WorldWideScience

Sample records for catalyst precursor anions

  1. Low temperature catalyst-assisted pyrolysis of polymer precursors to ...

    Indian Academy of Sciences (India)

    2017-11-15

    Nov 15, 2017 ... https://doi.org/10.1007/s12034-017-1495-9. Low temperature catalyst-assisted pyrolysis of polymer precursors to carbon. RAMYA ARAGA, SURESH KALI and CHANDRA S SHARMA. ∗. Creative and Advanced Research Based On Nanomaterials (CARBON) Laboratory, Department of Chemical ...

  2. Anionic PPV polymerization from the sulfinyl precursor route : Block copolymer formation from sequential addition of monomers

    NARCIS (Netherlands)

    Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

    2013-01-01

    The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to

  3. Non-PGM cathode catalysts for fuel cell application derived from heat treated heteroatomic amines precursors

    Energy Technology Data Exchange (ETDEWEB)

    Serov, Alexey; Halevi, Barr; Artyushkova, Kateryna; Atanassov, Plamen B; Martinez, Ulises A

    2017-04-25

    A method of preparing M-N--C catalysts utilizing a sacrificial support approach and inexpensive and readily available polymer precursors as the source of nitrogen and carbon is disclosed. Exemplary polymer precursors include non-porphyrin precursors with no initial catalytic activity. Examples of suitable non-catalytic non-porphyrin precursors include, but are not necessarily limited to low molecular weight precursors that form complexes with iron such as 4-aminoantipirine, phenylenediamine, hydroxysuccinimide, ethanolamine, and the like.

  4. Catalytic Hydrodechlorination of Trichlorobenzenes with Pd(PhenCl2 as Catalyst Precursor

    Directory of Open Access Journals (Sweden)

    Guanlin Zhang

    2015-01-01

    Full Text Available We reported the catalytic hydrodechlorination (HDC of trichlorobenzenes by an organometallic compound Pd(PhenCl2 as a catalyst precursor. The catalyst precursor was prepared by chemical coordination reaction and characterized by FTIR and 1H NMR techniques. The HDC performance of Pd(PhenCl2 as catalyst precursor was evaluated on 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes (TCBs. All TCBs could be converted to dechlorination products with high conversion. Products distribution was closely related with the substrate structures and C-Cl bond energies. A reasonable reaction mechanism was also proposed.

  5. The neuroleptic chlorpromazine inhibits the cationic and stimulates the anionic phospholipid precursor synthesis in human lymphocytes.

    Science.gov (United States)

    Staub, M; Stenger, A; Sumeg, R; Spasokoukotskaja, T; Fairbanks, L D; Simmonds, H A; Keszler, G

    2006-01-01

    The widely used neuroleptic drug chlorpromazine (CPZ) influences membrane functions at the levels of ionic channels and receptors as shown. Here we show the effect of short term treatments by CPZ (30 microM), on the nucleotide-containing phospholipid precursors in human lymphocyte primary cultures. During 60 minutes incubation of the cells, the CDP-ethanolamine (CDP-EA) content was only slightly reduced (87 to 76 pmol/10(6) cells), the amount of CDP-choline (CDP-Ch) was inhibited totally (from 25 to 0 pmol) upon the treatment with 30 microM CPZ under the same conditions. It has been shown earlier, that dCTP can be used as well as CTP for biosynthesis of phospholipids. Thus, the separation of the corresponding ribo- and deoxyribo-liponucleotides was developed. CPZ almost completely inhibited the synthesis of both dCDP-EA and dCDP-Ch under the same conditions The synthesis of the activated liponucleotide precursors, can be measured by incorporation of extracellular 14C-dCyt into both dCDP-EA and dCDP-Ch, as shown earlier. While the cationic deoxyribo-liponucleotide content (dCDP-Ch, dCDP-EA) was decreased, the labelling of the anionic phospholipid precursor dCDP-diacylglycerol (dCDP-DAG) was enhanced several times, it could be labelled only in the presence of CPZ from 14C-dCyd. Thus, a principal disturbance of the membrane phospholipid synthesis is presented (i.e., inhibition of the cationic and enhancement of the anionic dCDP-DAG synthesis). This profound influence on the membrane phospholipids by chlorpromazine, might be the primary effect that contributes to the wide spectrum of CPZ effects on neuronal cells.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Transesterification of propylene glycol methyl ether in chromatographic reactors using anion exchange resin as a catalyst.

    Science.gov (United States)

    Oh, Jungmin; Sreedhar, Balamurali; Donaldson, Megan E; Frank, Timothy C; Schultz, Alfred K; Bommarius, Andreas S; Kawajiri, Yoshiaki

    2016-09-30

    Reactive chromatography using an anion exchange resin is proposed for a transesterification reaction of propylene glycol methyl ether (DOWANOL™ PM) with ethyl acetate to produce propylene glycol methyl ether acetate (DOWANOL™ PMA). This reaction is studied in batch and chromatographic reactors catalyzed by an anion exchange resin. Several anion exchange resins are tested and compared based on the performance of resin as an adsorbent and a catalyst. A chromatographic column is packed with a selected catalyst, AMBERLITE™ IRA904, and both reaction and chromatographic elution are studied at different temperatures and feed concentrations. The resulting chromatograms are fitted to a mathematical model to obtain adsorption equilibrium and reaction kinetic parameters by the inverse method. Compared to esterification investigated in a previous study, transesterification has advantages such as a higher conversion at lower temperature and easy removal of the byproduct which may lead to higher productivity. Deactivation of anion exchange resins is observed and potential solutions are suggested. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Effect of Chlorine precursor in surface and cataytic properties of Fe/TiO2 Catalysts

    OpenAIRE

    López, Tessi; Pecchi, Gina; Moreno, Abel; García Fierro, José Luis; Gómez, R.; Reyes, P.

    2002-01-01

    Titania-supported iron (1wt%) catalysts were prepared by the sol-gel method using different gelation pH (3 and 9), metal precursors (FeCl2 and FeCl3) and calcination temperatures (873 and 1073K). Characterization data of calcined catalysts revealed that in all samples the dominant iron species is Fe3+ and the crystalline phase of the TiO2 substrate depends on the gelation pH and the metal precursor used. It was found that in the Fe/TiO2 ex-FeCl3 samples an important part of the iron ions beca...

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

    Science.gov (United States)

    Chung, Hoon Taek; Zelenay, Piotr

    2015-10-27

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

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

    DEFF Research Database (Denmark)

    Kondrat, Simon A.; Smith, Paul J.; Wells, Peter P.

    2016-01-01

    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 th...

  11. Catalytic hydrodechlorination of triclosan using a new class of anion-exchange-resin supported palladium catalysts.

    Science.gov (United States)

    Han, Bing; Liu, Wen; Li, Jingwen; Wang, Jin; Zhao, Dongye; Xu, Rui; Lin, Zhang

    2017-09-01

    We prepared a new class of anion-exchange-resin supported Pd catalysts for efficient hydrodechlorination of triclosan in water. The catalysts were prepared through an initial ion-exchange uptake of PdCl 4 2- and subsequent reduction of Pd(II) to Pd(0) nanoparticles at ambient temperature. Two standard strong-base anion exchange resins (IRA-900 and IRA-958) with different matrices (polystyrene and polyacrylic) were chosen as the supports. SEM and TEM images showed that Pd(0) nanoparticles were evenly attached on the resin surface with a mean size of 3-5 nm. The resin supported Pd catalysts (Pd@IRA-900 and Pd@IRA-958) were able to facilitate rapid and complete hydrodechlorination of triclosan. At a Pd loading of 2.0 wt.%, the observed pseudo first-order rate constant (k obs ) was 1.25 ± 0.06 and 1.6 ± 0.1 L/g/min for Pd@IRA-900 and Pd@IRA-958, respectively. The catalysts were more resistant to Cl - poisoning and natural organic matter fouling than other supported-Pd catalysts. The presence of 10 mM NaCl suppressed the k obs value by 31% and 23% for Pd@IRA-900 and Pd@IRA-958, whereas the presence of humic acid at 30 mg/L as TOC lowered the rates by 28% and 27%, respectively. The better performance of Pd@IRA-958 was attributed to the polymeric matrix properties (i.e., hydrophobicity, pore size, and surface area) as well as Pd particle size. GC/MS analyses indicated that very low concentrations of chlorinated intermediates were detected in the early stage of the hydrodechlorination process, with 2-phenoxyphenol being the main byproduct. The catalysts can be repeatedly used in multiple operations without significant bleeding. The catalysts eliminate the need for calcination in preparing conventional supported catalysts, and the resin supports conveniently facilitate control of Pd loading and material properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts

    Science.gov (United States)

    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

  13. Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

    Directory of Open Access Journals (Sweden)

    Arshid M. Ali

    2015-01-01

    Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

  14. Lanthanide amidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare-earth oxide thin films.

    Science.gov (United States)

    Edelmann, Frank T

    2009-08-01

    For decades, the organometallic chemistry of the rare earth elements was largely dominated by the cyclopentadienyl ligand and its ring-substituted derivatives. A hot topic in current organolanthanide chemistry is the search for alternative ligand sets which are able to satisfy the coordination requirements of the large lanthanide cations. Among the most successful approaches in this field is the use of amidinate ligands of the general type [RC(NR')(2)](-) (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe(3)) which can be regarded as steric cyclopentadienyl equivalents. Closely related are the guanidinate anions of the general type [R(2)NC(NR')(2)](-) (R = alkyl, SiMe(3); R' = alkyl, cycloalkyl, aryl, SiMe(3)). Two amidinate or guanidinate ligands can coordinate to a lanthanide ion to form a metallocene-like coordination environment which allows the isolation and characterization of stable though very reactive amide, alkyl, and hydride species. Mono- and trisubstituted lanthanide amidinate and guanidinate complexes are also readily available. Various rare earth amidinates and guanidinates have turned out to be very efficient homogeneous catalysts e.g. for ring-opening polymerization reactions. Moreover, certain alkyl-substituted lanthanide tris(amidinates) and tris(guanidinates) were found to be highly volatile and could thus be promising precursors for ALD (= Atomic Layer Deposition) and MOCVD (= Metal-Organic Chemical Vapor Deposition) processes in materials science and nanotechnology. This tutorial review covers the success story of lanthanide amidinates and guanidinates and their transition from mere laboratory curiosities to efficient homogeneous catalysts as well as ALD and MOCVD precursors.

  15. Influence of Pd-precursor on the acetoxylation activity of Pd-Sb/TiO{sub 2} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ben-homeid, A. [Benghazi Univ. (Libyan Arab Jamahiriya). Chemistry Dept.; Kalevaru, V.N.; Radnik, J.; Luecke, B.; Martin, A. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany)

    2013-11-01

    The impact of palladium precursors (e.g. chloride-PdCl{sub 2}; acetate-Pd(OAc){sub 2}; nitrate-Pd(NO{sub 3}){sub 2}) on the catalytic properties of Pd-Sb/TiO{sub 2} catalysts used for acetoxylation of toluene has been investigated. The catalysts were characterized by different techniques such as N{sub 2}-adsorption (BET-surface area and pore volume), XRD, TEM, CO-Chemisorption and XPS for better understanding of the catalytic properties of the catalysts. The acetate and nitrate-type precursors exhibited higher surface areas, pore volumes and higher dispersion of Pd, but displayed poor performance compared to chloride precursor. TEM analysis indicated that the size of Pd particles depended upon the nature of Pd-precursor. Among the three, chloride precursor exhibited bigger Pd particles. XPS results revealed that all the fresh catalysts irrespective of Pd-precursor contained Pd in oxidized state (i.e. Pd{sup +2}), while in the spent catalysts such oxidized Pd species were reduced. The catalytic performance was found to depend strongly on the nature of precursor used. Among the three, the catalysts prepared from chloride-type precursor showed much higher overall catalytic activity (68%) than those of nitrate and/or acetate type precursors. Moreover, these two precursors (acetate and nitrate) gave higher total oxidation products due to oxidative decomposition of mainly acetic acid. Furthermore, the catalyst prepared from Cl-precursor revealed easy deactivation due to coke deposition and also due to loss of Pd in the near-surface-region. (orig.)

  16. Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

    Science.gov (United States)

    Wang, Renhu; Li, Junhua

    2010-06-01

    Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

  17. Carbon Supported Ag Nanoparticles as High Performance Cathode Catalyst for Anion Exchange Membrane Fuel Cell

    Directory of Open Access Journals (Sweden)

    Le eXin

    2013-09-01

    Full Text Available A solution phase-based nanocapsule method was successfully developed to synthesize non-precious 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 disc 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 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 oC.

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

    Directory of Open Access Journals (Sweden)

    Eftichia Papadopoulou

    2016-02-01

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

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

    Directory of Open Access Journals (Sweden)

    Britta Kämpken

    2012-07-01

    Full Text Available In this work the applicability of neopentasilane (Si(SiH34 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.

  20. Effect of the amount of catalyst and chain-initiator on the anionic Polymerization of {epsilon}-caprolactam

    Energy Technology Data Exchange (ETDEWEB)

    Chung, D.W.; Oh, Y.T.; Park, Y.T. [Suwon University, Suwon (Korea)

    2001-01-01

    Monomer casting nylons were synthesized by casting anionic polymerization of {epsilon}-caprolactam. Polymerization rates, molecular weights of the products and the conversions were determined while varying the content of catalysts in the range of 0.2{approx}0.6 mol% and 0.1{approx}1.0 mol% for initiator. The polymerization rates were enhanced as the ration of catalysts to initiator increased. The maximum molecular weight was observed when the ration of catalysts to initiator was 0.8, and as the ratio increased the molecular weight decreased. On the other hand, when the ratio of catalysts to initiator was below 0.8, the conversions and the molecular weights were abruptly diminished due to the termination of growing chain. (author). 11 refs., 3 figs.

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

    Energy Technology Data Exchange (ETDEWEB)

    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 as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been characterized by molecular beam mass spectrometry (MBMS), laser-induced fluorescence (LIF), 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 e.u., 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 Xray 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 (NICS), quantum theory of atoms in molecules (QTAIM), and natural bond orbital (NBO) methods.

  2. The Influence of the Anionic Counter-Ion on the Activity of Ammonium Substituted Hoveyda-Type Olefin Metathesis Catalysts in Aqueous Media

    Science.gov (United States)

    Gułajski, Łukasz; Grela, Karol

    Polar olefin metathesis catalysts, bearing an ammonium group are presented. The electron withdrawing ammonium group not only activates the catalysts electronically, but at the same time makes the catalysts more hydrophilic. Catalysts can be therefore efficiently used not only in traditional media, such as methylene chloride and toluene, but also in technical-grade alcohols, alcohol— water mixtures and in neat water. Finally, in this overview the influence of the anionic counter-ion on the activity of ammonium substituted Hoveyda-type olefin metathesis catalysts in aqueous media is presented.

  3. Molecular Mixed-Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts.

    Science.gov (United States)

    Suseno, Sandy; McCrory, Charles C L; Tran, Rosalie; Gul, Sheraz; Yano, Junko; Agapie, Theodor

    2015-09-14

    Well-defined mixed-metal [CoMn3 O4 ] and [NiMn3 O4 ] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analyzed by various techniques to gain insight into the structure-function relationships of the electrocatalysts' heterometallic composition. Depending on preparation conditions, the Co-Mn oxide was found to change metal composition during catalysis, while the Ni-Mn oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3 O4 cubane-like geometry was maintained in the absence of thermal treatment (2-Ni). In contrast, the thermally generated 3-Ni develops an oxide-like extended structure. Both 2-Ni and 3-Ni undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen-evolving complex in Photosystem II, including the MMn3 O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed metal oxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Improving the Energy Efficiency of Direct Formate Fuel Cells with a Pd/C-CeO2 Anode Catalyst and Anion Exchange Ionomer in the Catalyst Layer

    Directory of Open Access Journals (Sweden)

    Hamish Andrew Miller

    2018-02-01

    Full Text Available This article describes the development of a high power density Direct Formate Fuel Cell (DFFC fed with potassium formate (KCOOH. The membrane electrode assembly (MEA contains no platinum metal. The cathode catalyst is FeCo/C combined with a commercial anion exchange membrane (AEM. To enhance the power output and energy efficiency we have employed a nanostructured Pd/C-CeO2 anode catalyst. The activity for the formate oxidation reaction (FOR is enhanced when compared to a Pd/C catalyst with the same Pd loading. Fuel cell tests at 60 °C show a peak power density of almost 250 mW cm−2. The discharge energy (14 kJ, faradic efficiency (89% and energy efficiency (46% were determined for a single fuel charge (30 mL of 4 M KCOOH and 4 M KOH. Energy analysis demonstrates that removal of the expensive KOH electrolyte is essential for the future development of these devices. To compensate we apply for the first time a polymeric ionomer in the catalyst layer of the anode electrode. A homopolymer is synthesized by the radical polymerization of vinyl benzene chloride followed by amination with 1,4-diazabicyclo[2.2.2]octane (DABCO. The energy delivered, energy efficiency and fuel consumption efficiency of DFFCs fed with 4 M KCOOH are doubled with the use of the ionomer.

  5. Synthesis of biodiesel using local natural zeolite as heterogeneous anion exchange catalyst

    Science.gov (United States)

    Hartono, R.; Wijanarko, A.; Hermansyah, H.

    2018-04-01

    Production of biodiesel using homogen catalyst: alkaline catalysts, acid catalysts, biocatalysts, and supercritical methanol are very inefficient, because these catalysts have a very high cost production of biodiesel and non-ecofriendly. The heterogeneous catalyst is then used to avoid adverse reaction of biodiesel production. The heterogeneous catalysts used is ion exchanger using natural zeolit catalists bayah banten (ZABBrht) and macroporous lewatit that can be used to produce biodiesel in the solid phase so that the separation is easier and can be used repeatedly. The results of biodiesel reach its optimum in engineering ion exchange catalyst natural zeolit bayah and macroporous lewatit which has been impregnated and calcinated at temperature 60 °C at reaction time 2 hours, are 94.8% and 95.24%, using 100 gr.KOH/100 mL Aquadest.

  6. Fluorescent phosphinimine as possible precursor to an anionic and fluorescent sensor for Tc-99

    Energy Technology Data Exchange (ETDEWEB)

    Arrigo, L.M.; Galenas, M.; Bassil, D.B.; Tucker, S.A.; Barnes, C.L. [Dept. of Chemistry, Univ. of Missouri, Columbia, MO (United States); Kannan, R. [Dept. of Radiology, Univ. of Missouri, Columbia, MO (United States); Katti, K.V. [Dept. of Radiology, Univ. of Missouri, Columbia, MO (United States); Dept. of Physics, Univ. of Missouri, Columbia, MO (United States); Univ. of Missouri Research Reactor (MURR), Univ. of Missouri, Columbia, MO (United States); Jurisson, S.S. [Dept. of Chemistry, Univ. of Missouri, Columbia, MO (United States); Dept. of Radiology, Univ. of Missouri, Columbia, MO (United States)

    2008-07-01

    The trimethylsilyl-protected phosphinimines (9-anthracenyl)Ph{sub 2}P=NSiMe{sub 3} and (1-naphthyl)Ph{sub 2}P=NSiMe{sub 3} and the ion pairs [(9-anthracenyl)Ph{sub 2}P=NH{sub 2}{sup +}][MO{sub 4}{sup -}] and [(1-naphthyl)Ph{sub 2}P=NH{sub 2}{sup +}][MO{sub 4}{sup -}] with M = Re or Tc were synthesized and characterized by {sup 1}H and {sup 31}P NMR, UV-Vis and fluorescence spectroscopy, elemental analysis, and/or single crystal X-ray diffraction. Radiochemical studies performed using {sup 99m}Tc and {sup 186}Re as the tracers for {sup 99}Tc and Re found the selectivity of the phosphiniminium cations for pertechnetate in the presence of a variety of anions found in the environment to be excellent. The crystallographic data reported for the structures are as follows: [(9-anthracenyl)Ph{sub 2}P=NH{sub 2}{sup +}][ReO{sub 4}{sup -}] (H{sub 21}C{sub 26}NO{sub 4}PRe) 2, monoclinic (P2{sub 1}/n), a = 11.3047(5) A, b = 16.3983(8) A, c = 12.2469(6) A, {beta} = 92.344(1) Z = 4; [(9-anthracenyl)Ph{sub 2}P=NH{sub 2}{sup +}][TcO{sub 4}{sup -}] (H{sub 21}C{sub 26}NO{sub 4}PTc) 3, monoclinic (P2{sub 1}/n), a = 11.3619(4) A, b = 12.2203(3) A, c = 25.7794(13) A, {beta} = 92.162(1) , Z = 4. (orig.)

