the isolated and oligomeric surface VO4 sites. Surprisingly, V2O5 NPs in the ∼1-2 nm range exhibit anomalously high propane ODH TOF values for the supported vanadia catalysts. This was found for all supported vanadium oxide catalysts examined. This comparative study with different V-precursors and synthesis methods and oxide supports finally resolves the debate in the catalysis literature about the dependence of TOF on the surface vanadium density that is related to the unusually high reactivity of small V2O5 NPs. PMID:23652298

  13. Enhanced Polymer Grafting from Multiwalled Carbon Nanotubes through Living Anionic Surface-Initiated Polymerization.

    SciTech Connect

    Sakellariou, Georgios; Ji, Haining; Mays, Jimmy; Baskaran, Durairaj

    2008-01-01

    Anionic surface-initiated polymerization of ethylene oxide and styrene has been performed using multiwalled carbon nanotubes (MWNTs) functionalized with anionic initiators. The surface of MWNTs was modified via covalent attachment of precursor anions such as 4-hydroxyethyl benzocyclobutene (BCBEO) and 1-benzocyclobutene-1 -phenylethylene (BCB-PE) through Diels-Alder cycloaddition at 235 C. Surface-functionalized MWNTs-g-(BCB-EO)n and MWNTs-g-(BCB-PE)n with 23 and 54 wt % precursor initiators, respectively, were used for the polymerizations. Alkoxide anion on the surface of MWNTs-g-(BCB-EO)n was generated through reaction with potassium triphenylmethane for the polymerization of ethylene oxide in tetrahydrofuran and phenyl substituted alkyllithium was generated from the surface of MWNTs-g-(BCB-PE)n using sec-butyllithium for the polymerization of styrene in benzene. In both cases, the initiation was found to be very slow because of the heterogeneous reaction medium. However, the MWNTs gradually dispersed in the reaction medium during the polymerization. A pale green color was noticed in the case of ethylene oxide polymerization and the color of initiator as well as the propagating anions was not discernible visually in styrene polymerization. Polymer grafted nanocomposites, MWNTs-g-(BCB-PEO)n and MWNTs-g-(BCB-PS)n containing a very high percentage of hairy polymer with a small fraction of MWNTs (<1 wt %) were obtained. The conversion of ethylene oxide and the weight percent of PEO on the surface of the MWNTs increased with increasing reaction time indicating a controlled polymerization. The polymer-grafted MWNTs were characterized using FTIR, 1H NMR, Raman spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and transmission electron microscopy (TEM). Size exclusion chromatography of the polymer grafted MWNTs revealed broad molecular weight distributions (1.3 < Mw/Mn < 1.8) indicating the presence of different sizes of polymer nanocomposites

  14. Development of Cu xFe/Al 2O 3 catalysts for the hydrogenation of carbon monoxide guided by magnetic methods, Mössbauer and infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Boellaard, E.; van Bruggen, J. M.; Geus, J. W.; van der Kraan, A. M.

    1993-04-01

    A copper-iron catalyst for the hydrogenation of carbon monoxide has been prepared using a supported stoichiometric cyanide complex. Conversion of the cyanide precursor to a metallic catalyst appeared to be a precious process. Copper and iron in the bimetallic particles easily separate by thermal treatment and upon exposure to carbon monoxide, as revealed from Mössbauer and infrared spectroscopy. During Fischer-Tropsch reaction the catalyst exhibits a rapid decline of activity. Magnetisation measurements on spent catalysts indicate that the deactivation is caused by a fast conversion of metallic iron to initially unstable carbides which transform ultimately to more stable carbides.

  15. High Yield C-Derivatization of Weakly Coordinating Carborane Anions

    PubMed Central

    Nava, Matthew J.