  7. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    Science.gov (United States)

    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 (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Ana Raquel de la Osa

    2016-07-01

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

  9. Thermal decomposition of precursors and physicochemical characteristics of titania supported vanadia catalysts

    International Nuclear Information System (INIS)

    Nalbandian, Lori; Lemonidou, Angeliki A.

    2004-01-01

    Titania supported vanadia catalysts (2.5, 5, and 11 wt.% V 2 O 5 ) were prepared by a wet impregnation technique and their thermal behavior, morphology as well as redox properties were examined by thermal analysis methods thermogravimetry (TGA), differential scanning calorimetry (DSC), temperature programmed-evolved gas analysis with mass spectroscopy, (EGA-MS), scanning electron microscopy (SEM), and temperature programmed reduction (TPR). The two Eurocat samples EL10V1 and EL10V8 containing 1 and 8 wt.% V 2 O 5 were also characterized using the same techniques. Thermal decomposition of vanadium oxide precursors (ammonium vanadyl oxalate) supported on TiO 2 as evidenced by thermal analysis, occurs in three successive steps, which are influenced by the surrounding atmosphere (oxidative, reductive, and inert). The presence of tower-like vanadia crystals in the sample with the highest vanadia loading (11 wt.% V 2 O 5 ) was identified by SEM. The H 2 -TPR experiments revealed that the reduction temperature is a factor of the vanadia loading and the type of support. Vanadia species supported on Norton titania are more reducible that those supported on Eurocat titania

  10. Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic ...

    Indian Academy of Sciences (India)

    Unknown

    hydrotalcite anionic clay for Friedel–Crafts type benzylation reactions. VASANT R CHOUDHARY*, RANI JHA and PANKAJ A CHOUDHARI. Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune 411 008,. India.

  11. Engineering Favorable Morphology and Structure of Fe-N-C Oxygen-Reduction Catalysts through Tuning of Nitrogen/Carbon Precursors.

    Science.gov (United States)

    Gupta, Shiva; Zhao, Shuai; Ogoke, Ogechi; Lin, Ye; Xu, Hui; Wu, Gang

    2017-02-22

    Structures and morphologies of Fe-N-C catalysts are believed to be crucial because of the number of active sites and local bonding structures governing the overall catalyst performance for the oxygen reduction reaction (ORR). However, the knowledge how to rationally design catalysts is still lacking. By combining different nitrogen/carbon precursors, including polyaniline (PANI), dicyandiamide (DCDA), and melamine (MLMN), we aim to tune catalyst morphology and structure to facilitate the ORR. Instead of the commonly studied single precursors, multiple precursors were used during the synthesis; this provides a new opportunity to promote catalyst activity and stability through a likely synergistic effect. The best-performing Fe-N-C catalyst derived from PANI+DCDA is superior to the individual PANI or DCDA-derived ones. In particular, when compared to the extensively explored PANI-derived catalysts, the binary precursors have an increased half-wave potential of 0.83 V and an enhanced electrochemical stability in challenging acidic media, indicating a significantly increased number of active sites and strengthened local bonding structures. Multiple key factors associated with the observed promotion are elucidated, including the optimal pore size distribution, highest electrochemically active surface area, presence of dominant amorphous carbon, and thick graphitic carbon layers with more pyridinic nitrogen edge sites likely bonded with active atomic iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A Microstructural Investigation of Gas Atomized Raney Type Al-27.5 at.%Ni Catalyst Precursor Alloys

    OpenAIRE

    Mullis, AM; Bigg, TD; Adkins, NJ

    2015-01-01

    Quantitative image analysis has been used to investigate the phase composition of gas atomized powders of a Raney type Ni catalyst precursor alloys of composition Al-27.5 at.% Ni in the powder size range 150-212 μm. We find that there are considerable variations in phase composition both between powders from the same batch and as a function distance from the particle surface within individual particles. Such variations may have significant implications for the future production and uptake of ...

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

    Directory of Open Access Journals (Sweden)

    Shirley Nakagaki

    2016-02-01

    Full Text Available 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 (CO32− 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.

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

    Science.gov (United States)

    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

    2014-04-11

    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.

  15. Facile Synthesis of Effcient and Selective Ruthenium Olefin Metathesis Catalysts with Sulfonate and Phosphate Ligands

    OpenAIRE

    Teo, Peili; Grubbs, Robert H.

    2010-01-01

    A series of novel, air-stable ruthenium NHC catalysts with sulfonate and phosphate anions have been prepared easily in one pot at high yields using commercially available precursors. The catalysts were found to be effective for ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis. The catalysts showed higher cis-selectivity in olefin cross-metathesis reactions as compared to earlier known ruthenium-based olefin metathesis catalysts, with allylbenzene and cis-1...

  16. Electrocatalytic oxidation of meso-erythritol in anion-exchange membrane alkaline fuel cell on PdAg/CNT catalyst

    Science.gov (United States)

    Benipal, Neeva; Qi, Ji; McSweeney, Ryan F.; Liang, Changhai; Li, Wenzhen

    2018-01-01

    C-C bond cleavage during electrocatalytic oxidation of glycerol and C3+ polyols often occurs and can significantly affect the Faradaic efficiency, fuel utilization, and output power density of a direct polyol fuel cell, although this has not been deeply investigated. With the goal of acquiring new knowledge of C-C bond breaking of polyols, this study examines the electrocatalytic oxidation of a C4 polyol meso-erythritol on carbon nanotube supported Pd-based catalysts (Pd/CNT, PdAg/CNT, and PdAg3/CNT) in an anion-exchange membrane fuel cell (AEMFC). Our results show that PdAg/CNT improves the fuel efficiency of meso-erythritol oxidation by contributing to the C-C bond cleavage of meso-erythritol in C3 and C2 chemicals. Based on the analysis of electro-oxidation products and half-cell cyclic voltammetry (CV) of intermediates, a meso-erythritol electro-oxidation pathway has been proposed to demonstrate that Ag is likely to assist Pd to promote the cleavage of C-C bonds of meso-erythritol.

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

    Science.gov (United States)

    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. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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...

  19. In situ Generated Ruthenium Catalyst Systems Bearing Diverse N-Heterocyclic Carbene Precursors for Atom-Economic Amide Synthesis from Alcohols and Amines.

    Science.gov (United States)

    Cheng, Hua; Xiong, Mao-Qian; Cheng, Chuan-Xiang; Wang, Hua-Jing; Lu, Qiang; Liu, Hong-Fu; Yao, Fu-Bin; Chen, Cheng; Verpoort, Francis

    2018-02-16

    The transition-metal-catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom-economic process. Among various catalyst systems, in situ generated N-heterocyclic carbene (NHC)-based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron-deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR-scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=-7.8 ppm in the 1 H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors : Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

    NARCIS (Netherlands)

    Buntara, Teddy; Noel, Sébastien; Phua, Pim Huat; Melián-Cabrera, Ignacio; Vries, Johannes G. de; Heeres, Hero J.

    1,6-hexanediol (1) is an important polymer precursor for the polyester industry. In this paper, exploratory catalyst screening studies on the synthesis of 1 from 1,2,6-hexanetriol (2) are described via two different routes. The latter is available by a two-step procedure from 5-hydroxymethylfurfural

  1. Molecularly Tailored Nickel Precursor and Support Yield a Stable Methane Dry Reforming Catalyst with Superior Metal Utilization.

    Science.gov (United States)

    Margossian, Tigran; Larmier, Kim; Kim, Sung Min; Krumeich, Frank; Fedorov, Alexey; Chen, Peter; Müller, Christoph R; Copéret, Christophe

    2017-05-24

    Syngas production via the dry reforming of methane (DRM) is a highly endothermic process conducted under harsh conditions; hence, the main difficulty resides in generating stable catalysts. This can, in principle, be achieved by reducing coke formation, sintering, and loss of metal through diffusion in the support. [{Ni(μ 2 -OCHO)(OCHO)(tmeda)} 2 (μ 2 -OH 2 )] (tmeda = tetramethylethylenediamine), readily synthesized and soluble in a broad range of solvents, was developed as a molecular precursor to form 2 nm Ni(0) nanoparticles on alumina, the commonly used support in DRM. While such small nanoparticles prevent coke deposition and increase the initial activity, operando X-ray Absorption Near-Edge Structure (XANES) spectroscopy confirms that deactivation largely occurs through the migration of Ni into the support. However, we show that Ni loss into the support can be mitigated through the Mg-doping of alumina, thereby increasing significantly the stability for DRM. The superior performance of our catalytic system is a direct consequence of the molecular design of the metal precursor and the support, resulting in a maximization of the amount of accessible metallic nickel in the form of small nanoparticles while preventing coke deposition.

  2. Development of Ni-Based Catalysts Derived from Hydrotalcite-Like Compounds Precursors for Synthesis Gas Production via Methane or Ethanol Reforming

    Directory of Open Access Journals (Sweden)

    Ya-Li Du

    2017-02-01

    Full Text Available As a favorably clean fuel, syngas (synthesis gas production has been the focus of concern in past decades. Substantial literatures reported the syngas production by various catalytic reforming reactions particularly in methane or ethanol reforming. Among the developed catalysts in these reforming processes, Ni-based catalysts from hydrotalcite-like compounds (HTLcs precursors have drawn considerable attention for their preferable structural traits. This review covers the recent literature reporting syngas production with Ni-based catalysts from HTLc precursors via methane or ethanol reforming. The discussion was initiated with catalyst preparation (including conventional and novel means, followed by subsequent thermal treatment processes, then composition design and the addition of promoters in these catalysts. As Ni-based catalysts have thermodynamic potential to deactivate because of carbon deposition or metal sintering, measures for dealing with these problems were finally summarized. To obtain optimal catalytic performances and resultantly better syngas production, based on analyzing the achievements of the references, some perspectives were finally proposed.

  3. Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

    International Nuclear Information System (INIS)

    Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

    2013-01-01

    Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

  4. High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ping; Barkholtz, Heather M.; Wang, Ying; Xu, Weilin; Liu, Dijia; Zhuang, Lin

    2017-12-01

    We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.

  5. Preparation of highly dispersed Ru-Sn bimetallic supported catalysts from the single source precursors Cp(PPh32Ru-SnX3 (X = Cl or Br

    Directory of Open Access Journals (Sweden)

    Ana Cláudia Bernardes Silva

    2003-06-01

    Full Text Available In this work highly dispersed Ru-Sn bimetallic catalysts have been prepared from organobimetallic Cp(PPh32Ru-SnX3 (X = Cl or Br complexes. These single source precursors can be easily impregnated in high surface area supports, such as activated carbon and sol-gel SiO2, and upon controlled thermal treatment the ligands are released as volatile products resulting in the formation of the bimetallic system Ru-Sn. Catalytic reactions, such as hydrodechlorination of CCl4 and chlorobenzene and TPR (Temperature Programmed Reduction experiments carried out with these RuSn catalysts suggested a strong interaction between Ruthenium and Tin. Mössbauer measurements showed that these materials when exposed to air are immediately oxidized to form Sn (IV. It was shown that upon controlled reduction conditions with H2 it is possible to reduce selectively Sn to different oxidation states and different phases. The Sn oxidation state showed significant effect on the catalytic hydrogenation of 1,5-cyclooctadiene. The use of these single source precursors with a controlled decomposition/reduction procedure allows the preparation of unique catalysts with an intimate interaction between the components ruthenium and tin and the possibility of varying the Sn oxidation state around the Ru metal.

  6. Treatment of a non-azo dye aqueous solution by CWAO in continuous reactor using a Ni catalyst derived from hydrotalcite-like precursor

    Energy Technology Data Exchange (ETDEWEB)

    Vallet, Ana, E-mail: avallet@quim.ucm.es [Grupo de Catalisis y Procesos de Separacion (CyPS), Departamento de Ingenieria Quimica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Besson, Michele, E-mail: michele.besson@ircelyon.univ-lyon1.fr [IRCELYON, Institut de recherches sur la catalyse et l' environnement de Lyon, UMR5256 CNRS-Universite Lyon1, 2 Avenue Albert Einstein, F-69626 Villeurbanne Cedex (France); Ovejero, Gabriel; Garcia, Juan [Grupo de Catalisis y Procesos de Separacion (CyPS), Departamento de Ingenieria Quimica, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Ni supported over hydrotalcite calcined precursors as catalyst. Black-Right-Pointing-Pointer Catalytic wet air oxidation in trickle bed reactor for Basic Yellow 11 removal. Black-Right-Pointing-Pointer Dye removal depends on temperature, initial dye concentration and flow rate. Black-Right-Pointing-Pointer The catalyst proved to be stable and efficient for the dye degradation. - Abstract: Catalytic wet air oxidation (CWAO) of a Basic Yellow 11 (BY11) aqueous solution, chosen as a model of a hardly biodegradable non-azo dye was carried out in a continuous-flow trickle-bed reactor, using nickel supported over hydrotalcite precursor calcined at 550 Degree-Sign C. An increase in the reaction temperature (120-180 Degree-Sign C), and a decrease in dye concentration (1000-3000 ppm) or liquid flow rate (0.1-0.7 mL min{sup -1}) enhanced the CWAO performance in a 30 and 19% for the variation of the temperature and concentration respectively. After a small leaching observed within the first hours, the catalyst proved to be very stable during the 65-day reaction. The CWAO process was found to be very efficient, achieving BY11 conversion up to 95% and TOC conversion up to 85% at 0.1 mL min{sup -1} and 180 Degree-Sign C under 5 MPa air.

  7. Development physicochemical and catalytic characteristics of Mo-containing catalysts for hydrotreatment based on various supports. 1. Adsorption of molybdate anions on the support surface

    International Nuclear Information System (INIS)

    Lur'e, M.A.; Kurest, I.Z.; Krasnopol'skaya, S.M.; Reznikov, S.A.; Babikov, A.F.; Shmidt, F.K.

    1994-01-01

    The amounts of basic OH-groups were determined by means of exchange by F-ions and the adsorption of Mo from acid and alkali ammonium paramolybdate (APM) solutions was investigated on the surface of hydrated titanium dioxide, γ-Al 2 O 3 and palygorskite-montmorillonite clay. The process is adequately described by the exchange equation at pH value of APM solution in excess of the isoelectric point (IEP) of the surface. At opposite correlation between pH of the solution and IEP the Langmuir model is adaptable. They concluded, on experimental data, that in the latter case OH-groups replaced by molybdate-anion stage of synthesis of catalyst. 22 refs., 3 figs

  8. From trash to resource: recovered-Pd from spent three-way catalysts as a precursor of an effective photo-catalyst for H 2 production

    KAUST Repository

    Gombac, V.

    2016-01-06

    The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, using [Pd(Me2dazdt)2](I3)2 (Me2dazdt = N,N′-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through the selective and safe recovery of palladium from model exhaust three-way catalysts (TWCs), is reported here. The photo-catalyst prepared by the impregnation/photo-reduction of palladium on the support showed improved performance in H2 production from methanol and in glycerol photo-reforming compared to reference photo-catalysts obtained from conventional Pd-salts. The reported results represent a case of successful palladium “recovery and re-employment” and thus constitute an example of green chemistry by providing, in one route, the environmentally friendly recovery of a critical metal and its employment in the renewable energy field.

  9. Ni/SiO2 Catalyst Prepared with Nickel Nitrate Precursor for Combination of CO2 Reforming and Partial Oxidation of Methane: Characterization and Deactivation Mechanism Investigation

    Directory of Open Access Journals (Sweden)

    Sufang He

    2015-01-01

    Full Text Available The performance of Ni/SiO2 catalyst in the process of combination of CO2 reforming and partial oxidation of methane to produce syngas was studied. The Ni/SiO2 catalysts were prepared by using incipient wetness impregnation method with nickel nitrate as a precursor and characterized by FT-IR, TG-DTA, UV-Raman, XRD, TEM, and H2-TPR. The metal nickel particles with the average size of 37.5 nm were highly dispersed over the catalyst, while the interaction between nickel particles and SiO2 support is relatively weak. The weak NiO-SiO2 interaction disappeared after repeating oxidation-reduction-oxidation in the fluidized bed reactor at 700°C, which resulted in the sintering of metal nickel particles. As a result, a rapid deactivation of the Ni/SiO2 catalysts was observed in 2.5 h reaction on stream.

  10. Direct observations of dynamic PtCo interactions in fuel cell catalyst precursors at the atomic level using E(S)TEM.

    Science.gov (United States)

    Ward, M R; Theobald, B; Sharman, J; Boyes, E D; Gai, P L

    2018-02-01

    Reduction reactions in practical bimetallic platinum-cobalt electrode catalyst precursors containing platinum, cobalt and cobalt oxides in hydrogen at 200, 450 and 700 °C for 6 h have been studied in situ using an aberration corrected environmental (scanning) transmission electron microscope (AC E(S)TEM). Little difference was observed in reduction at 200 °C but during and after reduction at 450 °C, small nanoparticles less than 3 nm in diameter with tetragonal PtCo structures were observed and limited Pt 3 Co ordering could be seen on the surfaces of larger nanoparticles. During and after reduction at 700 °C, fully ordered Pt 3 Co and PtCo nanoparticles larger than 4 nm were produced and the average nanoparticle size almost trebled relative to the fresh precursor. After reduction at 450 and 700 °C, most nanoparticles were disordered platinum/cobalt alloys with fcc structure. After reduction at 700 °C many of the smallest nanoparticles disappeared suggesting Ostwald ripening had occurred. Mechanisms concerning the thermal transformation of mixed cobalt and platinum species are discussed, offering new insights into the creation of bimetallic platinum-cobalt nanoparticles in fuel cell catalysts. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

  11. Thermodynamic analysis and chemical vapor deposition of multi-walled carbon nanotubes from pre-heated CH4 using Fe2O3 particles as catalyst precursor

    Science.gov (United States)

    Altay, Melek Cumbul; Eroglu, Serafettin

    2013-02-01

    The present study aims to investigate influence of pre-heating of CH4 on the growth of multi-walled carbon nanotubes (MWCNTs) using Fe2O3 particles as catalyst precursor. Equilibrium thermodynamic analyses in the systems of FeCOH and CH were performed to better understand the reduction of Fe2O3 by CH4 and to identify intermediate species which might promote growth of MWCNTs at the temperature range of 1000-1300 K. It was found that CH4 acted as reducing agent for Fe2O3 catalyst precursor which transformed to Fe3O4, FeO, Fe and Fe3C phases. This result was found to be in agreement with the thermodynamic prediction at 1200 and 1300 K. SEM-EDS analysis revealed that un-preheated CH4 yielded MWCNTs at 1200 K and a dense C coating at 1300 K. It was also observed that carbon was not formed at temperatures in the range of 1050-1150 K. Whereas, MWCNTs were grown at this temperature range from CH4 pre-heated at 1200 K. This result was attributed to the intermediate hydrocarbons, especially to C6H6, formed during pre-heating stage as thermodynamic analysis suggested. Mean diameter of the synthesized tubes was found to increase with growth time and temperature.