    2010-01-01

    Unlike the “parent” carborane anion CHB11H11−, halogenated carborane anions such as CHB11H5Br6− can be readily C-functionalized in high yield and purity, enhancing their utility as weakly coordinating anions. PMID:20450167

  16. Reversible photochromism of an N-salicylidene aniline anion.

    PubMed

    Jacquemin, Pierre-Loïc; Robeyns, Koen; Devillers, Michel; Garcia, Yann

    2014-01-21

    The first N-salicylidene aniline anion showing reversible solid state thermochromic and photochromic properties is described. The photo-isomerization involves a trans-keto form which is stabilized thanks to the local anion surrounding. This photochromic anion can be used as a guest for the preparation of hybrid materials by insertion into a cationic host matrix. PMID:24022381

  17. Evaluation of cation-anion interaction strength in ionic liquids.

    PubMed

    Fernandes, Ana M; Rocha, Marisa A A; Freire, Mara G; Marrucho, Isabel M; Coutinho, João A P; Santos, Luís M N B F

    2011-04-14

    Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry. PMID:21425809

  18. Low-temperature growth of nitrogen-doped carbon nanofibers by acetonitrile catalytic CVD using Ni-based catalysts

    NASA Astrophysics Data System (ADS)

    Iwasaki, Tomohiro; Makino, Yuri; Fukukawa, Makoto; Nakamura, Hideya; Watano, Satoru

    2016-06-01

    To synthesize nitrogen-doped carbon nanofibers (N-CNFs) at high growth rates and low temperatures less than 673 K, nickel species (metallic nickel and nickel oxide) supported on alumina particles were used as the catalysts for an acetonitrile catalytic chemical vapor deposition (CVD) process. The nickel:alumina mass ratio in the catalysts was fixed at 0.05:1. The catalyst precursors were prepared from various nickel salts (nitrate, chloride, sulfate, acetate, and lactate) and then calcined at 1073 K for 1 h in oxidative (air), reductive (hydrogen-containing argon), or inert (pure argon) atmospheres to activate the nickel-based catalysts. The effects of precursors and calcination atmosphere on the catalyst activity at low temperatures were studied. We found that the catalysts derived from nickel nitrate had relatively small crystallite sizes of nickel species and provided N-CNFs at high growth rates of 57 ± 4 g-CNF/g-Ni/h at 673 K in the CVD process using 10 vol% hydrogen-containing argon as the carrier gas of acetonitrile vapor, which were approximately 4 times larger than that of a conventional CVD process. The obtained results reveal that nitrate ions in the catalyst precursor and hydrogen in the carrier gas can contribute effectively to the activation of catalysts in low-temperature CVD. The fiber diameter and nitrogen content of N-CNFs synthesized at high growth rates were several tens of nanometers and 3.5 ± 0.3 at.%, respectively. Our catalysts and CVD process may lead to cost reductions in the production of N-CNFs.

  19. Fluorination process using catalyst

    DOEpatents

    Hochel, Robert C.; Saturday, Kathy A.

    1985-01-01

    A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

  20. Activation of Methane and Ethane as Mediated by the Triatomic Anion HNbN(-) : Electronic Structure Similarity with a Pt Atom.

    PubMed

    Ma, Jia-Bi; Xu, Lin-Lin; Liu, Qing-Yu; He, Sheng-Gui

    2016-04-11

    Investigations of the intrinsic properties of gas-phase transition metal nitride (TMN) ions represent one approach to gain a fundamental understanding of the active sites of TMN catalysts, the activities and electronic structures of which are known to be comparable to those of noble metal catalysts. Herein, we investigate the structures and reactivities of the triatomic anions HNbN(-) by means of mass spectrometry and photoelectron imaging spectroscopy, in conjunction with density functional theory calculations. The HNbN(-) anions are capable of activating CH4 and C2 H6 through oxidative addition, exhibiting similar reactivities to free Pt atoms. The similar electronic structures of HNbN(-) and Pt, especially the active orbitals, are responsible for this resemblance. Compared to the inert NbN(-) , the coordination of the H atom in HNbN(-) is indispensable. New insights into how to replace noble metals with TMNs may be derived from this combined experimental/computational study. PMID:26954294