  12. Lead nitroprusside: A new precursor for the synthesis of the multiferroic Pb{sub 2}Fe{sub 2}O{sub 5,} an anion-deficient perovskite

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Diego M. [Instituto de Química Inorgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, 4000 San Miguel de Tucumán (Argentina); Nieva, Gladys [Centro Atómico Bariloche, Instituto Balseiro, Comisión Nacional de Energía Atómica, Universidad Nacional de Cuyo, 8400 San Carlos de Bariloche (Argentina); Franco, Diego G. [Centro Atómico Bariloche, Instituto Balseiro, Comisión Nacional de Energía Atómica, Universidad Nacional de Cuyo, 8400 San Carlos de Bariloche (Argentina); Instituto de Investigaciones en Fisicoquímica de Córdoba (INFIQC – CONICET), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Gómez, María Inés [Instituto de Química Inorgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, 4000 San Miguel de Tucumán (Argentina); and others

    2013-08-15

    In order to investigate the formation of multiferroic oxide Pb{sub 2}Fe{sub 2}O{sub 5}, the thermal decomposition of Pb[Fe(CN){sub 5}NO] has been studied. The complex precursor and the thermal decomposition products were characterized by IR and Raman spectroscopy, thermal analysis, powder X-ray diffraction (PXRD), scanning electron microscopy and magnetic measurements. The crystal structure of Pb[Fe(CN){sub 5}NO] was refined by Rietveld analysis. It crystallizes in the orthorhombic system, space group Pnma. The thermal decomposition in air produces highly pure Pb{sub 2}Fe{sub 2}O{sub 5} as final product. This oxide is an anion deficient perovskite with an incommensurate superstructure. The magnetic measurements confirm that Pb{sub 2}Fe{sub 2}O{sub 5} shows a weak ferromagnetic signal probably due to disorder in the perfect antiferromagnetic structure or spin canting. The estimated ordering temperature from the fit of a phenomenological model was 520 K. The SEM images reveal that the thermal decomposition of Pb[Fe(CN){sub 5}NO] produces Pb{sub 2}Fe{sub 2}O{sub 5} with small particle size. - Highlights: • Pb[Fe(CN){sub 5}NO] was synthesized and characterized. • Pb[Fe(CN){sub 5}NO] belongs to orthorhombic crystal system, space group Pnma. • Pb{sub 2}Fe{sub 2}O{sub 5} was obtained by thermal decomposition of Pb[Fe(CN){sub 5}NO]. • Pb{sub 2}Fe{sub 2}O{sub 5} is a weak ferromagnet due to spin canting. • Ordering temperature of Pb{sub 2}Fe{sub 2}O{sub 5} from the fit of a phenomenological model was 520 K. - Graphical abstract: Field cooling (FC) and zero field cooling (ZFC) magnetization curves at H = 10 and 1000 Oe for Pb{sub 2}Fe{sub 2}O{sub 5} obtained at 750 °C. Remnant magnetization after applying H = 1 T, FC procedure at 0.8 Oe. The fitted expression (see text) yield an ordering temperature T{sub o} = 520 K. Display Omitted.

  13. ZIF-8 with Ferrocene Encapsulated: A Promising Precursor to Single-Atom Fe Embedded Nitrogen-Doped Carbon as Highly Efficient Catalyst for Oxygen Electroreduction.

    Science.gov (United States)

    Wang, Jinpeng; Han, Guokang; Wang, Liguang; Du, Lei; Chen, Guangyu; Gao, Yunzhi; Ma, Yulin; Du, Chunyu; Cheng, Xinqun; Zuo, Pengjian; Yin, Geping

    2018-03-05

    The oxygen reduction reaction (ORR) plays an important role in the fields of energy storage and conversion technologies, including metal-air batteries and fuel cells. The development of nonprecious metal electrocatalysts with both high ORR activity and durability to replace the currently used costly Pt-based catalyst is critical and still a major challenge. Herein, a facile and scalable method is reported to prepare ZIF-8 with single ferrocene molecules trapped within its cavities (Fc@ZIF-8), which is utilized as precursor to porous single-atom Fe embedded nitrogen-doped carbon (Fe-N-C) during high temperature pyrolysis. The catalyst shows a half-wave potential (E 1/2 ) of 0.904 V, 67 mV higher than commercial Pt/C catalyst (0.837 V), which is among the best compared with reported results for ORR. Significant electrochemical properties are attributed to the special configuration of Fc@ZIF-8 transforming into a highly dispersed iron-nitrogen coordination moieties embedded carbon matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Sol-gel 3-glycidoxypropyltriethoxysilane finishing on different fabrics: The role of precursor concentration and catalyst on the textile performances and cytotoxic activity.

    Science.gov (United States)

    Plutino, M R; Colleoni, C; Donelli, I; Freddi, G; Guido, E; Maschi, O; Mezzi, A; Rosace, G

    2017-11-15

    In this paper, the influence of 3-glycidoxypropyltriethoxysilane (GPTES) based organic-inorganic coatings on the properties of treated textile fabrics was studied. All experimental results were deeply analyzed and thereafter correlated with the employed silica precursor concentration and with the presence of the BF 3 OEt 2 (Boron trifluoride diethyl etherate), used as epoxy ring opening catalyst. SEM analysis, FT-IR spectroscopy, X-ray Photoelectron Spectroscopy (XPS), thermogravimetric analysis (TGA) and washing fastness tests of the sol-gel treated cotton fabric samples were firstly exploited in order to characterize the morphological and structural features of the achieved coatings. Finally, the influence of the resulting nanohybrid coatings was explored in terms of abrasion resistance, tensile strength and elongation properties of treated cotton, polyester and silk fabrics. The catalyst amounts seem to strongly improve the formation of coatings, but still they do not influence the wear resistance of treated textile fabrics to the same extent. Indeed, it was found that increasing catalyst/GPTES ratio leads to a more cross linked inorganic 3D-network. GPTES itself was not found to affect the bulk properties of the selected textile and the resulting coatings were not so rigid to hardly modify the mechanical properties of the treated samples. Finally, it is worth mentioning that in all case the obtained 3-glycidoxypropyltriethoxysilane-based chemical finishing have shown no cytotoxic effects on human skin cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jose F. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; La Porte, Nathan T. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Mauck, Catherine M. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Wasielewski, Michael R. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA

    2017-01-01

    The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI-˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 Vvs.SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI-˙*) oxidation potential of -2.1 Vvs.SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO2 reduction catalysts. However, once an electron is transferred from NDI-˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we have designed a molecular triad system comprising an NDI-˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO)3carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI-˙ to NDI-˙* is followed by ultrafast reduction of DPA to DPA-˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI-˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.

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

    KAUST Repository

    Renard, Laetitia

    2014-03-06

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

  17. Preparation of Pt-Re/Vulcan carbon nanocomposites using a single-source molecular precursor and relative performance as a direct methanol fuel cell electrooxidation catalyst.

    Science.gov (United States)

    Anderson, Angela D; Deluga, Gregg A; Moore, Joshua T; Vergne, Matthew J; Hercules, David M; Kenik, Edward A; Lukehart, C M

    2004-09-01

    Pt-Re/Vulcan carbon powder nanocomposites have been prepared with total metal loadings of 18 wt.% and 40 wt.% using a new non-cluster (1:1)-PtRe bimetallic precursor as the source of metal. Pt-Re nanoparticles having an average diameter of ca. 6 nm and atomic stoichiometry near 1:1 are formed. TEM, on-particle HR-EDS, and powder XRD data are consistent with the formation of Pt-Re alloy nanoparticles having a hexagonal unit cell with cell constants of a = 2.77 A and c = 4.47 A. A nanocomposite prepared at higher total metal loading under more rigorous thermal treatment also contains Pt-Re alloy nanoparticles having a fcc unit cell structure (a = 3.95 A). The precise dependence of Pt-Re nanocrystal structure on the thermal history of the nanocomposite specimen has not been investigated in detail. While these Pt-Re/carbon nanocomposites are active as anode catalysts in operating direct methanol fuel cells, the measured performance is less than that of commercial Pt-Ru/carbon catalysts and has marginal practical importance.

  18. Continuous-Flow O-Alkylation of Biobased Derivatives with Dialkyl Carbonates in the Presence of Magnesium-Aluminium Hydrotalcites as Catalyst Precursors.

    Science.gov (United States)

    Cattelan, Lisa; Perosa, Alvise; Riello, Piero; Maschmeyer, Thomas; Selva, Maurizio

    2017-04-10

    The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal, solketal, glycerol carbonate, furfuryl alcohol and tetrahydrofurfuryl alcohol with non-toxic dialkyl carbonates (dimethyl and diethyl carbonate) were explored under continuous-flow (CF) conditions in the presence of three Na-exchanged Y- and X-faujasites (FAUs) and four Mg-Al hydrotalcites (HTs). Compared to previous etherification protocols mediated by dialkyl carbonates, the reported procedure offers substantial improvements not only in terms of (chemo)selectivity but also for the recyclability of the catalysts, workup, ease of product purification and, importantly, process intensification. Characterisation studies proved that both HT30 and KW2000 hydrotalcites acted as catalyst precursors: during the thermal activation pre-treatments, the typical lamellar structure of the hydrotalcite was broken down gradually into a MgO-like phase (periclase) or rather a magnesia-alumina solid solution, which was the genuine catalytic phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Effect of the nickel precursor on the impregnation and drying of γ-Al2O3 catalyst bodies: a UV-vis and IR micro-spectroscopic study

    NARCIS (Netherlands)

    Espinosa Alonso, L.; de Jong, K.P.; Weckhuysen, B.M.

    2008-01-01

    The elemental preparation steps of impregnation and drying of Ni/g-Al2O3 catalyst bodies have been studied by combining UV-vis and IR microspectroscopy. The influence of the number of chelating ligands in [Ni(en)x(H2O)6-2x]2+ precursor complexes (with en ) ethylenediamine and x ) 0-3) has been

  20. A practical synthesis of xylo- and arabinofuranoside precursors by diastereoselective reduction using Corey-Bakshi-Shibata catalyst.

    Science.gov (United States)

    Utley, Lynn M; Maldonado, Jessica; Awad, Ahmed M

    2018-01-02

    The Corey-Bakshi-Shibata (CBS) catalyst provides an efficient mechanism to reduce ketones and achieve desired enantiopure alcohols. Herein, the diastereoselective reduction of C-2' and C-3'-keto ribofuranoside derivatives to the corresponding arabino- and xylofuranosides in greater than 95% diastereomeric excess is reported. The stereo-directed substitution with an azido group as well as the synthesis of prodrugs cytarabine and vidarabine are also described. The reported strategy offers superior diastereoselectivity, shorter reaction times, and obviates cooling required with comparable protocols involving achiral reductants.

  1. The fluxional amine gold(III) complex as an excellent catalyst and precursor of biologically active acyclic carbenes.

    Science.gov (United States)

    Montanel-Pérez, Sara; Herrera, Raquel P; Laguna, Antonio; Villacampa, M Dolores; Gimeno, M Concepción

    2015-05-21

    A new amine gold(III) complex [Au(C6F5)2(DPA)]ClO4 with the di-(2-picolyl)amine (DPA) ligand has been synthesised. In the solid state the complex has a chiral amine nitrogen because the ligand coordinates to the gold centre through one nitrogen atom from a pyridine and through the NH moiety, whereas in solution it shows a fluxional behaviour with a rapid exchange between the pyridine sites. This complex can be used as an excellent synton to prepare new gold(III) carbene complexes by the reaction with isocyanide CNR. The resulting gold(III) derivatives have unprecedented bidentate C^N acyclic carbene ligands. All the complexes have been spectroscopically and structurally characterized. Taking advantage of the fluxional behaviour of the amine complex, its catalytic properties have been tested in several reactions with the formation of C-C and C-N bonds. The complex showed excellent activity with total conversion, without the presence of a co-catalyst, and with a catalyst loading as low as 0.1%. These complexes also present biological properties, and cytotoxicity studies have been performed in vitro against three tumour human cell lines, Jurkat (T-cell leukaemia), MiaPaca2 (pancreatic carcinoma) and A549 (lung carcinoma). Some of them showed excellent cytotoxic activity compared with the reference cisplatin.

  2. Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. Probing the limits of anion `noncoordination` via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study

    Energy Technology Data Exchange (ETDEWEB)

    Jia, L.; Yang, X.; Stern, C.L.; Marks, T.J. [Northwestern Univ., Evanston, IL (United States)

    1997-03-04

    The silyl-functionalized/protected derivatives of the tetrakis(perfluoroaryl)borate anions, B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) have been synthesized, and a series of stable, highly reactive Zr and Th ion-paired methyl and hydride catalysts have been isolated using these anions. In contrast, the analogous B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene methyl complexes are not stable at room temperature; however, B(C{sub 6}F{sub 5}){sub 4}{sup -}-based zirconocene hydride complexes can be isolated. The relative coordinative ability of the series of fluoroarylborates with respect to metallocene cations has been evaluated on the basis of spectroscopic and reactivity data. The polymerization activity of the zirconocene catalysts reaches a maximum when B(C{sub 6}F{sub 4}TBS){sub 4}{sup -} and B(C{sub 6}F{sub 4}TIPS){sub 4}{sup -} are counteranions, and the polymerization activity of the Zr constrained geometry catalyst reaches a maximum in aromatic solvents due to arene coordination when B(C{sub 6}F{sub 5}){sub 4}{sup -} is the counteranion. 37 refs., 5 figs., 7 tabs.

  3. Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

    2013-11-01

    Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

  4. Supported chromium-molybdenum and tungsten sulfide catalysts

    International Nuclear Information System (INIS)

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

    1988-01-01

    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. Anion-π catalysis.

    Science.gov (United States)

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

    2014-02-05

    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

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

    KAUST Repository

    Riache, Nassima

    2015-01-01

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

  7. Steam Reforming of Bio-Ethanol to Produce Hydrogen over Co/CeO2 Catalysts Derived from Ce1−xCoxO2−y Precursors

    Directory of Open Access Journals (Sweden)

    Yanyong Liu

    2016-02-01

    Full Text Available A series of Ce1−xCoxO2−y precursors were prepared by homogeneous precipitation using urea as a precipitant. The Co/CeO2 catalysts obtained from the Ce1−xCoxO2−y precursors were used for the steam reforming of ethanol to produce hydrogen. Co ions could enter the CeO2 lattices to form Ce1−xCoxO2−y mixed oxides at x ≤ 0.2 using the homogeneous precipitation (hp method. CeO2 was an excellent support for Co metal in the steam reforming of ethanol because a strong interaction between support and metal (SISM exists in the Co/CeO2 catalysts. Because Co/CeO2 (hp prepared by homogeneous precipitation possessed a high BET surface area and small Co metal particles, Co/CeO2 (hp showed a higher ethanol conversion than the Co/CeO2 catalysts prepared using the co-precipitation (cp method and the impregnation (im method. The selectivity of CO2 over Co/CeO2 (hp increased with increasing reaction temperature at from 573 to 673 K, and decreased with increasing reaction temperature above 673 K due to the increase of CO formation. The carbonaceous deposits formed on the catalyst surface during the reaction caused a slow deactivation in the steam reforming of ethanol over Co/CeO2 (hp. The catalytic activity of the used catalysts could be regenerated by an oxidation-reduction treatment, calcined in air at 723 K and then reduced by H2 at 673 K.

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

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Eero eSalminen

    2014-02-01

    Full Text Available 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.

  10. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  11. Halloysite-derived nitrogen doped carbon electrocatalysts for anion exchange membrane fuel cells

    Science.gov (United States)

    Lu, Yaxiang; Wang, Lianqin; Preuß, Kathrin; Qiao, Mo; Titirici, Maria-Magdalena; Varcoe, John; Cai, Qiong

    2017-12-01

    Developing the low-cost, highly active carbonaceous materials for oxygen reduction reaction (ORR) catalysts has been a high-priority research direction for durable fuel cells. In this paper, two novel N-doped carbonaceous materials with flaky and rod-like morphology using the natural halloysite as template are obtained from urea nitrogen source as well as glucose (denoted as GU) and furfural (denoted as FU) carbon precursors, respectively, which can be directly applied as metal-free electrocatalysts for ORR in alkaline electrolyte. Importantly, compared with a benchmark Pt/C (20wt%) catalyst, the as-prepared carbon catalysts demonstrate higher retention in diffusion limiting current density (after 3000 cycles) and enhanced methanol tolerances with only 50-60mV negative shift in half-wave potentials. In addition, electrocatalytic activity, durability and methanol tolerant capability of the two N-doped carbon catalysts are systematically evaluated, and the underneath reasons of the outperformance of rod-like catalysts over the flaky are revealed. At last, the produced carbonaceous catalysts are also used as cathodes in the single cell H2/O2 anion exchange membrane fuel cell (AEMFC), in which the rod-like FU delivers a peak power density as high as 703 mW cm-2 (vs. 1106 mW cm-2 with a Pt/C benchmark cathode catalyst).

  12. Green synthesis of iron nanoparticles and their application as a Fenton-like catalyst for the degradation of aqueous cationic and anionic dyes

    OpenAIRE

    Shahwan, Talal; Abu-Sirriah, Sadieh; Nairat, Muath; Boyacı, Ezel; Eroğlu, Ahmet E.; Scott, Thomas B.; Hallam, Keith R.

    2011-01-01

    Iron nanoparticles were produced using extracts of green tea leaves (GT-Fe NPs). The materials were characterized using TEM, SEM/EDX, XPS, XRD, and FTIR techniques and were shown to contain mainly iron oxide and iron oxohydroxide. The obtained nanoparticles were then utilized as a Fenton-like catalyst for decolorization of aqueous solutions containing methylene blue (MB) and methyl orange (MO) dyes. The related experiments investigated the removal kinetics and the effect of concentration for ...

  13. Reactive layer-by-layer deposition of poly(ethylene imine) and a precursor of TiO2: influence of the sodium chloride concentration on the film growth, interaction with hexacyanoferrate anions, and particle distribution in the film.

    Science.gov (United States)

    Ladhari, Nadia; Ringwald, Christian; Ersen, Ovidiu; Florea, Ileana; Hemmerlé, Joseph; Ball, Vincent

    2011-06-21

    Films prepared according to a layer-by-layer (LBL) manner find increasing importance in many applications such as coatings with dedicated optical or electronic properties, particularly when including nanomaterials. An alternative way to prepare such hybrid layer-by-layer coatings is to perform sol-gel chemistry in a layer-by-layer manner. In this article, we highlight the importance of the NaCl concentration as a parameter to control the growth as well as the properties of LBL films made from poly(ethylene imine) as the organic counterpart and titanium IV (bisammoniumlactato)dihydroxyde ([Ti(lac)(2)(OH)(2)](2-)) as the precursor of TiO(2). An increase in the sodium chloride concentration leads to the faster growth of the film and to a decrease in the number of hexacyanoferrate anions remaining in the film after a buffer rinse. This may be due to a progressive increase in the fraction of negatively charged TiO(2) as suggested by transmission electron microscopy. In the presence of 0.5 M NaCl, the fraction of TiO(2) is close to 60% in mass. As a surprising finding, the films produced from 0.15 M NaCl are not homogeneously filled with TiO(2) even if the film is produced in an LBL fashion. The increased concentration of TiO(2) at the film-solution interface could constitute a barrier for the incorporation of the negatively charged redox probe. © 2011 American Chemical Society

  14. The impact of copper in LaNi{sub 1-x}Cu{sub x}O{sub 3} perovskite-like structures used as catalyst precursors for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Vlach, K.; Hoang, D.L.; Armbruster, U.; Martin, A. [Leibniz-Institut fuer Katalyse e.V. an der Universitaet Rostock (Germany)

    2013-11-01

    This work deals with the synthesis of perovskite-like catalyst precursors (LaNi{sub 1-x}Cu{sub x}O{sub 3} with x = 0, 0.2, 0.5, 0.8, 1). These precursors were used to catalyse the dry reforming of methane (DRM) reaction carried out at 973 K, CH{sub 4}/CO{sub 2} = 1 and a GHSV = 18,000 ml/g/h. The precursors were transformed during the course of the reaction to give Ni-Cu/La{sub 2}O{sub 3} solids. We found out that the activity increases with raising Ni content but small Cu admixture suppresses the coke formation substantially. XRD and TEM measurements showed that the transformation led to the formation of small metallic Ni and/or Cu particles. In addition also alloying can be observed. The best catalytic system with respect to activity and suppressed carbon deposition was Ni{sub 0.8}-Cu{sub 0.2}/La{sub 2}O{sub 3} (X{sub CH4} = 61%, X{sub CO2} = 67%). (orig.)

  15. Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

    Science.gov (United States)

    McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

    2017-04-26

    A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

  16. Synthesis of self-supported non-precious metal catalysts for oxygen reduction reaction with preserved nanostructures from the polyaniline nanofiber precursor

    DEFF Research Database (Denmark)

    Hu, Yang; Zhao, Xiao; Huang, Yunjie

    2013-01-01

    Non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) are an active subject of recent research on proton exchange membrane fuel cells. In this study, we report a new approach to preparation of self-supported and nano-structured NPMCs using pre-prepared polyaniline (PANI...