  1. FCC catalyst selection

    SciTech Connect

    Carter, G.D.L. ); McElhiney, G. )

    1989-09-01

    This paper discusses a commonly used technique for comparing FCC catalytic selectivities based on the ASTM microactivity test (MAT) procedure, ASTM D-3907-80. In its original form the ASTM test provides only very limited information on selectivity. However, extension of the ASTM MAT procedure by using additional product analyses gives a microselectivity test capable of providing detailed yield structure information. This modified MAT procedure thus provides a cost-effective and rapid means of comparing many catalysts.

  2. Steam reforming catalyst

    DOEpatents

    Kramarz, Kurt W.; Bloom, Ira D.; Kumar, Romesh; Ahmed, Shabbir; Wilkenhoener, Rolf; Krumpelt, Michael

    2001-01-01

    A method of forming a hydrogen rich gas from a source of hydrocarbon fuel. A vapor of the hydrocarbon fuel and steam is brought in contact with a two-part catalyst having a dehydrogenation powder portion and an oxide-ion conducting powder portion at a temperature not less than about 770.degree.C. for a time sufficient to generate the hydrogen rich. The H.sub.2 content of the hydrogen gas is greater than about 70 percent by volume. The dehydrogenation portion of the catalyst includes a group VIII metal, and the oxide-ion conducting portion is selected from a ceramic oxide from the group crystallizing in the fluorite or perovskite structure and mixtures thereof. The oxide-ion conducting portion of the catalyst is a ceramic powder of one or more of ZrO.sub.2, CeO.sub.2, Bi.sub.2 O.sub.3, (BiVO).sub.4, and LaGaO.sub.3.

  3. Hydrotreating catalyst selection

    SciTech Connect

    Kellett, T.F.; Trevino, C.A.; Sartor, A.F.

    1980-01-01

    Hydrotreating catalyst selection can be correctly made in most cases by using a decision tree developed for choosing between the commonly used cobalt/molybdenum and nickel/molybdenum. The decision suggests the use of Co/Mo for desulfurizing straight-run feeds (except naphtha) and Ni/Mo for hydrogen uptake (saturating aromatics, treating fluid catalytic-cracking (FCC) feedstocks, improving color or thermal stability, and increasing the octane number) with any feed, and for denitrogenation of cracked feeds or mixed feeds with greater than or equal to 20% cracked materials. For desulfurization of cracked or mixed feeds and for desulfurization or denitrogenation of naphtha, the selection depends on the reaction conditions. Pilot-plant studies with the second-generation commercial Shell 344 (Co/Mo) and Shell 324 (Ni/Mo) catalysts used in hydrotreating vacuum gas oils, flashed distillate, or heavy catalytically cracked gas oil supported the predictions made with the decision tree, but the better performance of the Ni/Mo catalyst in desulfurizing a 20% coker/80% straight-run naphtha at low partial pressures of hydrogen was an unexpected result.

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

    DOEpatents

    Zelenay, Piotr; Wu, Gang

    2014-04-29

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

  5. Use of Pillared Clay-Based Catalysts for Wastewater Treatment Through Fenton-Like Processes

    NASA Astrophysics Data System (ADS)

    Herney-Ramírez, J.; Madeira, Luis M.

    Clays, both natural and physical-chemically modified, are attractive materials for the preparation of supported catalysts. In this chapter, a review is made regarding the use of pillared interlayered clays (PILCs) in heterogeneous Fenton-like advanced oxidation processes. Their applications in pollutants degradation is summarized, with particular emphasis on the effect of the main operating conditions (e.g., initial H2O2 or parent compound concentration, catalyst load, pH, or temperature) on oxidation efficiency. Special attention is also given to the type of catalyst or precursor used, to the importance and advantages of the heterogeneous versus homogeneous process, and to significant aspects like catalyst stability. Among the technological issues that are of concern, the importance of using continuous flow reactors (e.g., fixed-bed) is discussed. Finally, some mechanistic studies are reviewed as well as modeling works, based on phenomenological or semi-empiric models (e.g., using statistic tools like design of experiments).