  17. Performance of polyethylene based radiation grafted anion exchange membrane with polystyrene-b-poly (ethylene/butylene)-b-polystyrene based ionomer using NiCo2O4 catalyst for water electrolysis

    Science.gov (United States)

    Gupta, Gaurav; Scott, Keith; Mamlouk, Mohamed

    2018-01-01

    A soluble anion exchange ionomer with high OH- ion conductivity comparable to that of H+ conductivity of Nafion is synthesised by chloromethylation of polystyrene-b-poly (ethylene/butylene)-b-polystyrene (SEBS) and used with NiCo2O4 electro-catalyst for water electrolysis. The ionomer has an ion exchange capacity of 1.9 mmol g-1 and ionic conductivity of 0.14 S cm-2 at 50 °C. The cell voltage at 20 °C at 100 mA cm-2 is 1.77 and 1.72 V in, 0.1 and 1.0 M NaOH, respectively, for an optimum loading of 10 mg cm-2 NiCo2O4. At 10 mg cm-2 NiCo2O4 electrolyser cell performance is at least equal to or superior to that of IrO2 at 2 mg cm-2 with excellent stability over 1 h. When the catalyst is sprayed on the GDL instead of CCM, the performance is further improved to 1.65 V at 100 mA cm-2 at 60 °C & 0.1 M KOH. The limited AEM electrolyser performance when operating with deionised water in comparison to PEM and alkaline electrolyser arises from the sluggish OER in the AEM environment equivalent to pH of 11.5 and the two orders of magnitude lower HER activity with respect to acid medium combined with the high Tafel slope of 120 mV dec-1.

  18. Effect of Catalyst Precursor and Its Pretreatment on the Amount of ß-Pd Hydride Phase and HDS Activity of Pd-Pt/Silica-Alumina

    Czech Academy of Sciences Publication Activity Database

    Vít, Zdeněk; Gulková, Daniela; Kaluža, Luděk; Boaro, M.

    2014-01-01

    Roč. 146, SI (2014), s. 213-220 ISSN 0926-3373. [International Conference on Environmental Catalysis /7./. Lyon, 02.09.2012-06.09.2012] R&D Projects: GA ČR GA104/09/0751; GA ČR GAP106/11/0902 Institutional support: RVO:67985858 Keywords : Pd-Pt catalyst * hydrodesulfurization * Pd hydride Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 7.435, year: 2014

  19. Co-generation of electricity and syngas on proton-conducting solid oxide fuel cell with a perovskite layer as a precursor of a highly efficient reforming catalyst

    Science.gov (United States)

    Wan, Tingting; Zhu, Ankang; Guo, Youmin; Wang, Chunchang; Huang, Shouguo; Chen, Huili; Yang, Guangming; Wang, Wei; Shao, Zongping

    2017-04-01

    In this study, a proton conducting solid oxide fuel cell (layered H+-SOFC) is prepared by introducing a La2NiO4perovskite oxide with a Ruddlesden-Popper structure as a catalyst layer onto a conventional NiO + BaZr0.4Ce0.4Y0.2O3-δ (NiO + BZCY4) anode for in situ CO2 dry reforming of methane. The roles of the La2NiO4 catalyst layer on the reforming activity, coking tolerance, electrocatalytic activity and operational stability of the anodes are systematically studied. The La2NiO4 catalyst layer exhibits greater catalytic performance than the NiO + BZCY4 anode during the CO2 dry reforming of methane. An outstanding coking resistance capability is also demonstrated. The layered H+-SOFC consumes H2 produced in situ at the anode and delivers a much higher power output than the conventional cell with the NiO + BZCY4 anode. The improved coking resistance of the layered H+-SOFC results in a steady output voltage of ∼0.6 V under a constant current density of 200 mA cm-2. In summary, the H+-SOFC with La2NiO4 perovskite oxide is a potential energy conversion device for CO2 conversion and utilization with co-generation of electricity and syngas.

  20. SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

    Directory of Open Access Journals (Sweden)

    Seyed Mehdi Sajjadi

    2015-05-01

    Full Text Available Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH and zirconyl nitrate solution (ZNS, was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS. FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

  1. Syngas production from CO2-reforming of CH4 over sol-gel synthesized Ni-Co/Al2O3-MgOZrO2 nanocatalyst: effect of ZrO2 precursor on catalyst properties and performance

    International Nuclear Information System (INIS)

    Sajjadi, Seyed Mehdi; Haghighi, Mohammad; Rahmani, Farhad

    2015-01-01

    Ni-Co/Al 2 O 3 -MgO-ZrO 2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO 2 -reforming of CH 4 . XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH 4 and CO 2 conversions were 97.2 and 99% at 850 °C, respectively. Furthermore, NCAMZZNS demonstrated a stable yield with H 2 /CO close to unit value during the 1440 min stability test. (author)

  2. Model Ziegler-type hydrogenation catalyst precursors, [(1,5-COD)M(mu-O2C8H15)]2 (M = Ir and Rh): synthesis, characterization, and demonstration of catalytic activity en route to identifying the true industrial hydrogenation catalysts.

    Science.gov (United States)

    Alley, William M; Girard, Chase W; Ozkar, Saim; Finke, Richard G

    2009-02-02

    The compounds [(1,5-COD)M(mu-O2C8H15)]2 (COD = cyclooctadiene, M = Ir (1) or Rh (2), O2C8H15 = 2-ethylhexanoate) were synthesized by addition of Bu3NH(2-ethylhexanoate) or Na(2-ethylhexanoate) to acetone suspensions of [(1,5-COD)Ir(mu-Cl)]2 or [(1,5-COD)Rh(mu-Cl)]2, respectively. The synthesis of such well-defined second and third row model precursors is key to determining the true nature of commercial Ziegler-type hydrogenation catalysts (i.e., catalysts made from the combination of a non-zerovalent, group 8-10 transition metal precatalyst and a trialkylaluminum cocatalyst), an unsolved, approximately 40 year old problem. The characterizations of 1 and 2 were accomplished by elemental analysis, melting point, FAB-MS, FT-IR, UV-vis, NMR spectroscopy, and single crystal X-ray diffraction. The complexes, C32H54Ir2O4 and C32H54O4Rh2, are isostructural: monoclinic, P2(1)/n, Z = 4. The lattice constants for 1 are a = 15.7748(5) A, b = 9.8962(3) A, c = 20.8847(7) A, beta = 108.408(2) degrees. The lattice constants for 2 are a = 15.7608(4) A, b = 9.9032(3) A, c = 20.8259(5) A, beta = 108.527(1) degrees. Complexes 1 and 2 are dimeric, bridged by the 2-ethylhexanoates, and with one 1,5-COD ligand bound to each metal. The formally 16 electron metal atoms are in square ligand planes with dihedral angles between the planes of 56.5 degrees for 1 and 58.1 degrees for 2. The M-M distances of 3.2776(2) and 3.3390(4) A for 1 and 2, respectively, fall in the range of similar structures thought to have some M-M interaction despite the lack of a formal M-M bond. Demonstration that active Ziegler-type hydrogenation catalysts are made when 1 or 2 combine with AlEt3 is provided, results that open the door to the use of 1 and 2 as well-defined third and second row congeners, respectively, of Ziegler-type hydrogenation catalysts. These compounds have proven important in addressing the previously unsolved problem of the true nature of the catalyst in industrial Ziegler-type hydrogenation

  3. Synthesis of non-symmetrically sulphonated phosphine sulphonate based Pd(II) catalyst salts for olefin polymerisation reactions.

    Science.gov (United States)

    Anselment, Timo M J; Anderson, Carly E; Rieger, Bernhard; Boeddinghaus, M Bele; Fässler, Thomas F

    2011-09-07

    Direct sulphonation of 2-(diphenylphosphino)benzenesulphonic acid was extensively studied. The non-symmetrically functionalised reaction products obtained, related to the widely applied water soluble phosphine ligands m,m,m-TPPTS and m,m-TPPDS, display chelating κ(2)-(P,O)-coordination to Pd(II) metal centres. Phase transfer reaction of rac-o,m-TPPDS as the potassium salt with 18-crown-6 and complexation to Pd(II) gives the novel anionic catalyst precursor [K(18-crown-6)](2)[κ(2)(P,O){rac-o,m-TPPDS}PdMeCl] suitable for olefin polymerisation reactions. Ethene homo- and co-polymerisation reactions with polar functionalised olefins were investigated with this anionic phosphine sulphonate Pd(II)-based pre-catalyst salt. This journal is © The Royal Society of Chemistry 2011

  4. Palladium Catalyzed Heck Arylation of 2,3-Dihydrofuran—Effect of the Palladium Precursor

    Directory of Open Access Journals (Sweden)

    Adam Morel

    2014-06-01

    Full Text Available Heck arylation of 2,3-dihydrofuran with iodobenzene was carried out in systems consisting of different palladium precursors (Pd2(dba3, Pd(acac2, PdCl2(cod, [PdCl(allyl]2, PdCl2(PhCN2, PdCl2(PPh32 and ionic liquids (CILs with L-prolinate or L-lactate anions. All the tested CILs caused remarkable increases of the conversion values and in all of the reactions 2-phenyl-2,3-dihydrofuran (3 was obtained as the main product with a yield of up to 59.2%. The highest conversions of iodobenzene were achieved for the [PdCl(allyl]2 precursor. Formation of Pd(0 nanoparticles, representing the resting state of the catalyst, was evidenced by TEM.

  5. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  6. La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

    Science.gov (United States)

    Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

    La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

  7. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes

    2012-01-01

    Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared...

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

    Science.gov (United States)

    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

  9. Co-Assembled Supported Catalysts: Synthesis of Nano-Structured Supported Catalysts with Hierarchic Pores through Combined Flow and Radiation Induced Co-Assembled Nano-Reactors

    OpenAIRE

    Galip Akay

    2016-01-01

    A novel generic method of silica supported catalyst system generation from a fluid state is presented. The technique is based on the combined flow and radiation (such as microwave, thermal or UV) induced co-assembly of the support and catalyst precursors forming nano-reactors, followed by catalyst precursor decomposition. The transformation from the precursor to supported catalyst oxide state can be controlled from a few seconds to several minutes. The resulting nano-structured micro-porous s...

  10. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Song, Peng-Yuan; Xu, Ming; Zhang, Wei-De, E-mail: zhangwd@scut.edu.cn

    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.

  12. Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials

    Directory of Open Access Journals (Sweden)

    Peter Hesemann

    2014-04-01

    Full Text Available The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA, mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches.

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

    Science.gov (United States)

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

    2003-12-30

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

  14. Thermoset precursor

    International Nuclear Information System (INIS)

    Yamamoto, Y.

    1983-04-01

    This invention pertains to a distinctive thermoset precursor which is prepared by mixing a resin composition (A) which can be hardened by ionizing radiation, and a resin composition (B) which can be hardened by heat but cannot be hardened by, or is resistant to, ionizing radiation, and by coating or impregnating a molding or other substrate with a sheet or film of this mixture and irradiating this with an ionizing radiation. The principal components of composition (A) and (B) can be the following: (1) an acrylate or methacrylate and an epoxy resin and an epoxy resin hardener; (2) an unsaturated polyester resin and epoxy resin and an epoxy resin hardener; (3) a diacrylate or dimethacrylate or polyethylene glycol and an epoxy resin; (4) an epoxy acrylates or epoxy methacrylate obtained by the addition reaction of epoxy resin and acrylic or methacrylic acid

  15. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

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

    Science.gov (United States)

    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. Copyright © 2015. Published by Elsevier B.V.

  17. The Use of C-MnO2 as Hybrid Precursor Support for a Pt/C-MnxO1+x Catalyst with Enhanced Activity for the Methanol Oxidation Reaction (MOR

    Directory of Open Access Journals (Sweden)

    Alessandro H.A. Monteverde Videla

    2015-07-01

    Full Text Available Platinum (Pt nanoparticles are deposited on a hybrid support (C-MnO2 according to a polyol method. The home-made catalyst, resulted as Pt/C-MnxO1+x, is compared with two different commercial platinum based materials (Pt/C and PtRu/C. The synthesized catalyst is characterized by means of FESEM, XRD, ICP-MS, XPS and μRS analyses. MnO2 is synthesized and deposited over a commercial grade of carbon (Vulcan XC72 by facile reduction of potassium permanganate in acidic solution. Pt nanoparticles are synthesized on the hybrid support by a polyol thermal assisted method (microwave irradiation, followed by an annealing at 600 °C. The obtained catalyst displays a support constituted by a mixture of manganese oxides (Mn2O3 and Mn3O4 with a Pt loading of 19 wt. %. The electro-catalytic activity towards MOR is assessed by RDE in acid conditions (0.5 M H2SO4, evaluating the ability to oxidize methanol in 1 M concentration. The synthesized Pt/C-MnxO1+x catalyst shows good activity as well as good stability compared to the commercial Pt/C based catalyst.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-02-20

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov

    2009-03-03

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

  1. A kinetic and spectroscopic study on the copper catalyzed oxidative coupling polymerization of 2,6-dimethylphenol. X-ray structure of the catalyst precursor tetrakis(N-methylimidazole)bis(nitrato)copper(II)

    NARCIS (Netherlands)

    Baesjou, PJ; Driessen, WL; Challa, G; Reedijk, J

    1996-01-01

    The complex of copper(II) nitrate with N-methylimidazole (Nmiz) ligand has been studied as a catalyst for the oxidative coupling of 2,6-dimethylphenol by means of kinetic and spectroscopic measurements. The order of the reaction in copper is fractional and depends on the N/Cu ratio and the base/Cu

  2. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula as shown in the accompanying diagram where R is branched lower alkyl, such as t-butyl.

  3. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin J. (Evanston, IL); Ja, Li (Chicago, IL); Yang, Xinmin (Evanston, IL)

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-01

    A method is described for 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 and 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.

  5. Chelated ruthenium catalysts for Z-selective olefin metathesis.

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H

    2011-06-08

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands that catalyze highly Z-selective olefin metathesis. A very simple and convenient procedure for the synthesis of such catalysts has been developed. Intramolecular C-H bond activation of the NHC ligand, promoted by anion ligand substitution, forms the appropriate chelate for stereocontrolled olefin metathesis.

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

    Indian Academy of Sciences (India)

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

  7. [(≢SiO)TaVCl2Me2]: A well-defined silica-supported tantalum(V) surface complex as catalyst precursor for the selective cocatalyst-free trimerization of ethylene

    KAUST Repository

    Chen, Yin

    2012-10-22

    On the surface of it: In the absence of co-catalyst, a well-defined silica-supported surface organometallic complex [(≢SiO)Ta VCl2Me2] selectively catalyzes the oligomerization of ethylene. The use of surface organometallic species allows three different pathways to be determined for the reduction of TaV to TaIII species under pressure of ethylene. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Metallocene catalyst containing bulky organic group

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin J. (Evanston, IL); Ja, Li (Chicago, IL); Yang, Xinmin (Evanston, IL)

    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.

  9. Metallocene catalyst containing bulky organic group

    Science.gov (United States)

    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.

  10. Syngas production from CO{sub 2}-reforming of CH{sub 4} over sol-gel synthesized Ni-Co/Al{sub 2}O{sub 3}-MgOZrO{sub 2} nanocatalyst: effect of ZrO{sub 2} precursor on catalyst properties and performance

    Energy Technology Data Exchange (ETDEWEB)

    Sajjadi, Seyed Mehdi; Haghighi, Mohammad; Rahmani, Farhad, E-mail: haghighi@sut.ac.ir [Reactor and Catalysis Research Center, Sahand University of Technology, Tabriz (Iran, Islamic Republic of)

    2015-05-15

    Ni-Co/Al{sub 2}O{sub 3}-MgO-ZrO{sub 2} nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO{sub 2}-reforming of CH{sub 4}. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH{sub 4} and CO{sub 2} conversions were 97.2 and 99% at 850 °C, respectively. Furthermore, NCAMZZNS demonstrated a stable yield with H{sub 2}/CO close to unit value during the 1440 min stability test. (author)

  11. EFFECTS OF CATALYST MORPHOLOGY ON HYDROTREATING REACTIONS

    Directory of Open Access Journals (Sweden)

    TYE CHING THIAN

    2008-08-01

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

  12. Influence of cobalt precursor and of its decomposition on the synthesis of cobalt nano-particles on silica for the optimization of the Fischer-Tropsch catalysts; Influence du precurseur de cobalt et de sa decomposition sur la synthese de nanoparticules de cobalt sur silice dans le cadre de l'optimisation des catalyseurs Fischer-Tropsch

    Energy Technology Data Exchange (ETDEWEB)

    Girardon, J.S.; Khodakov, A.Y.; Constant-Griboval, A. [Universite des sciences et technologies de Lille, Lab. de catalyse de Lille, UMR 8010, 59 - Villeneuve D' Ascq (France)

    2004-07-01

    In order to synthesize Fischer-Tropsch catalysts more active and selective in heavy hydrocarbons, the understanding at the molecular level of the chemical processes which occur during synthesis is a strategic stake. This work is based in one hand on the use of different cobalt precursors (acetate (Ac) and nitrate (N)) and in another hand on the influence of the decomposition temperature of these precursors on the formation of cobalt nano-particles. An UV-visible study shows that the impregnated cobalt coming from the two types of precursors is in an octahedral environment before its decomposition. The XRD, UV-visible and XANES-EXAFS studies show, after decomposition in air (400 C, 5 hours), that the sample prepared from cobalt nitrate (N400) presents a Co{sub 3}O{sub 4} phase. This phase is not detected in the case of the cobalt acetate (Ac400). These observations are in agreement with the results of the catalytic tests which show that the solid N400 is eight times more than the solid Ac400. A softer decomposition at 170 C during 70 hours of the cobalt acetate (Ac170) has allowed to minimize the formation of cobalt silicate for Co{sub 3}O{sub 4} and to increase of more than three times the catalytic activity. In the case of cobalt nitrate, the XRD analysis of the solids obtained after a softer decomposition (150 C and 100 C) has revealed a decrease of the size of the cobalt nano-particles. The catalytic conversion remains the same than with N400 but a better C{sub 5}{sup +} selectivity is observed. (O.M.)

  13. Anionic and zwitterionic copper(I) complexes incorporating an anionic N-heterocyclic carbene decorated with a malonate backbone: synthesis, structure and catalytic applications.

    Science.gov (United States)

    César, Vincent; Barthes, Cécile; Farré, Yoann C; Cuisiat, Stéphane V; Vacher, Bernard Y; Brousses, Rémy; Lugan, Noël; Lavigne, Guy

    2013-05-28

    The anionic malonate-derived N-heterocyclic carbenes (maloNHCs) react cleanly and rapidly with copper chloride to generate the anionic complexes of type [(maloNHC)CuCl]·Li, which crystallize in the solid state either in an oligomeric trimer arrangement or in polymeric helixes depending on the substitution pattern and the solvent. Ten zwitterionic heteroleptic Cu(I) complexes combining the anionic maloNHC and a neutral imidazol-2-ylidene are also obtained in a very selective manner and fully characterized. Whereas the anionic complexes are relatively active catalysts for the hydrosilylation of carbonyl compounds, the zwitterionic complexes reveal to be efficient and extremely robust pre-catalysts for the intramolecular cyclopropanation reaction of a diazo ester and outperform the corresponding cationic Cu(i) complexes with classical imidazol-2-ylidenes.

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

    Science.gov (United States)

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

    2017-09-12

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

  15. Formation of carbon nanosheets via simultaneous activation and catalytic carbonization of macroporous anion-exchange resin for supercapacitors application.

    Science.gov (United States)

    Peng, Hui; Ma, Guofu; Sun, Kanjun; Mu, Jingjing; Zhang, Zhe; Lei, Ziqiang

    2014-12-10

    Two-dimensional mesoporous carbon nanosheets (CNSs) have been prepared via simultaneous activation and catalytic carbonization route using macroporous anion-exchange resin (AER) as carbon precursor and ZnCl2 and FeCl3 as activating agent and catalyst, respectively. The iron catalyst in the skeleton of the AER may lead to carburization to form a sheetlike structure during the carbonization process. The obtained CNSs have a large number of mesopores, a maximum specific surface area of 1764.9 m(2) g(-1), and large pore volume of 1.38 cm(3) g(-1). As an electrode material for supercapacitors application, the CNSs electrode possesses a large specific capacitance of 283 F g(-1) at 0.5 A g(-1) and excellent rate capability (64% retention ratio even at 50 A g(-1)) in 6 mol L(-1) KOH. Furthermore, CNSs symmetric supercapacitor exhibits specific energies of 17.2 W h kg(-1) at a power density of 224 W kg(-1) operated in the voltage range of 0-1.8 V in 0.5 mol L(-1) Na2SO4 aqueous electrolyte, and outstanding cyclability (retains about 96% initial capacitance after 5000 cycles).

  16. Silica supported nickel catalysts : Tracer studies.

    OpenAIRE

    Sharratt, Andrew Paul.

    1991-01-01

    A series of silica supported catalysts were prepared by impregnation of the support materials with a nickel(II) nitrate precursor under standard conditions. The catalysts and silicas were characterised using temperature programmed reduction (TPR) techniques, neutron diffraction, small angle neutron scattering, and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR). These analyses revealed one significant variable in the silicas:- the surface concentration of strained siloxane ring...

  17. Potentiometric anion selective sensors

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Reinhoudt, David

    1999-01-01

    In comparison with selective receptors (and sensors) for cationic species, work on the selective complexation and detection of anions is of more recent date. There are three important components for a sensor, a transducer element, a membrane material that separates the transducer element and the

  18. Degradation of anionic surfactants using the reactor based on dielectric barrier discharge

    Directory of Open Access Journals (Sweden)

    Aonyas Munera Mustafa

    2016-01-01

    Full Text Available Two anionic surfactants (sodium lauryl sulfate - SDS and sodium dodecylbenzenesulfonate - SDBS were treated with dielectric barrier discharge. Loss of surfactant activity, decrease of chemical oxygen demand and total organic carbon as well as lower toxicity of degradation products were determined. Effects of catalysts - hydrogen peroxide and iron (II, on parameters mentioned above, were determined. Catalysts affect the degradation of SDBS and in the case of SDS catalysts have no effect on degradation. Both catalysts induce the decrease of COD and TOC values. Toxicity of solutions after the plasma treatment is lower in all the systems tested. [Projekat Ministarstva nauke Republike Srbije, br. OI 172030

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

    Science.gov (United States)

    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

  20. Catalysts preparing

    International Nuclear Information System (INIS)

    Normatov, I.Sh.; Mirsaidov, U.M.

    2003-01-01

    One of the base area of zeolites industry using is catalysis. The catalytic properties of zeolites use in the carbonated reactions in the petrochemistry. Last years zeolite catalysts use in oxidative-reduction processes

  1. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

  2. Photo-oxidation catalysts

    Science.gov (United States)

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

    2009-07-14

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

  3. Catalyst containing oxygen transport membrane

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    2014-01-01

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

  6. Co-Assembled Supported Catalysts: Synthesis of Nano-Structured Supported Catalysts with Hierarchic Pores through Combined Flow and Radiation Induced Co-Assembled Nano-Reactors

    Directory of Open Access Journals (Sweden)

    Galip Akay

    2016-05-01

    Full Text Available A novel generic method of silica supported catalyst system generation from a fluid state is presented. The technique is based on the combined flow and radiation (such as microwave, thermal or UV induced co-assembly of the support and catalyst precursors forming nano-reactors, followed by catalyst precursor decomposition. The transformation from the precursor to supported catalyst oxide state can be controlled from a few seconds to several minutes. The resulting nano-structured micro-porous silica supported catalyst system has a surface area approaching 300 m2/g and X-ray Diffraction (XRD-based catalyst size controlled in the range of 1–10 nm in which the catalyst structure appears as lamellar sheets sandwiched between the catalyst support. These catalyst characteristics are dependent primarily on the processing history as well as the catalyst (Fe, Co and Ni studied when the catalyst/support molar ratio is typically 0.1–2. In addition, Ca, Mn and Cu were used as co-catalysts with Fe and Co in the evaluation of the mechanism of catalyst generation. Based on extensive XRD, Scanning Electron Microscopy (SEM and Transmission Electron Microscopy (TEM studies, the micro- and nano-structure of the catalyst system were evaluated. It was found that the catalyst and silica support form extensive 0.6–2 nm thick lamellar sheets of 10–100 nm planar dimensions. In these lamellae, the alternate silica support and catalyst layer appear in the form of a bar-code structure. When these lamellae structures pack, they form the walls of a micro-porous catalyst system which typically has a density of 0.2 g/cm3. A tentative mechanism of catalyst nano-structure formation is provided based on the rheology and fluid mechanics of the catalyst/support precursor fluid as well as co-assembly nano-reactor formation during processing. In order to achieve these structures and characteristics, catalyst support must be in the form of silane coated silica nano

  7. Highly dispersed metal catalyst

    Science.gov (United States)

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

    2016-11-08

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

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

    African Journals Online (AJOL)

    effect on the catalyst structure and eventual catalytic behaviour of the reduced metal. Worley and coworkers5,6 investigated the effect of Rh precursor materials on alumina-supported catalysts and found that the catalysts prepared by using Rh(NO3)3 were more easily reduced to metallic Rh0 than samples prepared using.

  9. Bimetal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Ng, K. Y. Simon; Salley, Steve O.; Wang, Huali

    2017-10-03

    A catalyst comprises a carbide or nitride of a metal and a promoter element. The metal is selected from the group consisting of Mo, W, Co, Fe, Rh or Mn, and the promoter element is selected from the group consisting of Ni, Co, Al, Si, S or P, provided that the metal and the promoter element are different. The catalyst also comprises a mesoporous support having a surface area of at least about 170 m.sup.2 g.sup.-1, wherein the carbide or nitride of the metal and the promoter element is supported by the mesoporous support, and is in a non-sulfided form and in an amorphous form.

  10. Catalyst Architecture

    DEFF Research Database (Denmark)

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

    2014-01-01

    How can architecture promote the enriching experiences of the tolerant, the democratic, and the learning city - a city worth living in, worth supporting and worth investing in? Catalyst Architecture comprises architectural projects, which, by virtue of their location, context and their combination...... of programs, have a role in mediating positive social and/or cultural development. In this sense, we talk about architecture as a catalyst for: sustainable adaptation of the city’s infrastructure appropriate renovation of dilapidated urban districts strengthening of social cohesiveness in the city development...

  11. Alum an Efficient Catalyst for Erlenmeyer Synthesis

    African Journals Online (AJOL)

    NICO

    found to be useful precursors for the synthesis of amino acids,2 peptides,3 and ... tuted imidazoles,21h etc. However, there are no examples of the use of alum as a catalyst for the synthesis of azlactone deriva- tives. 2. Result and Discussion .... 12 P.S. Rao and R.V. Venkataratnam, Indian J. Chem, 1994, 33B, 984–985.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan, Song; Kirby, S.; Schmidt, E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    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.

  13. Impregnation alternatives for Fe-based coal liquefaction catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, R.K.; Armstong, B.T.; Givens, E.N. [Univ. of Kentucky, Lexington, KY (United States)

    1994-12-31

    Because of the cost effective and environmentally compatible nature of Fe, attention has been directed towards improving the utilization of this metal in direct coal liquefaction. Among the several factors thought to affect catalyst activity, much of this work has focused on dispersion. Weller and Pelipetz reported the importance of catalyst dispersion, based on experiments with a wide variety of catalysts in solvent-free liquefaction studies. And in the presence of solvent, other studies have demonstrated the advantages of adding the precursor by impregnation over its addition in the form of particulates. In general, a high surface/volume ratio, along with intimate contact between the active catalyst and coal, are thought to be the controlling factors. Dispersion, as normally inferred from changes in catalyst activity, may be affected by the mode of addition, the presence of solvent, and the initial composition of the precursor (e.g., soluble organometallics); and for coal-impregnated catalyst precursors, the choice of impregnation solvent and impregnation conditions. A variety of innovative strategies have been developed to introduce catalyst precursors to the liquefaction reaction while seeking to maintain particle size and distribution. These have included the use of emulsions and colloids, direct addition of ultra-fine particles to the slurry`s addition of oil soluble organometallics and carbonyls, ion exchange and impregnating the coal. This paper describes the results of liquefaction experiments carried out with the impregnation of subbituminous coal with iron.

  14. Coal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kroenig, W.

    1944-02-11

    Some considerations in the selection of a catalyst for the liquid phase of coal hydrogenation are discussed. Some of the previous history of such selections is mentioned. At one stage of the development, the principal catalyst had been iron sulfate (FeSO/sub 4/.7H/sub 2/O). Later, for reasons of cost and availability of large supplies, selections had turned to mixtures of iron sulfate and one or another of some iron oxide- and aluminum oxide-containing byproducts of aluminum manufacture, namely Bayermasse, Luxamsse, or Lautamasse. Much of the discussion centered on optimal proportions for such mixtures, particularly as related to pH values of resulting coal pastes. Upper Silesian coal was more alkaline than Ruhr coal, and Bayermasse, etc., were quite alkaline. Thus, since the iron sulfate served as a partial neutralizer for the coal as well as a catalyst, it seemed necessary to increase the proportions of iron sulfate in the catalyst mixture when processing coal of greater alkalinity. A further reason for a greater proportion of iron sulfate seemed to be that most of the catalytic activity of the iron came from the ferrous iron of iron sulfate rather than from the ferric iron of the other materials. Ferrous-ferric ratios also seemed to indicate that Luxmasse or Lautamasse might be better catalyst components than Bayermasse but their water content sometimes caused handling problems, so Bayermasse had been more widely used. Formation of deposits in the preheater was more likely due to the Bayermasse than to the iron sulfate; sodium sulfide could help to prevent them.

  15. Identification of inorganic anions by gas chromatography/mass spectrometry.

    Science.gov (United States)

    Sakayanagi, Masataka; Yamada, Yaeko; Sakabe, Chikako; Watanabe, Kunio; Harigaya, Yoshihiro

    2006-03-10

    Inorganic anions were identified by using gas chromatography/mass spectrometry (GC/MS). Derivatization of the anions was achieved with pentafluorobenzyl p-toluenesulphonate (PFB-Tos) as the reaction reagent and a crown ether as a phase transfer catalyst. When PFB-Br was used as the reaction reagent, the retention time of it was close to those of the derivatized inorganic anions and interfered with the analysis. In contrast, the retention time of PFB-Tos differed greatly from the PFB derivatives of the inorganic anions and the compounds of interest could be detected without interference. Although the PFB derivatives of SO4, S2O3, CO3, ClO4, and ClO3 could not be detected, the derivatives of F, Cl, Br, I, CN, OCN, SCN, N3, NO3, and NO2 were detected using PFB-Tos as the derivatizing reagent. The inorganic anions were detectable within 30 ng approximately, which is of sufficient sensitivity for use in forensic chemistry. Accurate mass number was measured for each PFB derivative by high-resolution mass spectrometry (HRMS) within a measurement error of 2 millimass units (mmu), which allowed determination of the compositional formula from the mass number. In addition, actual analysis was performed successively by our method using trial samples of matrix.

  16. Preparation of electrocatalysts by reduction of precursors with sodium citrate

    OpenAIRE

    Briskeby, Stein Trygve; Tsypkin, Mikhail; Tunold, Reidar; Sunde, Svein

    2014-01-01

    In this work synthesis of Pt/C catalysts by reduction of H2PtCl6 with sodium citrate has been investigated. The strong pH-dependence of citrate as a reducing and stabilizing agent has been explored, and an optimum pH range for production of well dispersed catalysts is proposed. To achieve stabilizing and reducing conditions, the presence of both citrate anions and protonated citrates are required. This is achieved in an intermediate pH range between pKa2 and pKa3 (4.76 and 6.4) of citric acid...

  17. Epoxidation of Alkenes with Aqueous Hydrogen Peroxide and Quaternary Ammonium Bicarbonate Catalysts

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Kegnæs, Søren

    2013-01-01

    A range of solid and liquid catalysts containing bicarbonate anions were synthesised and tested for the epoxidation of alkenes with aqueous hydrogen peroxide. The combination of bicarbonate anions and quaternary ammonium cations opens up for new catalytic systems that can help to overcome...

  18. Precursors and BRST symmetry

    Science.gov (United States)

    de Boer, Jan; Freivogel, Ben; Kabir, Laurens; Lokhande, Sagar F.

    2017-07-01

    In the AdS/CFT correspondence, bulk information appears to be encoded in the CFT in a redundant way. A local bulk field corresponds to many different non-local CFT operators (precursors). We recast this ambiguity in the language of BRST symmetry, and propose that in the large N limit, the difference between two precursors is a BRST exact and ghost-free term. This definition of precursor ambiguities has the advantage that it generalizes to any gauge theory. Using the BRST formalism and working in a simple model with global symmetries, we re-derive a precursor ambiguity appearing in earlier work. Finally, we show within this model that the obtained ambiguity has the right number of parameters to explain the freedom to localize precursors within different spatial regions of the boundary order by order in the large N expansion.

  19. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    OpenAIRE

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis.

  20. Vanadium oxide monolayer catalysts. I. Preparation, characterization, and thermal stability

    NARCIS (Netherlands)

    Roozeboom, F.; Fransen, T.; Mars, P.; Gellings, P.J.

    1979-01-01

    Vanadium oxide catalysts of the monolayer type have been prepared by means of chemisorption of vanadate(V)-anions from aqueous solutions and by chemisorption of gaseous V2O3(OH)4. Using Al2O3, Cr2O3, TiO2, CeO2 and ZrO2, catalysts with an approximately complete monomolecular layer of vanadium(V)

  1. Moessbauer investigations of the Fe-Cu-Mn catalysts for Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Spanu, V.; Filoti, G.; Ilie, I.; Zamfirescu, E.

    1990-01-01

    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 H 2 or in a H 2 +CO mixture. The influence of the reduction and reaction conditions on the catalyst structure was investigated. (orig.)

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

    KAUST Repository

    Takanabe, Kazuhiro

    2018-01-04

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

  3. Catalyst Architecture

    DEFF Research Database (Denmark)

    Catalyst Architecture’ takes its point of departure in a broadened understanding of the role of architecture in relation to developmental problems in large cities. Architectural projects frame particular functions and via their form language, they can provide the user with an aesthetic experience....... The broadened understanding of architecture consists in that an architectural project, by virtue of its placement in the context and of its composition of programs, can have a mediating role in a positive or cultural development of the district in question. In this sense, we talk about architecture as catalyst...... cities on the planet have growing pains and social cohesiveness is under pressure from an increased difference between rich and poor, social segregation, ghettoes, immigration of guest workers and refugees, commercial mass tourism etc. In this context, it is important to ask which role architecture...

  4. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Unknown

    trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange properties together with surface basicity making them materials of importance ...

  5. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange ...

  6. Earthquakes: hydrogeochemical precursors

    Science.gov (United States)

    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.

  7. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis.

    Science.gov (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel

    2015-03-04

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  8. Studies concerning the anion ex-change resins catalyzed esterification of epichlorohydrin with organic acids

    Directory of Open Access Journals (Sweden)

    E.I. Muresan

    2009-09-01

    Full Text Available The paper studies the esterification of carboxylic acids with epichlorohydrin over two macroporous strong base anion exchange resins with different polymer matrix. For both resins, the influence of reaction parameters (temperature, catalyst loading, molar ratio on the reaction rate and the yields of the two isomeric esters were investigated.

  9. Amphibian tachykinin precursor.

    Science.gov (United States)

    Li, Jianxu; Liu, Tongguang; Xu, Xueqing; Wang, Xu; Wu, Min; Yang, Hailong; Lai, Ren

    2006-12-01

    The precursor of amphibian tachykinin has not been found although more than 30 tachykinins have been isolated from amphibians since 1964. In this report, two tachykinin-like peptides are identified from the skin secretions of the frog, Odorrana grahami. Their amino acid sequences are DDTEDLANKFIGLM-NH(2) (named tachykinin OG1) and DDASDRAKKFYGLM-NH(2) that is the same with ranamargarin found in Rana margaretae, respectively, with a conserved FXGLM-NH(2) C-terminal consensus motif. By cDNA cloning, their precursors were screened from the skin cDNA library of O. grahami. The precursors are composed of 61 amino acid (aa) residues including a signal peptide followed by an acidic spacer peptide and one copy of mature tachykinin-like peptide. Their overall structure is different from structures of other tachykinin precursors such as human protachykinin 1 precursor containing 143 aa including one copy of substance P (SP) and neurokinin A (NKA), and ascidian tachykinin 1 precursor containing 164 aa including two copies of tachykinin-like peptides. The current results demonstrate that the biosynthesis mode of tachykinins in amphibians is different from other animals.

  10. Topotactic intercalation of a bulky organic anion (thiacalix[4]arene) into LDH through an osmotic swelling/restoration reaction in formamide.

    Science.gov (United States)

    Huang, Gailing; Ma, Shulan; Zhao, Xinhua; Yang, Xiaojing; Ooi, Kenta

    2009-01-21

    Utilizing the osmotic swelling of LDH in formamide, for the first time, the bulky thiacalix[4]arene anion is introduced, leading to the recovery of LDH layers, and the hexagonal prism morphology of the precursor is well retained.

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

    Science.gov (United States)

    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.

  12. CO2 Hydrogenation over Ru/χ-Al2O3 Catalyst

    Science.gov (United States)

    Jeenjumras, Kanyanat; Piticharoenphun, Sunthon; Mekasuwandumrong, Okorn

    2018-02-01

    The hydrogenation of CO2 was investigated over Ru/χ-Al2O3 catalyst prepared by thermal decomposition of gibbsite which was followed with impregnation using different types of ruthenium precursors. The performance of the catalysts was examined by the temperature programmed reaction of CO2 with H2. The Ru/χ-Al2O3 catalyst prepared using ruthenium (III) nitrosyl nitrate solution as the Ru source (RNN) exhibited the best performance, compared to other Ru precursors. The physiochemical properties of each catalyst were characterized using XRD diffraction, N2 physisorption and H2 chemisorption.

  13. Simple preparation of Fenton catalyst@bacterial cellulose for waste water treatment

    Science.gov (United States)

    Wibowo, Arie; Febi Indrawan, Radian; Triadhi, Untung; Hasdi Aimon, Akfiny; Iskandar, Ferry; Ardy, Husaini

    2018-02-01

    Heterogeneous fenton catalyst is one of the attractive technologies for destruction of persistent and non-biodegradable pollutant in wastewater, because it can be used in wide range of pH and recyclable. Herein, commercial bacterial celluloses (BCs) were used as an alternative support of fenton catalyst to improve their catalytic activity. Scanning Electron Microscope (SEM) observations indicated that the presence of BCs and decreasing precursor concentration might promote formation of smaller particle sizes of catalyst from 3.5 μm of bare catalyst to 0.7 μm of catalyst@BC. UV-vis measurement showed that fast degradation of dyes with half-time degradation at around 25 min was observed in sample using catalyst@BCs with precursor concentration of 0.01 M. Successful preparation of heterogeneous fenton catalyst with smaller particle size and better catalytic activity is important for their application in wastewater treatment.

  14. An introduction to catalyst

    International Nuclear Information System (INIS)

    Jeon, Hak Je

    1988-11-01

    This book explains basic conception of catalyst such as definition, velocity of chemical reaction and velocity of catalyst reaction, absorption with absorption energy and chemical absorption, pore structure with the role of pore and measurement of pore structure, catalyst activity on solid structure, electrical property on catalyst activity, choice and design of catalyst, catalytic reaction with reaction velocity and chemical equilibrium and reaction velocity model, measurement of reaction velocity and material analysis, catalyst for mixed compound, catalyst for solid acid and catalyst for supported metal.

  15. Anion effect on the control of morphology for NiC2O4·2H2O nanostructures as precursors for synthesis of Ni(OH)2 and NiO nanostructures and their application for removing heavy metal ions of cadmium(II) and lead(II).

    Science.gov (United States)

    Behnoudnia, Fatemeh; Dehghani, Hossein

    2014-03-07

    In this work, one-dimensional (1-D) and three-dimensional (3-D) nickel oxalate dihydrate nanostructures have been selectively prepared by a one-step and surfactant-free solvothermal approach. This preparation procedure can control the product morphology by varying the reaction temperature and anions such as nitrates, acetates, chlorides and sulfates. The morphology of nickel oxalate dihydrate changed from non-uniform sheets and ribbons to nanorods with higher temperatures while changing the initial anion converted nanorods to dandelion-like nanostructures. Field emission scanning electron microscopy (FESEM) shows that the sizes of the nickel oxalate dihydrate nanorods are about 3 μm in length and the dandelion-like nanostructures have an average diameter of around 10 μm. Furthermore, the adsorption of the heavy metal ions of cadmium(ii) and lead(ii) with nanostructured nickel compounds was investigated. The results indicate the NiO and Ni(OH)2 nanostructures can effectively adsorb cadmium(ii) and lead(ii) ions from aqueous solution.

  16. Fischer-Tropsch Synthesis over Iron Manganese Catalysts: Effect of Preparation and Operating Conditions on Catalyst Performance

    Directory of Open Access Journals (Sweden)

    Ali A. Mirzaei

    2009-01-01

    molar basis which is the most active catalyst for the conversion of synthesis gas to light olefins. The effects of different promoters and supports with loading of optimum support on the catalytic performance of catalysts are also studied. It was found that the catalyst containing 50%Fe/50%Mn/5 wt.%Al2O3 is an optimum-modified catalyst. The catalytic performance of optimal catalyst has been studied in operation conditions such as a range of reaction temperatures, H2/CO molar feed ratios and a range of total pressures. Characterization of both precursors and calcined catalysts is carried out by powder X-ray diffraction (XRD, scanning electron microscopy (SEM, BET specific surface area and thermal analysis methods such as TGA and DSC.