  6. Resolving Interparticle Heterogeneities in Composition and Hydrogenation Performance between Individual Supported Silver on Silica Catalysts

    PubMed Central

    2015-01-01

    Supported metal nanoparticle catalysts are commonly obtained through deposition of metal precursors onto the support using incipient wetness impregnation. Typically, empirical relations between metal nanoparticle structure and catalytic performance are inferred from ensemble averaged data in combination with high-resolution electron microscopy. This approach clearly underestimates the importance of heterogeneities present in a supported metal catalyst batch. Here we show for the first time how incipient wetness impregnation leads to 10-fold variations in silver loading between individual submillimeter-sized silica support granules. This heterogeneity has a profound impact on the catalytic performance, with 100-fold variations in hydrogenation performance at the same level. In a straightforward fashion, optical microscopy interlinks single support particle level catalytic measurements to structural and compositional information. These detailed correlations reveal the optimal silver loading. A thorough consideration of catalyst heterogeneity and the impact thereof on the catalytic performance is indispensable in the development of catalysts. PMID:26618052

  7. Premarital precursors of marital infidelity.

    PubMed

    Allen, Elizabeth S; Rhoades, Galena Kline; Stanley, Scott M; Markman, Howard J; Williams, Tamara; Melton, Jessica; Clements, Mari L

    2008-06-01

    Premarital precursors of infidelity were evaluated in a sample of 72 couples (N = 144) who were taking part in a longitudinal study of marriage. Premarital self-report and observational data were compared for couples who experienced infidelity and those who did not experience infidelity in the first years of marriage. Couples in which the male engaged in marital infidelity were characterized, premaritally, by significantly lower male sexual satisfaction, lower male positive communication, and higher female invalidation, whereas couples in which the female went on to engage in infidelity were characterized, premaritally, by significantly lower levels of female positive communication, higher levels of male and female negative communication, and higher levels of male and female invalidation. Implications of the findings for future research on the prediction and prevention of infidelity are discussed. PMID:18605124

  8. Precursors for Carbon Nitride Synthesis

    SciTech Connect

    Prashantha, M.; Gopal, E. S. R.; Ramesh, K.

    2011-07-15

    Nano structured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition. Pyrrole (C{sub 4}H{sub 5}N), Pyrrolidine (C{sub 4}H{sub 9}N), Azabenzimidazole (C{sub 6}H{sub 5}N{sub 3}) and Triazine (C{sub 6}H{sub 15}N{sub 3}) were used as precursors. The vibrational modes observed for C-N and C = N from FTIR spectra confirms the bonding of nitrogen with carbon. XPS core level spectra of C 1s and N 1s also show the formation of bonding between carbon and nitrogen atoms. The nitrogen content in the prepared samples was found to be around 25 atomic %.

  9. The chemistry of gold as an anion.

    PubMed

    Jansen, Martin

    2008-09-01

    Due to relativistic and classical shell structure effects, the 6s orbital of gold is significantly contracted and energetically stabilized. This is reflected by a strikingly high electron affinity, and a distinct tendency to adopt negatively polarized valence states. This tutorial review focuses on the chemistry of gold as an anion, displaying the integral ionic charge number of 1-. Two synthetic approaches to compounds containing monoatomic gold anions have become available: (1) reacting elemental gold with molten caesium and an oxide, e.g. Cs2O; (2) metathesis reactions involving Au- dissolved in liquid ammonia. Both procedures have proven to be rather versatile. Aurides synthesized along these routes are surveyed, in particular with respect to their structures and bonding properties. PMID:18762832

  10. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-16

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I{sub 3} revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  11. Specific anion effects in Artemia salina.