  17. Low Temperature Catalyst Assisted Pyrolysis of Polymer Precursors ...

    Indian Academy of Sciences (India)

    34

    [23] J. C. D. Jesus, I. González, A. Quevedo, T. Puerta, Thermal decomposition of nickel acetate tetrahydrate: an integrated study by TGA, QMS and XPS techniques, J. Mol. Catal. A Chem. 228 (2005) 283–291. [24] S. Sharma, A. Sharma, Y-K. Cho, M. Madou, Increased graphitization in electrospun single suspended carbon ...

  18. Dipyrrolyl Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts

    Science.gov (United States)

    Hock, Adam; Schrock, Richard R.; Hoveyda, Amir H.

    2008-01-01

    Addition of two equivalents of lithium pyrrolide to Mo(NR)(CHCMe2R')(OTf)2(DME) (OTf = OSO2CF3; R = 2,6-i-Pr2C6H3, 1-adamantyl, or 2,6-Br2-4-MeC6H2; R' = Me or Ph) produces Mo(NR)(CHCMe2R')(NC4H4)2 complexes in good yield. All compounds can be recrystallized readily from toluene or mixtures of pentane and ether and are sensitive to air and moisture. An X-ray structure of a 2,6-diisopropylphenylimido species shows it to be an unsymmetric dimer, {Mo(NAr)(syn-CHCMe2Ph)(η5-NC4H4)(η1-NC4H4)}{Mo(NAr)(syn-CHCMe2Ph)(η1-NC4H4)2}, in which the nitrogen in the η5-pyrrolyl bound to one Mo behaves as a donor to the other Mo. All complexes are fluxional on the NMR time scale at room temperature, with one symmetric species being observed on the NMR time scale at 50 °C in toluene-d8. The dimers react with PMe3 (at Mo) or B(C6F5)3 (at a η5-NC4H4 nitrogen) to give monomeric products in high yield. They also react rapidly with two equivalents of monoalcohols (e.g., Me3COH or (CF3)2MeCOH) or one equivalent of a biphenol or binaphthol to give two equivalents of pyrrole and bisalkoxide or diolate complexes in ~100% yield. PMID:17165793

  19. Low temperature catalyst-assisted pyrolysis of polymer precursors to ...

    Indian Academy of Sciences (India)

    2017-11-15

    org/ 10.1007/ s12034-017-1495-9) contains supplementary material, which is available to authorized users. removal of nitrogen from PAN by reducing the decomposition temperature [14,15]. Among the different polymers, PAN ...

  20. Low Temperature Catalyst Assisted Pyrolysis of Polymer Precursors ...

    Indian Academy of Sciences (India)

    34

    ) by following .... Hydrogen weight % is high for PAN-0.5% NiAc-400 °C because of the presence of acetate groups in NiAc. As the temperature increases, the acetate groups decomposed and hydrogen content was ..... Surface area per volume.

  1. Pentaarylfullerenes as noncoordinating cyclopentadienyl anions

    NARCIS (Netherlands)

    Bouwkamp, Marco W.; Meetsma, Auke

    2009-01-01

    The first example of an early-transition-metal complex involving a pentaarylfullerene was prepared. Instead of half-sandwich complexes, solvent separated ion pairs were obtained in which the pentaarylfullerene moiety acts as noncoordinating cyclopentadienyl anion.

  2. An enantioselective synthesis of optically pure azaferrocenyl anions - First general and practical approach to chiral azaferrocenes

    DEFF Research Database (Denmark)

    Seitzberg, Jimmi Gerner; Søtofte, Inger; Johannsen, Mogens

    2001-01-01

    Herein we report a very simple route that allows the construction of a variety of optically pure azaferrocenyl compounds. The key feature is the preparation of optically pure 2-azaferrocenyl anions, which can serve as precursors for the construction of novel chiral azaferrocenyl complexes....

  3. Scalable synthesis of palladium nanoparticle catalysts by atomic layer deposition

    International Nuclear Information System (INIS)

    Liang Xinhua; Lyon, Lauren B.; Jiang Yingbing; Weimer, Alan W.

    2012-01-01

    Atomic layer deposition (ALD) was used to produce Pd/Al 2 O 3 catalysts using sequential exposures of Pd(II) hexafluoroacetylacetonate and formalin at 200 °C in a fluidized bed reactor. The ALD-prepared Pd/alumina catalysts were characterized by various methods including hydrogen chemisorption, XPS, and TEM, and compared with a commercially available 1 wt% Pd/alumina catalyst, which was also characterized. The content of Pd on alumina support and the size of Pd nanoparticles can be controlled by the number of ALD-coating cycles and the dose time of the Pd precursor. One layer of organic component from the Pd precursor remained on the Pd particle surface. The ALD 0.9 wt% Pd/alumina had greater active metal surface area and percent metal dispersion than the commercial 1 wt% Pd/alumina catalyst. The ALD and commercial catalysts were subjected to catalytic testing to determine their relative activities for glucose oxidation to gluconic acid in aqueous solution. The ALD 0.9 wt% Pd/alumina catalyst had comparable activity as compared to the commercial 1 wt% Pd catalyst. No noticeable amount of Pd leaching was observed for the ALD-prepared catalysts during the vigorously stirred reaction.

  4. Facile synthesis of hollow silica nanospheres employing anionic PMANa templates

    Science.gov (United States)

    Shi, Yan; Takai, Chika; Shirai, Takashi; Fuji, Masayoshi

    2015-05-01

    This article presents a facile and green route to the synthesis of hollow silica particles by means of anionic particles of poly(sodium methacrylate) (PMANa) as templates. This method was composed of the following three steps: formation of PMANa particles in ethanol by nanoprecipitation, the deposition of silica shell on the polymer cores through sol-gel process of tetraethylorthosilicate under catalysis of ammonia, and removal of the polymer templates by washing with water. The templates' size can be controlled in the range of about 70-140 nm by altering the ratio of ethanol to water, the polymer solution concentration, the ethanol amount in polymer solution, and the silica shell thickness can be adjusted between 15 and 30 nm by varying the ratio of silica precursor to the polymer cores. A tentative interpretation about the silica-coating process on the anionic PMANa particles was also proposed according to the experimental results.

  5. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    Science.gov (United States)

    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

  6. Bound anionic states of adenine

    Energy Technology Data Exchange (ETDEWEB)

    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

  7. Precursor Additive Manufacturing Inventions

    Science.gov (United States)

    Roberts, C.; Bourell, D.

    2018-03-01

    Most modern Additive Manufacturing (AM) processes were invented and commercialized in a short period of time spanning 1984-2000. This paper reports on AM processes invented in the 1974-1987 time period, known as precursor AM processes. The critical difference between the two periods is public knowledge and utilization of distributed computing.

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

    Energy Technology Data Exchange (ETDEWEB)

    Plazenet, G.

    2001-10-01

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

  9. Low temperature catalysts for methanol production

    Science.gov (United States)

    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.

  10. Low temperature catalysts for methanol production

    Science.gov (United States)

    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. Selective adsorption of manganese onto cobalt for optimized Mn/Co/TiO2 Fischer-Tropsch catalysts

    NARCIS (Netherlands)

    Feltes, T.E.; Espinosa-Alonso, L.; de Smit, E.|info:eu-repo/dai/nl/304824232; D'Souza, L.; Meyer, R.J.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Regalbuto, J.R.

    2013-01-01

    The Strong Electrostatic Adsorption (SEA) method was applied to the rational design of a promoted Co catalyst for Fischer–Tropsch (FT) synthesis. A series of Mn/Co/TiO2 catalysts were prepared by selective deposition of the [MnO4] anion onto the supported Co3O4 phase. Qualitative ICP-OES and XPS

  12. Ionic Block Copolymers for Anion Exchange Membranes

    Science.gov (United States)

    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. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst.

    Science.gov (United States)

    Occhipinti, Giovanni; Hansen, Fredrik R; Törnroos, Karl W; Jensen, Vidar R

    2013-03-06

    A one-step substitution of a single chloride anion of the Grubbs-Hoveyda second-generation catalyst with a 2,4,6-triphenylbenzenethiolate ligand resulted in an active olefin metathesis catalyst with remarkable Z selectivity, reaching 96% in metathesis homocoupling of terminal olefins. High turnover numbers (up to 2000 for homocoupling of 1-octene) were obtained along with sustained appreciable Z selectivity (>85%). Apart from the Z selectivity, many properties of the new catalyst, such as robustness toward oxygen and water as well as a tendency to isomerize substrates and react with internal olefin products, resemble those of the parent catalyst.

  14. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst

    Science.gov (United States)

    Tabari, Daniel S.; Tolentino, Daniel R.; Schrodi, Yann

    2013-01-01

    1st Generation Hoveyda-Grubbs olefin metathesis catalyst was purposely decomposed in the presence of ethylene yielding inorganic species that are inactive in the ring-closing metathesis (RCM) of benchmark substrate diethyldiallyl malonate (DEDAM). The decomposed catalyst was treated with 1-(3,5-diisopropoxyphenyl)-1-phenylprop-2-yn-1-ol (3) to generate an olefin metathesis active ruthenium indenylidene-ether complex in 43 % yield. This complex was also prepared independently by reacting RuCl2(p-cymene)(PCy3) with organic precursor 3. The activity of the isolated reactivated catalyst in the RCM of DEDAM is similar to that of the independently prepared complex. PMID:23355756

  15. A Highly Active and Selective Manganese Oxide Promoted Cobalt-on-Silica Fischer-Tropsch Catalyst

    NARCIS (Netherlands)

    den Breejen, Johan P.|info:eu-repo/dai/nl/304837318; Frey, Anne M.|info:eu-repo/dai/nl/341358851; Yang, Jia; Holmen, Anders; van Schooneveld, Matti M.|info:eu-repo/dai/nl/315032863; de Groot, Frank M. F.|info:eu-repo/dai/nl/08747610X; Stephan, Odile; Bitter, Johannes H.|info:eu-repo/dai/nl/160581435; de Jong, Krijn P.|info:eu-repo/dai/nl/06885580X

    A highly active and selective manganese oxide-promoted silica-supported cobalt catalyst for the Fischer-Tropsch reaction is reported. Co/MnO/SiO2 catalysts were prepared via impregnation of a cobalt nitrate and manganese nitrate precursor, followed by drying and calcination in an NO/He flow. The

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

    Energy Technology Data Exchange (ETDEWEB)

    Chunshan Song; Schobert, H.H.; Parfitt, D.P. [and others

    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.

  17. Propene Hydroformylation by Supported Aqueous-phase Rh-NORBOS Catalysts

    DEFF Research Database (Denmark)

    Riisager, Anders; Eriksen, Kim Michael; Hjortkjær, Jes

    2003-01-01

    The gas-phase hydroformylation reaction of propene using supported aqueous-phase (SAP) Rh-NORBOS modified catalysts in a continuous flow reactor has been examined. SAP catalysts supported on six different support materials were made by wet impregnation using solutions of the precursor complex Rh...

  18. Ammonia synthesis over multi-promoted iron catalysts obtained by high-energy ball-milling

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Jiang, Jianzhong; Mørup, Steen

    1999-01-01

    The feasibility of producing ammonia synthesis catalysts from high-energy ball-milling of a simple mixture of the constituent oxides has been investigated. The effect of ball-milling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show...

  19. Síntese e caracterização de perovskitas LaNi(1-xCo xO3 como precursores de catalisadores para a conversão do metano a gás de síntese pela reforma com CO2 Preparation and characterization of LaNi(1-xCo xO3 perovskites as catalyst precursors for synthesis gas generation by CO2 reforming of methane

    Directory of Open Access Journals (Sweden)

    Sania Maria de Lima

    2007-04-01

    Full Text Available LaNiO3 perovskite was modified by partial substitution of nickel by cobalt in order to increase the stability and resistance to carbon deposition during the methane CO2 reforming. The results showed that a suitable combination of precipitation and calcination steps resulted in oxides with the desired structure and with important properties for application in heterogeneous catalysis. The partial substitution of Ni by Co resulted in lower rates of conversion of both the reactants, but the catalyst stability was highly increased. The LaNi0.3Co0.7O3 catalyst, calcined at 800 ºC, was the most active under the reaction conditions.

  20. Precursor effect on the property and catalytic behavior of Fe-TS-1 in butadiene epoxidation

    Science.gov (United States)

    Wu, Mei; Zhao, Huahua; Yang, Jian; Zhao, Jun; Song, Huanling; Chou, Lingjun

    2017-11-01

    The effect of iron precursor on the property and catalytic behavior of iron modified titanium silicalite molecular sieve (Fe-TS-1) catalysts in butadiene selective epoxidation has been studied. Three Fe-TS-1 catalysts were prepared, using iron nitrate, iron chloride and iron sulfate as precursors, which played an important role in adjusting the textural properties and chemical states of TS-1. Of the prepared Fe-TS-1 catalysts, those modified by iron nitrate (FN-TS-1) exhibited a significant enhanced performance in butadiene selective epoxidation compared to those derived from iron sulfate (FS-TS-1) or iron chloride (FC-TS-1) precursors. To obtain a deep understanding of their structure-performance relationship, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature programmed desorption of NH3 (NH3-TPD), Diffuse reflectance UV-Vis spectra (DR UV-Vis), Fourier transformed infrared spectra (FT-IR) and thermal gravimetric analysis (TGA) were conducted to characterize Fe-TS-1 catalysts. Experimental results indicated that textural structures and acid sites of modified catalysts as well as the type of Fe species influenced by the precursors were all responsible for the activity and product distribution.

  1. Globins Scavenge Sulfur Trioxide Anion Radical*

    Science.gov (United States)

    Gardner, Paul R.; Gardner, Daniel P.; Gardner, Alexander P.

    2015-01-01

    Ferrous myoglobin was oxidized by sulfur trioxide anion radical (STAR) during the free radical chain oxidation of sulfite. Oxidation was inhibited by the STAR scavenger GSH and by the heme ligand CO. Bimolecular rate constants for the reaction of STAR with several ferrous globins and biomolecules were determined by kinetic competition. Reaction rate constants for myoglobin, hemoglobin, neuroglobin, and flavohemoglobin are large at 38, 120, 2,600, and ≥ 7,500 × 106 m−1 s−1, respectively, and correlate with redox potentials. Measured rate constants for O2, GSH, ascorbate, and NAD(P)H are also large at ∼100, 10, 130, and 30 × 106 m−1 s−1, respectively, but nevertheless allow for favorable competition by globins and a capacity for STAR scavenging in vivo. Saccharomyces cerevisiae lacking sulfite oxidase and deleted of flavohemoglobin showed an O2-dependent growth impairment with nonfermentable substrates that was exacerbated by sulfide, a precursor to mitochondrial sulfite formation. Higher O2 exposures inactivated the superoxide-sensitive mitochondrial aconitase in cells, and hypoxia elicited both aconitase and NADP+-isocitrate dehydrogenase activity losses. Roles for STAR-derived peroxysulfate radical, superoxide radical, and sulfo-NAD(P) in the mechanism of STAR toxicity and flavohemoglobin protection in yeast are suggested. PMID:26381408

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Ação promotora do berílio em catalisadores da síntese do estireno Promotor action of beryllium in catalysts for styrene production

    Directory of Open Access Journals (Sweden)

    Mário Nilo Mendes Barbosa

    1997-10-01

    Full Text Available The catalytic dehydrogenation of ethylbenzene in presence of steam is the main commercial route to produce styrene. The industrial catalysts are potassium- and chromia-doped hematite which show low surface areas leading to bad performance and short life. In order to develop catalysts with high areas, the effect of beryllium on the textural properties and on the catalytic performance of this iron oxide was studied. The influence of the amount of the dopant, the starting material and the calcination temperature were also studied. In sample preparations, iron and beryllium salts (nitrate or sulfate were hydrolyzed with ammonia and then calcinated. The experiments followed a factorial design with two variables in two levels (Fe/Be= 3 and 7; calcination temperature= 500 and 700ºC. Solids without any dopant were also prepared. Samples were characterized by elemental analysis, infrared spectroscopy, surface area and porosity measurements, X-ray diffraction, DSC and TG. The catalysts were tested in a microreactor at 524ºC and 1 atm, by using a mole ratio of steam/ ethylbenzene=10. The selectivity was measured by monitoring styrene, benzene and toluene formation. It was found that the effect of beryllium on the characteristics of hematite and on its catalytic performance depends on the starting material and on the amount of dopant. Surface areas increased due to the dopant as well as the nature of the precursor; samples produced by beryllium sulfate showed higher areas. Beryllium-doped solids showed a higher catalytic activity when compared to pure hematite, but no significant influence of the anion of starting material was noted. It can be concluded that beryllium acts as both textural and structural promoter. Samples with Fe/Be= 3, heated at 500ºC, lead to the highest conversion and were the most selective. However, catalysts prepared from beryllium sulfate are the most promising to ethylbenzene dehydrogenation due to their high surface area which

  4. Calcium-tolerant anionic surfactants

    NARCIS (Netherlands)

    Kooreman, Alexander

    1995-01-01

    One of the problems of applying anionic surfactants in, for example, laundry detergents is the precipitation of calcium salts. Much effort has been directed towards avoiding precipitation. There are at least three ways for tackling the problem. The first involves the use of a large quantity of

  5. Quantum mechanics of toroidal anions

    International Nuclear Information System (INIS)

    Afanas'ev, G.N.

    1990-01-01

    We consider a toroidal solenoid with an electric charge attached to it. It turns out that statistical properties of the wave function describing interacting toroidal anions depend on both their relative position and orientation. The influence of the particular gauge choice on the exchange properties of the wave function is studied. 30 refs.; 6 figs

  6. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  7. Anion binding in biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    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 L{sub 3} (2p{sub 3/2}) 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.

  8. Anion binding in biological systems

    International Nuclear Information System (INIS)

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

    2009-01-01

    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 L 3 (2p 3/2 ) 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.

  9. Anion binding in biological systems

    Science.gov (United States)

    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.

  10. Precursor of color superconductivity

    Energy Technology Data Exchange (ETDEWEB)

    Kitazawa, M. [Kyoto Univ., Dept. of Physics, Kyoto (Japan); Koide, T.; Kunihiro, T. [Kyoto Univ., Yukawa Institute for Theoretical Physics, Kyoto (Japan); Nemoto, Y. [Brookhaven National Laboratory, RIKEN BNL Research Center, Upton, NY (United States)

    2002-09-01

    We investigate possible precursory phenomena of color superconductivity in quark matter at finite temperature T with use of a simple Nambu-Jona-Lasinio model. It is found that the fluctuating pair field exists with a prominent strength even well above the critical temperature T{sub c}. We show that the collective pair field has a complex energy located in the second Riemann sheet, which approaches the origin as T is lowered to T{sub c}. We discuss the possible relevance of the precursor to the observables to be detected in heavy ion collisions. (author)

  11. Synthesis, characterization and catalytic application of Ni catalysts ...

    Indian Academy of Sciences (India)

    Alumina and alumina–zirconia mixed oxides were compared as supports to prepare nickel catalysts. The oxideswere prepared by the sol–gel method using aluminum tri-sec-butoxide and zirconium (IV) propoxide as precursors, andits physicochemical properties were determined by BET, TGA, DTA, XRD, SEM and TEM.

  12. Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

    DEFF Research Database (Denmark)

    Bjørgum, Erlend; Chen, De; Bakken, Mari G.

    2005-01-01

    precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

  13. Anion exchange membrane fuel cells: Current status and remaining challenges

    Science.gov (United States)

    Gottesfeld, Shimshon; Dekel, Dario R.; Page, Miles; Bae, Chulsung; Yan, Yushan; Zelenay, Piotr; Kim, Yu Seung

    2018-01-01

    The anion exchange membrane fuel cell (AEMFC) is an attractive alternative to acidic proton exchange membrane fuel cells, which to date have required platinum-based catalysts, as well as acid-tolerant stack hardware. The AEMFC could use non-platinum-group metal catalysts and less expensive metal hardware thanks to the high pH of the electrolyte. Over the last decade, substantial progress has been made in improving the performance and durability of the AEMFC through the development of new materials and the optimization of system design and operation conditions. In this perspective article, we describe the current status of AEMFCs as having reached beginning of life performance very close to that of PEMFCs when using ultra-low loadings of Pt, while advancing towards operation on non-platinum-group metal catalysts alone. In the latter sections, we identify the remaining technical challenges, which require further research and development, focusing on the materials and operational factors that critically impact AEMFC performance and/or durability. These perspectives may provide useful insights for the development of next-generation of AEMFCs.