    PubMed

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero

    2015-09-01

    The specific anion effect on the vitality of Artemia salina was investigated by measuring the Lethal Time LT50 of the crustaceans in the presence of different sodium salts solutions at room temperature and at the same ionic strength as natural seawater. Fluoride, thiocyanate and perchlorate are the most toxic agents, while chloride, bromide and sulfate are well tolerated. The rates of oxygen consumption of brine shrimps were recorded in mixed NaCl+NaF or NaCl+NaSCN solutions as a function of time. The results are discussed in terms of the Hofmeister series, and suggest that, besides the biochemical processes that involve F(-), SCN(-) and ClO4(-), the different physico-chemical properties of the strong kosmotropic and chaotropic anions may contribute in determining their strong toxicity for A. salina. PMID:25978674

  12. Anion effects to deliver enhanced iridium catalysts for hydrogen isotope exchange processes.

    PubMed

    Kennedy, Alan R; Kerr, William J; Moir, Rory; Reid, Marc

    2014-10-28

    Synthesis of a series of iridium(I) complexes of the type [(COD)Ir(IMes)(PPh3)]X (X = BF4, OTf, and BArF) has been established. Application of these species in mild hydrogen isotope exchange processes revealed more efficient catalysis and, further, a wider solvent scope when employing larger, more weakly coordinating counterions. PMID:25208265

  13. Anion formation by neutral resonant ionization

    NASA Astrophysics Data System (ADS)

    Vogel, John S.

    2015-10-01

    A collision-radiation model of the cesium plasma that forms within a pitted or recessed sample in a Middleton-type sputter ion source showed that excited states of Cs formed. These excited states of neutral Cs undergo resonant electron transfer with neutral sputtered atoms of AMS samples to produce the accelerated anions. Numerous reported effects from over 30 years are readily explained by this mechanism, including several that puzzled Middleton.

  14. Cooling dynamics of carbon cluster anions

    NASA Astrophysics Data System (ADS)

    Shiromaru, H.; Furukawa, T.; Ito, G.; Kono, N.; Tanuma, H.; Matsumoto, J.; Goto, M.; Majima, T.; Sundén, A. E. K.; Najafian, K.; Pettersson, M. S.; Dynefors, B.; Hansen, K.; Azuma, T.

    2015-09-01

    A series of ion storage experiments on small carbon cluster anions was conducted to understand size-dependent cooling processes. The laser-induced delayed electron detachment time profile show clear even/odd alternation due to the presence of the electronic cooling. The time evolution of the internal energy distribution was simulated for Cn- (n=4 to 7) with a common procedure taking vibrational and electronic cooling into account.

  15. Lowest autodetachment state of the water anion

    NASA Astrophysics Data System (ADS)

    Houfek, Karel; Čížek, Martin

    2016-05-01

    The potential energy surface of the ground state of the water anion H2O- is carefully mapped using multireference CI calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O-+H2 and OH-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The autodetachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O- + H2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slighly off the linear geometry and is separated by a saddle from the autodetachment region. The autodetachment region is directly accessible from the OH-+H asymptote. For the molecular geometries in the autodetachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  16. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  17. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  18. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

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

    1987-01-01

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

  19. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

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

  20. Functional analyses and treatment of precursor behavior.

    PubMed

    Najdowski, Adel C; Wallace, Michele D; Ellsworth, Carrie L; MacAleese, Alicia N; Cleveland, Jackie M

    2008-01-01

    Functional analysis has been demonstrated to be an effective method to identify environmental variables that maintain problem behavior. However, there are cases when conducting functional analyses of severe problem behavior may be contraindicated. The current study applied functional analysis procedures to a class of behavior that preceded severe problem behavior (precursor behavior) and evaluated treatments based on the outcomes of the functional analyses of precursor behavior. Responding for all participants was differentiated during the functional analyses, and individualized treatments eliminated precursor behavior. These results suggest that functional analysis of precursor behavior may offer an alternative, indirect method to assess the operant function of severe problem behavior. PMID:18468282