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

    Science.gov (United States)

    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.

  15. Gallium based low-interaction anions

    Science.gov (United States)

    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.

  16. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad

    2016-08-18

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

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

    Science.gov (United States)

    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.

  18. Fundamental investigations of catalyst nanoparticles

    DEFF Research Database (Denmark)

    Elkjær, Christian Fink

    different topics, each related to different aspects of nanoparticle dynamics and catalysis. The first topic is the reduction of a homogeneous solid state precursor to form the catalytically active phase which is metal nanoparticles on an inert support. Here, we have reduced Cu phyllosilicate to Cu on silica......Heterogeneous catalysis, the conversion of chemicals by the use of a suitable solid state catalyst, is a very important technology in modern society and it is involved in the production of up to 90% of all chemicals. Catalysis has in this way played a significant role in the technological...... and economic development in the 20th century. There is however a downside to this development and we are seeing significant pollution and pressure on resources. Catalysis therefore has an increasingly important role in limiting pollution and optimizing the use of resources. This development will depend on our...

  19. The anion-binding polyanion: a molecular cobalt vanadium oxide with anion-sensitive visual response.

    Science.gov (United States)

    Seliverstov, Andrey; Forster, Johannes; Heiland, Magdalena; Unfried, Johannes; Streb, Carsten

    2014-07-25

    An anionic molecular cobalt vanadium oxide cluster, (n-Bu4N)3[Co(AcO)V4O12] and its use as anion binding site is reported. Cluster formation is controlled by an anion-dependent dynamic solution equilibrium. Reversible anion binding in solution leads to significant spectral changes, allowing the ratiometric optical detection of the anion concentration in situ, even under harsh thermal conditions (T = 90 °C). Comparative studies showed that the spectral response is dependent on the type of anion so that carboxylates, weakly coordinating anions and halides can be distinguished.

  20. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  1. Raney copper catalysts for the water-gas shift reaction - II. Initial catalyst optimisation

    CSIR Research Space (South Africa)

    Mellor, JR

    1997-12-23

    Full Text Available -Zn-A1 catalyst. During the controlled passivation Table 2 Crystalline phase of alloys B, C and D and their product Raney copper catalysts before and after reaction Alloy Precursor alloy phases Cat. phases before reaction a Cat. phases after reaction a... L; dry gas composition=10% CO/90% N2; CO : H20=I : 22.5; catalyst volume=2i0.1 ml): (O)=Cat. A Cu(69.3)Zn(6.9)Al( 19.5); (~)=cat. B Cu(73.6)Zn(10.9)AI(14.8); (W1)=cat. C Cu(72.4)Zn(13.3)Al(12.9); ({))=cat. D Cu(61.5)Zn(15.1)AI(19.1). It can...

  2. Laser cooling of molecular anions.

    Science.gov (United States)

    Yzombard, Pauline; Hamamda, Mehdi; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

    2015-05-29

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarize the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C_{2}^{-}, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photodetachment process is present, as well as Doppler laser cooling of trapped C_{2}^{-}, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources, and antimatter physics.

  3. Laser Cooling of Molecular Anions

    CERN Document Server

    Yzombard, Pauline; Gerber, Sebastian; Doser, Michael; Comparat, Daniel

    2015-01-01

    We propose a scheme for laser cooling of negatively charged molecules. We briefly summarise the requirements for such laser cooling and we identify a number of potential candidates. A detailed computation study with C$\\_2^-$, the most studied molecular anion, is carried out. Simulations of 3D laser cooling in a gas phase show that this molecule could be cooled down to below 1 mK in only a few tens of milliseconds, using standard lasers. Sisyphus cooling, where no photo-detachment process is present, as well as Doppler laser cooling of trapped C$\\_2^-$, are also simulated. This cooling scheme has an impact on the study of cold molecules, molecular anions, charged particle sources and antimatter physics.

  4. Design of heterogeneous catalysts

    DEFF Research Database (Denmark)

    Frey, Anne Mette

    The title of my PhD thesis is “Design of Heterogeneous Catalysts”. Three reactions have been investigated: the methanation reaction, the Fischer-Tropsch reaction, and the NH3-based selective catalytic reduction (SCR) of NO. The experimental work performed in connection with the methanation reaction...... hydrogenation. For both systems a maximum in catalytic activity was found for some of the bimetallic catalysts being superior to the monometallic catalysts. This resulted in volcano curves for all investigated systems. In the Fischer-Tropsch reaction promotion of cobalt catalysts with manganese was studied...... well, and the best catalyst prepared had a C5+ yield almost a factor of two higher than a standard air calcined Co catalyst. In the NH3-SCR reaction it is desirable to develop an active and stable catalyst for NOx removal in automotive applications, since the traditionally used vanadium-based catalyst...

  5. Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces.

    Science.gov (United States)

    Zhao, Yingjie; Cotelle, Yoann; Avestro, Alyssa-Jennifer; Sakai, Naomi; Matile, Stefan

    2015-09-16

    Here we provide experimental evidence for anion-π catalysis of enamine chemistry and for asymmetric anion-π catalysis. A proline for enamine formation on one side and a glutamic acid for nitronate protonation on the other side are placed to make the enamine addition to nitroolefins occur on the aromatic surface of π-acidic naphthalenediimides. With increasing π acidity of the formally trifunctional catalysts, rate and enantioselectivity of the reaction increase. Mismatched and more flexible controls reveal that the importance of rigidified, precisely sculpted architectures increases with increasing π acidity as well. The absolute configuration of stereogenic sulfoxide acceptors at the edge of the π-acidic surface has a profound influence on asymmetric anion-π catalysis and, if perfectly matched, affords the highest enantio- and diastereoselectivity.

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

    Science.gov (United States)

    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.

  7. Identified EM Earthquake Precursors

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    Byambasuren O

    2017-02-01

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

  9. The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

    Science.gov (United States)

    Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

    2017-11-06

    The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y  > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

  10. Near-fatal persistent anion- and osmolal-gap acidosis due to massive gamma-butyrolactone/ethanol intoxication

    NARCIS (Netherlands)

    Heytens, Luc; Neels, Hugo; van Regenmortel, Niels; van den Brink, Wim; Henckes, Manu; Schouwers, Sofie; Dockx, Greet; Crunelle, Cleo L.

    2015-01-01

    We report a case of an ethanol and massive gamma-butyrolactone (GBL) intoxication, the precursor of the recreational drug gamma-hydroxybutyric acid (GHB), resulting in life-threatening metabolic acidosis (pH 6.5) with a highly increased anion- and osmolal gap. Rapid analysis using gas chromatography

  11. Tools to discover anionic and nonionic polyfluorinated alkyl surfactants by liquid chromatography electrospray ionisation mass spectrometry

    DEFF Research Database (Denmark)

    Trier, Xenia; Granby, Kit; Christensen, Jan H.

    2011-01-01

    A tiered approach is proposed for the discovery of unknown anionic and nonionic polyfluorinated alkyl surfactants (PFASs) by reversed phase ultra high performance liquid chromatography (UHPLC) – negative electrospray ionisation – quadrupole time of flight mass spectrometry (UHPLC–ESI−–QTOF–MS). T......A tiered approach is proposed for the discovery of unknown anionic and nonionic polyfluorinated alkyl surfactants (PFASs) by reversed phase ultra high performance liquid chromatography (UHPLC) – negative electrospray ionisation – quadrupole time of flight mass spectrometry (UHPLC...... such as [M−H+solvent]− and [(M−H)(M−H+Na)n]− were used to confirm the identity of the precursor ions. In relation to quantification of PFASs, we discuss how their surfactancy influence the ESI processes, challenge their handling in solution and choices of precursor-to-product ions for MSMS of e...

  12. Tritium labelling of PACAP-38 using a synthetic diiodinated precursor peptide

    DEFF Research Database (Denmark)

    Pedersen, Martin Holst Friborg; Baun, Michael

    2012-01-01

    In the interest of developing efficient methods for tritium labelling peptides, we here demonstrate the successful labelling of PACAP-38 (pituitary adenylate cyclase-activating polypeptide), a 38-mer peptide, using a synthetic diiodinated PACAP-38 precursor. In this example, we employ standard...... hydrogenation chemistry with the use of a heterogeneous palladium catalyst and carrier-free tritium gas on a tritium manifold system....

  13. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan

    2003-01-01

    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  14. Decreased anion gap in polyclonal hypergammaglobulinemia.

    Science.gov (United States)

    Qujeq, Durdi; Mohiti, Javad

    2002-02-01

    The anion gap has proved a valuable tool in the diagnosis of various forms of acid-base disorders, although the importance of slight rises in the anion gap remains unclear. The concept of the anion gap is often misunderstood and misapplied. The relationship between gammaglobulins and the serum anion gap has not received much attention except for reports of a narrowing of the gap associated with certain monoclonal immunoglobulin G gammopathies. We present patients with polyclonal gammopathy, the magnitude of which correlated strongly and negatively with the anion gap. The anion gap can be readily calculated from routine laboratory data, and anion gap was calculated as ([Na] +[K])- ([Cl] + [HCO3]). Serum anion gaps were determined in 206 patients with polyclonal hypergammaglobulinemia and 63 healthy subjects. Serum sodium and potassium ions concentration were determined by flame photometry. Serum bicarbonate level was measured as total carbon dioxide content. Serum chloride level was determined by chlorimetric titration with silver ions. All patients with polyclonal hypergammaglobulinemia had a statistically significant reduction in their mean serum anion gaps (6.4 +/- 1.2 mmol/L) when compared with normal control volunteers (15.3 +/- 2.4 mmol/L), p anion gap and gammaglobulins concentration.

  15. Methods of making textured catalysts

    Science.gov (United States)

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    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.

  16. Catalyst Alloys Processing

    Science.gov (United States)

    Tan, Xincai

    2014-10-01

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

  17. Alloy catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel alloy catalyst material for use in the synthesis of hydrogen peroxide from oxygen and hydrogen, or from oxygen and water. The present invention also relates to a cathode and an electrochemical cell comprising the novel catalyst material, and the process use...... of the novel catalyst material for synthesising hydrogen peroxide from oxygen and hydrogen, or from oxygen and water....

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

    Science.gov (United States)

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

  19. Fe3C-based oxygen reduction catalysts: synthesis, hollow spherical structures and applications in fuel cells

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2015-01-01

    We present a detailed study of a novel Fe3C-based spherical catalyst with respect to synthetic parameters, nanostructure formation, ORR active sites and fuel cell demonstration. The catalyst is synthesized by high temperature autoclave pyrolysis using decomposing precursors. Below 500 °C, melamine...

  20. Environmental behavior of inorganic anions

    International Nuclear Information System (INIS)

    Garland, T.R.; Cataldo, D.A.; Fellows, R.J.; Wildung, R.E.

    1987-01-01

    Recent efforts have addressed two aspects of anion behavior in the soil/plant system. The first involves evaluation of the gaseous component of the terrestrial iodine cycle in soils and plants. Field analyses of 129 I in soils and vegetation adjacent to a fuels reprocessing facility, which was idle for 10 years prior to the study, indicated that there may be a significant gaseous component to the terrestrial iodine cycle. Soil substrates, including a silt-sand, organic forest soil, quartz sand, and a sterilized soil, were amended with radioiodide, and the rates and quality of the volatile components evaluated

  1. METHOD OF PURIFYING CATALYSTS

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  3. New Trends in Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2014-07-01

    Full Text Available Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growing fields in science and is proven by the promising applications in several fields, such as green chemistry and environmental catalysis, in the synthesis of single-walled carbon nanotubes, as modifiers of Ni catalysts for methane steam and dry reforming reactions and in biological and electrochemistry applications. The range of reactions catalyzed by gold, as well as the suitability of different supports and the influence of the preparation conditions have been widely explored and optimized in applied research [2]. Gold catalysts appeared to be very different from the other noble metal-based catalysts, due to their marked dependence on the preparation method, which is crucial for the genesis of the catalytic activity. Several methods, including deposition-precipitation, chemical vapor deposition and cation adsorption, have been applied for the preparation of gold catalysts over reducible oxides, like TiO2. Among these methods, deposition-precipitation has been the most frequently employed method for Au loading, and it involves the use of tetrachloroauric (III acid as a precursor. On the other hand, the number of articles dealing with Au-loaded acidic supports is smaller than that on basic supports, possibly because the deposition of [AuCl4]− or [AuOHxCl4−x]− species on acidic supports is difficult, due to their very low point of zero charge. Despite this challenge, several groups have reported the use of acidic zeolites as supports for gold. Zeolites

  4. Interstellar Anions: The Role of Quantum Chemistry.

    Science.gov (United States)

    Fortenberry, Ryan C

    2015-10-01

    Six anions have been conclusively detected in the interstellar medium (ISM). They all arrived within a five-year window ending five years ago. Why have no new anions been detected? It is likely a lack of laboratory data for novel anions. This work reviews the role that valence and dipole-bound excited states may play in the formation, detection, and lifetime of anions that may yet be observed in the ISM and how quantum chemistry enhances this understanding. The list of interstellar anions has certainly not been exhausted by any means, but electronic, spectroscopic, and structural data must be provided to aid in any future detections. Quantum chemistry has the flexibility and completeness to provide a full picture of these systems and has shown exceptional accuracies of late. The work reviewed herein gives an overview of what quantum chemical computations have produced and will continue to provide related to anions and how this will enhance both laboratory experiment and astronomical observation.

  5. Clinical usefulness of the serum anion gap.

    Science.gov (United States)

    Lee, Sik; Kang, Kyung Pyo; Kang, Sung Kyew

    2006-03-01

    The anion gap in the serum is useful in the interpretation of acid-base disorders and in the diagnosis of other conditions. In the early 1980s, ion-selective electrodes for specific ionic species were introduced for the measurement of serum electrolytes. This new method has caused a shift of the anion gap from 12±4 mEq/L down 6±3 mEq/L. It is worthy for clinicians to understand the range of normal anion gap and the measuring methods for serum sodium and chloride in the laboratories that support their practice. While an increase in the anion gap is almost always caused by retained unmeasured anions, a decrease in the anion gap can be generated by multiple mechanisms.

  6. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T; Biddy, Mary J.; Kruger, Jacob S.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-10-17

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

  7. Hydroxide catalysts for lignin depolymerization

    Energy Technology Data Exchange (ETDEWEB)

    Beckham, Gregg T.; Biddy, Mary J.; Chmely, Stephen C.; Sturgeon, Matthew

    2017-04-25

    Solid base catalysts and their use for the base-catalyzed depolymerization (BCD) of lignin to compounds such as aromatics are presented herein. Exemplary catalysts include layered double hydroxides (LDHs) as recyclable, heterogeneous catalysts for BCD of lignin.

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

    Science.gov (United States)

    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.

  9. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

    Science.gov (United States)

    Feder, Harold M.; Rathke, Jerome W.

    1979-01-01

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

  10. Review of cell performance in anion exchange membrane fuel cells

    Science.gov (United States)

    Dekel, Dario R.

    2018-01-01

    Anion exchange membrane fuel cells (AEMFCs) have recently received increasing attention since in principle they allow for the use of non-precious metal catalysts, which dramatically reduces the cost per kilowatt of power in fuel cell devices. Until not long ago, the main barrier in the development of AEMFCs was the availability of highly conductive anion exchange membranes (AEMs); however, improvements on this front in the past decade show that newly developed AEMs have already reached high levels of conductivity, leading to satisfactory cell performance. In recent years, a growing number of research studies have reported AEMFC performance results. In the last three years, new records in performance were achieved. Most of the literature reporting cell performance is based on hydrogen-AEMFCs, although an increasing number of studies have also reported the use of fuels others than hydrogen - such as alcohols, non-alcohol C-based fuels, as well as N-based fuels. This article reviews the cell performance and performance stability achieved in AEMFCs through the years since the first reports in the early 2000s.

  11. Improved Low-Temperature Activity of V2O5-WO3/TiO2 for Denitration Using Different Vanadium Precursors

    OpenAIRE

    Lina Gan; Feng Guo; Jian Yu; Guangwen Xu

    2016-01-01

    This work tested two V2O5-WO3/TiO2 catalysts with different vanadium precursors for selective catalytic reduction (SCR) of flue gas NO using NH3 at 150–450 °C. While catalyst A was prepared using ammonium metavanadate (NH4VO3) through incipient impregnation, catalyst B was made according to the solvothermal method using vanadyl acetylacetonate (VO(acac)2) as the vanadium precursor. The catalytic evaluation for denitration was in a laboratory fixed bed reactor using simulated flue gas under co...

  12. Magnetic solid acid catalyst for biodiesel synthesis from waste oil

    International Nuclear Information System (INIS)

    Li, Junqiao; Liang, Xuezheng

    2017-01-01

    Highlights: • A new magnetic solid acid has been synthesized. • A new solid acid showed high activities for biodiesel synthesis from waste oils under mild condition. • A simple magnetic separation and high stability were the key properties of the new catalyst. - Abstract: A new magnetic solid acid catalyst was synthesized by immobilizing an ionic liquid precursor obtained from (3-aminopropyl)trimethoxysilane onto a magnetic core. The magnetic solid acid catalyst has a core–shell structure, and the acid sites on the shell were easily accessible to reactants. The catalytic activities of the magnetic solid acid were investigated by biodiesel synthesis from waste oils. The solid acid exhibited a higher activity than traditional acid catalysts and the ionic liquid precursor. The core–shell structure and magnetic attraction between the particles provided strong ionic interactions, resulting in the high activity and stability. The main characteristics of the magnetic solid acid catalyst were as follows: easily accessible acidic sites, simple magnetic separation and high waste oil utilization.

  13. Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

    Science.gov (United States)

    Navaee, Aso; Salimi, Abdollah

    2018-05-01

    Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

  14. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    1999-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the

  15. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  16. Nanostructured catalyst supports

    Science.gov (United States)

    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.

  17. Catalyst for hydrocarbon conversion

    International Nuclear Information System (INIS)

    Duhaut, P.; Miquel, J.

    1975-01-01

    A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

  18. Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

  19. Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

    Science.gov (United States)

    Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

    2018-06-01

    In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

  20. Palladium catalyst system comprising zwitterion and/or acid-​functionalized ionic liquid

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

  1. Graphitised Carbon Nanofibres as Catalyst Support for PEMFC

    DEFF Research Database (Denmark)

    Yli-Rantala, E.; Pasanen, A.; Kauranen, P.

    2011-01-01

    Graphitised carbon nanofibres (G-CNFs) show superior thermal stability and corrosion resistance in PEM fuel cell environment over traditional carbon black (CB) and carbon nanotube catalyst supports. However, G-CNFs have an inert surface with only very limited amount of surface defects...... (PANI) precursor. The modified surfaces were studied by FTIR and XPS and the electrochemical characterization, including long-term Pt stability tests, was performed using a low-temperature PEMFC single cell. The performance and stability of the G-CNF supported catalysts were compared with a CB supported...

  2. La2O3/CaO CATALYSTS AND ITS APPLICATION IN THE OXIDATIVE COUPLING OF METHANE

    OpenAIRE

    Garrido-Schaeffer, A.; Dedios Yenque, G.; Ponce Alvaréz, S.

    2014-01-01

    La2O3/CaO catalysts were prepared at different weight percentages of La2O3.Por the coprecipitation method described porRaO, CaCO3 is prepared and then it was impregnated in a solution of La (NO) 3.6H2O thus obtaining the catalyst precursor . precursors dried at 393K and calcined at 973K, obtaining 0-15% La2O3/CaO catalysts. XRF elemental qualitative analysis was performed. By FTIR carbonates adsorbed species was observed. The presence of La2O3 and CaO phases was confirmed by XRD and BET surfa...

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

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Robert [National Energy Technology Laboratory; Damodaran, Krishnan [Department of Chemistry, University of Pittsburgh; Luebke, David [National Energy Technology Laboratory; Nulwala, Hunaid [National Energy Technology Laboratory

    2013-04-18

    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.

  4. Chemistry of nitrile anions in the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Carles, S.; Le Garrec, J.-L.; Biennier, L. [Institut de Physique de Rennes, Département de Physique Moléculaire, Astrophysique de Laboratoire, UMR CNRS 6251, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France); Guillemin, J.-C. [Institut des Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837,35708 Rennes Cedex 7 (France)

    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.

  5. ANIONS FUNCTIONS IN TRANSITION METALS COORDINATION COMPOUNDS

    Directory of Open Access Journals (Sweden)

    T. V. Koksharova

    2016-04-01

    Full Text Available The effect of anions on the structure and properties of coordination compounds of transition metals has been discussed. The examples of changes in the composition of the formed complexes by replacement of the anion are given: metal ratio to a neutral ligand, the composition of the inner sphere, the direction of template synthesis. Anions can determine the presence of isomers in complexes with different ligands. Examples of conformational, ionization isomerism, inner sphere bond isomerization are given. The nature of the coordination polyhedron is highly sensitive to the replacement of the anion too. Examples of coordination compounds where the anion change causes a change in coordination capacity of neutral ligands and the strength of their bonds with the metal, coordination number and geometry of the inner sphere, the organization of molecular structures (the structure of the hydrogen bond networks and the degree of polymerization, crystal packing. The anions significantly affect the binding of the solvent molecules, complexes magnetic and luminescent properties, they can change the compound color, the mechanisms of thermolysis. Anions make a very noticeable influence on possible redox processes following the complexation in some cases. Anions in the coordination sphere can change catalytic and biochemical processes as well as the ways of interaction of metal ions with drugs.

  6. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Unknown

    Indian Academy of Sciences. 671. The many ways of making anionic ... In all these cases, the negative charge is compensated for by the inclusion of positive ions in the interlayer region, by virtue ..... as anionic clays. Acknowledgements. The authors thank the Department of Science and Technology, New Delhi for financial.

  7. Test procedure for anion exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    Plutonium from stored nitrate solutions will be sorbed onto anion exchange resins and converted to storable plutonium dioxide. Useful information will be simultaneously gained on the thermal stability and ion exchange capacity of four commercially available anion exchange resins over several years and under severe degradative conditions. This information will prove useful in predicting the safe and efficient lifetimes of these resins

  8. Hydrogen in anion vacancies of semiconductors

    Science.gov (United States)

    Du, Mao-Hua; Singh, David

    2009-03-01

    Hydrogen typically terminates the dangling bonds around vacancies in semiconductors, thereby, partially or completely passivating the vacancies. However, it has been shown recently that hydrogen in anion vacancies of many semiconductors, such as ZnO, MgO, InN, SnO2, and GaN, takes multi-coordinated structures and acts as shallow donors, providing n-type conductivity to the materials. We study the hydrogen in the anion vacancies of a series of II-VI and III-V semiconductors using density functional calculations. The results on these materials show that, in the anion vacancies of polar II-VI semiconductors, the hydrogen is usually anionic and is coordinated with more than one cation atoms as a result of the relatively high ionicity of the host materials. The hydrogen coordination number depends on the host anion size. On the other hand, in more covalent semiconductors such as some III-V semiconductors, the single cation-H bonding configuration may become most stable. In the anion vacancies of ZnX and CdX where X represents anions, hydrogen is typically amphoteric except for oxides, in which the small anion size prohibits the formation of the cation-cation bond that is required for the acceptor configuration.

  9. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...

  10. Fungal growth on anion surfactant medium.

    Science.gov (United States)

    Hamada, Nobuo; Abe, Niichiro

    2009-12-01

    Before the present study, no fungi using anion surfactant as a nutrient had been identified, although some fungi were known to use nonion surfactant. Washing water collected from 63 washing machines was inoculated onto 0.1% LAS (Sodium dodecyl benzenesulfonate) anion surfactant media to identify fungi that can feed on anion-surfactant. Small dark colonies of fungi were found on several of the Petri-dishes from 12 days after inoculation. These were identified as Cladophialophora boppii and Exophiala spinifera using morphological features and rDNA data. A number of the isolates of C. boppii specifically were recognized as using anion surfactant as a nutrient. The growth characteristics of the two fungal species were examined on surfactant media of three kinds. Apart from anion surfactant, the fungi were also able to grow on nonion surfactant and on soap. The application of these fungi for environmental cleansing after detergent pollution is also discussed.

  11. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

    Full Text Available 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.

  12. Closing the gap on unmeasured anions

    Science.gov (United States)

    Kellum, John A

    2003-01-01

    Many critically ill and injured patients, especially those with metabolic acidosis, have abnormally high levels of unmeasured anions in their blood. At the same time, such patients are prone to hypoalbuminemia, which makes the traditional anion gap calculation inaccurate. Thus, little is known about the epidemiology and clinical consequences of an excess in unmeasured anions in the blood. Indeed, even the etiology of these "missing ions" is often unclear. Unfortunately, more precise means of quantifying unmeasured anions, such as the strong ion gap (SIG), are cumbersome to use clinically. However, a simple means of correcting the anion gap can be used to estimate SIG and may provide additional insight into this common clinical problem. PMID:12793870

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-11-06

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

  14. Synthesis and characterization of CNTs using polypropylene waste as precursor

    Energy Technology Data Exchange (ETDEWEB)

    Bajad, Ganesh S. [Department of Chemical Engineering, Visvesvaraya National Institute of Technology, Nagpur 440010 (India); Tiwari, Saurabh K. [Department of Chemical Engineering, Indian Institute of Technology Bombay, Powai, Mumbai 400076 (India); Vijayakumar, R.P., E-mail: vijayakumarrp@che.vnit.ac.in [Department of Chemical Engineering, Visvesvaraya National Institute of Technology, Nagpur 440010 (India)

    2015-04-15

    Graphical abstract: - Highlights: • A facile method for producing CNTs from polypropylene waste is proposed. • Optimization of Ni/Mo mole ratio using RSM suggests the adequacy of cubic model. • Process parameters were optimized by RSM using Box–Behnken four factorial design. • Maximum desirability of one suggested that 514% of CNTs would yield over Ni{sub 4}Mo{sub 0.2}MgO{sub 1}. • Increase in Ni/Mo ratio from 0.5 to 20, inner diameter of CNTs decreases from 25 to 2 nm. - Abstract: We study the synthesis of MWCNTs using polypropylene waste as a precursor and Ni/Mo/MgO as a catalyst by the combustion technique. Molar ratios of Ni, Mo and MgO in the Ni/Mo/MgO catalyst were optimized using response surface methodology (RSM) to obtain the maximum yield of CNTs. The mole ratio 4/0.2/1 was found to yield more carbon product. Further, process parameters such as combustion temperature, combustion time, polymer and catalyst weight were optimized by RSM using Box–Behnken three-level and four-factorial design. The best possible combination of process parameters (combustion time of 10 min, combustion temperature of 800 °C, polymer weight of 5 g and catalyst weight of 150 mg) for maximum yield of CNTs was obtained. HRTEM indicates that the diameter of CNTs depends on the catalyst composition used for the synthesis of CNTs. The results of the study indicate a facile method for producing CNTs from polypropylene waste.

  15. Synthesis and characterization of CNTs using polypropylene waste as precursor

    International Nuclear Information System (INIS)

    Bajad, Ganesh S.; Tiwari, Saurabh K.; Vijayakumar, R.P.

    2015-01-01

    Graphical abstract: - Highlights: • A facile method for producing CNTs from polypropylene waste is proposed. • Optimization of Ni/Mo mole ratio using RSM suggests the adequacy of cubic model. • Process parameters were optimized by RSM using Box–Behnken four factorial design. • Maximum desirability of one suggested that 514% of CNTs would yield over Ni 4 Mo 0.2 MgO 1 . • Increase in Ni/Mo ratio from 0.5 to 20, inner diameter of CNTs decreases from 25 to 2 nm. - Abstract: We study the synthesis of MWCNTs using polypropylene waste as a precursor and Ni/Mo/MgO as a catalyst by the combustion technique. Molar ratios of Ni, Mo and MgO in the Ni/Mo/MgO catalyst were optimized using response surface methodology (RSM) to obtain the maximum yield of CNTs. The mole ratio 4/0.2/1 was found to yield more carbon product. Further, process parameters such as combustion temperature, combustion time, polymer and catalyst weight were optimized by RSM using Box–Behnken three-level and four-factorial design. The best possible combination of process parameters (combustion time of 10 min, combustion temperature of 800 °C, polymer weight of 5 g and catalyst weight of 150 mg) for maximum yield of CNTs was obtained. HRTEM indicates that the diameter of CNTs depends on the catalyst composition used for the synthesis of CNTs. The results of the study indicate a facile method for producing CNTs from polypropylene waste

  16. Investigating the Structure and Reactivity of Azolyl-Based Copper(I)–NHC Complexes: The Role of the Anionic Ligand

    KAUST Repository

    Trose, Michael

    2017-11-01

    A family of copper(I)–NHC azolyl complexes was synthesized and deployed in the hydrosilylation of dicyclo-hexylketone to probe the role of the anionic ligand on catalytic performance. The azolyl ligand is shown to have a crucial role in catalytic activity without the need for additives, and this at very low catalyst loading.

  17. Effects of the ratio of Cu/Co and metal precursors on the catalytic activity over Cu-Co/Al2O3 prepared using the polyol process

    International Nuclear Information System (INIS)

    Lu Chiyuan; Tseng, H.-H.; Wey Mingyen; Liu Lingyi; Chuang, K.-H.

    2009-01-01

    Cu-Co bimetallic catalysts were prepared using a simple polyol process. The effects of various metal precursors (nitrate, acetate, and chloride) and Cu/Co ratios on the activities of the catalysts were evaluated for toluene oxidation and NO reduction. The results indicated that the use of the metal precursor Cu-Co acetate in preparing the bimetallic catalysts resulted in good metal dispersion and high catalytic activity. When the atomic Cu/Co ratio was 0.21 in the Al 2 O 3 -supported catalyst, the dispersion of active sites was promoted by the Cu, and the catalytic activity was stable over the reaction time. CuO and Cu 0 species and large particle sizes (20 nm) formed when the Co loading weight in the catalyst increased, and conversion decreased. When the reaction temperature was 300 deg. C, NO and toluene were able to be simultaneously removed with high conversion rates (83% and 98%)

  18. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty

    2007-10-01

    Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

  19. Study of spent hydrorefining catalysts

    International Nuclear Information System (INIS)

    Gellerman, M.M.; Aliev, R.R.; Sidel'kovskaya, V.G.

    1993-01-01

    Aluminonickelmolybdenum catalysts for diesel fuel hydrorefining have been studied by DTA, XSPS, and diffuse reflection spectroscopy. Chemical and phase states of molybdenum compounds in samples of fresh catalyst, regenerated one after one year operation, and clogged with coke catalyst after five year operation, are determined. Chemical reactions and crystal-phase transformations of the molybdenum compounds during catalyst deactivation and regeneration are discussed

  20. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

    Abrams, B. L.; Vesborg, Peter Christian Kjærgaard

    2013-01-01

    on titania (V2O5-WO3/TiO2) as the example catalyst. The main photocatalysts examined for mineralization of organic compounds were TiO2 and MoS2. It is important to obtain insight into the catalyst structure-to-activity relationship in order to understand and locate the active site(s). In this chapter......The properties of catalysts used in environmental remediation are described here through specific examples in heterogeneous catalysis and photocatalysis. In the area of heterogeneous catalysis, selective catalytic reduction (SCR) of NOx was used as an example reaction with vanadia and tungsta...

  1. Anion Gap Blood Test: MedlinePlus Lab Test Information

    Science.gov (United States)

    ... https://medlineplus.gov/labtests/aniongapbloodtest.html Anion Gap Blood Test To use the sharing features on this page, please enable JavaScript. What is an Anion Gap Blood Test? An anion gap blood test is a way ...

  2. Activated Carbon-Supported Tetrapropylammonium Perruthenate Catalysts for Acetylene Hydrochlorination

    Directory of Open Access Journals (Sweden)

    Xing Li

    2017-10-01

    Full Text Available The Ru-based catalysts, including Ru/AC (activated carbon, TPAP (tetrapropylammonium perruthenate/AC, TPAP/AC-HNO3, and TPAP/AC-HCl, were prepared and assessed for the direct synthesis of vinyl chloride monomer. The results indicate that the TPAP/AC-HCl catalyst exhibits the best performance with the conversion falling from 97% to 91% in 48 hours’ reaction under the conditions of 180 °C, a GHSV(C2H2 of 180 h−1, and the feed ratio VHCl/VC2H2 of 1.15. The substitution of RuCl3 precursor with high valent TPAP species leads to more ruthenium oxides active species in the catalysts; the acidification treatment of carrier in TPAP/AC catalyst can produce an enhanced interaction between the active species and the modified functional groups on the carrier, and it is beneficial to inhibit the carbon deposition and sintering of ruthenium species in the reaction process, greatly increase the adsorption ability of reactants, and further increase the amount of dominating active species in the catalysts, thus improving the catalytic performance. This also provides a promising strategy to explore high efficient and economic mercury-free catalysts for the hydrochlorination of acetylene.

  3. Catalyst for microelectromechanical systems microreactors

    Science.gov (United States)

    Morse, Jeffrey D [Martinez, CA; Sopchak, David A [Livermore, CA; Upadhye, Ravindra S [Pleasanton, CA; Reynolds, John G [San Ramon, CA; Satcher, Joseph H [Patterson, CA; Gash, Alex E [Brentwood, CA

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Catalysts and method

    Science.gov (United States)

    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.

  6. Epoxidation catalyst and process

    Science.gov (United States)

    Linic, Suljo; Christopher, Phillip

    2010-10-26

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

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

    Science.gov (United States)

    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

  8. Latent olefin metathesis catalysts

    OpenAIRE

    Monsaert, Stijn; Lozano Vila, Ana; Drozdzak, Renata; Van Der Voort, Pascal; Verpoort, Francis

    2009-01-01

    Olefin metathesis is a versatile synthetic tool for the redistribution of alkylidene fragments at carbon-carbon double bonds. This field, and more specifically the development of task-specific, latent catalysts, attracts emerging industrial and academic interest. This tutorial review aims to provide the reader with a concise overview of early breakthroughs and recent key developments in the endeavor to develop latent olefin metathesis catalysts, and to illustrate their use by prominent exampl...

  9. Plasmatron-catalyst system

    Science.gov (United States)

    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.

  10. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    Science.gov (United States)

    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.

  11. Clinical Usefulness of the Serum Anion Gap

    OpenAIRE

    Lee, Sik; Kang, Kyung Pyo; Kang, Sung Kyew

    2006-01-01

    The anion gap in the serum is useful in the interpretation of acid-base disorders and in the diagnosis of other conditions. In the early 1980s, ion-selective electrodes for specific ionic species were introduced for the measurement of serum electrolytes. This new method has caused a shift of the anion gap from 12±4 mEq/L down 6±3 mEq/L. It is worthy for clinicians to understand the range of normal anion gap and the measuring methods for serum sodium and chloride in the laboratories that suppo...

  12. MODERN TECHNOLOGY OF ANIONIC POLYMERIZATION MONOMERS

    Directory of Open Access Journals (Sweden)

    A. V. Tkachev

    2013-01-01

    Full Text Available The preconditions of use in the manufacture of automobile tyres of vulcanizates-based mortar butadienestyrene rubber with a high content of 1.2 links butadiene and statistical distribution of styrene are formulated. Set out scientific researches in the field of anionic co-polymerization of diene and vinyl aromatic monomers. Formulation of catalytic systems applied in processes of anionic copolymerization of monomers are given. The reasons of formation of gel in the process of anionic polymerization of monomers and terms of their elimination are considered.

  13. Highly Active and Stable Fe-N-C Catalyst for Oxygen Depolarized Cathode Applications.

    Science.gov (United States)

    Li, Jingkun; Jia, Qingying; Ghoshal, Shraboni; Liang, Wentao; Mukerjee, Sanjeev

    2017-09-19

    Anion immunity toward the oxygen reduction reaction (ORR) has tremendous implications in electrocatalysis with applications for fuel cells, metal-air batteries, and oxygen depolarized cathodes (ODCs) in the anodic evolution of chlorine. The necessity of exploring ORR catalysts with immunity to anion adsorption is particularly significant considering that platinum group metal (PGM) catalysts are costly and highly vulnerable to impurities such as halides. Herein, we report a metal organic framework (MOF)-derived Fe-N-C catalyst that exhibits a dramatically improved half-wave potential of 240 mV compared to the state-of-the-art Rh x S y /C catalyst in a rotating disk electrode in the presence of Cl - . The Fe-N 4 active sites in Fe-N-C are intrinsically immune to Cl - poisoning, in contrast to Pt/C, which is severely susceptible to Cl - poisoning. As a result, the activity of Fe-N-C decreases only marginally in the presence of Cl - , far exceeding that of Pt/C. The viability of this catalyst as ODCs is further demonstrated in real-life hydrochloric acid electrolyzers using highly concentrated HCl solution saturated with Cl 2 gas as the electrolyte. The introduction of Fe-N-C materials as ODC catalysts here overcomes the limitations of (i) the low intrinsic ORR activity of Rh x S y /C as the state-of-the-art ODC catalyst; (ii) the vulnerability to Cl - poisoning of Pt/C as the state-of-the-art ORR catalyst; and (iii) the high cost of precious metals in these two materials, resulting in a cost-effective ODC catalyst with the overall performance exceeding that of all previously reported materials.

  14. Benzoate Anion-Intercalated Layered Cobalt Hydroxide Nanoarray: An Efficient Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Ge, Ruixiang; Ren, Xiang; Ji, Xuqiang; Liu, Zhiang; Du, Gu; Asiri, Abdullah M; Sun, Xuping; Chen, Liang

    2017-10-23

    Efficient oxygen evolution reaction (OER) catalysts are highly desired to improve the overall efficiency of electrochemical water splitting. We develop a benzoate anion-intercalated layered cobalt hydroxide nanobelt array on nickel foam (benzoate-Co(OH) 2 /NF) through a one-pot hydrothermal process. As a 3 D electrode, benzoate-Co(OH) 2 /NF with an expanded interlayer spacing (14.72 Å) drives a high OER catalytic current density of 50 mA cm -2 at an overpotential of 291 mV, outperforming its carbonate anion-intercalated counterpart with a lower interlayer spacing of 8.81 Å (337 mV overpotential at 50 mA cm -2 ). Moreover, this benzoate-Co(OH) 2 /NF can maintain its catalytic activity for 21 h. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Characterization of anion exchange ionomers in hybrid polymer electrolyte fuel cells.

    Science.gov (United States)

    Unlü, Murat; Zhou, Junfeng; Anestis-Richard, Irene; Kohl, Paul A

    2010-12-17

    Anion exchange ionomers (AEI) synthesized here were characterized by use of a novel fuel cell configuration. The new analysis method involves assembling the AEI electrode of interest as the cathode in a hybrid, acid/alkaline, fuel cell configuration. The hybrid cell includes a conventional proton conducting anode/membrane half-cell along with the anionic conductor of interest at the cathode. Electrochemical impedance spectroscopy and voltammetry were used to evaluate the performance of the hybrid AEI-containing fuel cell with H₂ and O₂. In particular, the AEI electrode response in impedance spectroscopy was easily identified because the contributions from other components are largely minimized in the presented hybrid cell configuration. The properties of ionomers used in the AEI electrode were shown to have a substantial effect on the electrode performance. Low catalyst utilization, due to high water uptake and low conductivity, was identified as the major causes of poor performance in AEI electrodes.

  16. Al-doped single-crystalline SiC nanowires synthesized by pyrolysis of polymer precursors.

    Science.gov (United States)

    Yang, Weiyou; Gao, Fengmei; Fan, Yi; An, Linan

    2010-07-01

    Al-doped 6H-SiC nanowires are synthesized by catalyst-assisted pyrolysis of polymer precursors. The obtained nanowires were characterized using scanning electron microscopy, X-ray diffraction, transmission electron microscopy and selective area electron diffraction. We demonstrate that doping concentrations can be controlled by tailoring the Al concentrations in the precursors. We also find that Al-doping has a profound effect on the morphology and emission behavior of the SiC nanowires. The current results suggest a simple technique for synthesizing Al-doped SiC nanomaterials in a controlled manner, which are promising for applications in optical and electronic nanodevices.

  17. Mixed oxides derived from layered double hydroxides as novel catalysts for phenol photodegradation

    Science.gov (United States)

    Puscasu, C. M.; Carja, G.; Mureseanu, M.; Zaharia, C.

    2017-08-01

    The removal of organic pollutants is nowadays a very challenging aspect of the environmental research. There are strong interests to develop novel semiconducting photocatalysts able to efficiently promote advanced oxidation reactions. The development of photocatalysts based on the mixtures of mixed oxides derived from layered double hydroxides (LDHs) - a family of naturally occurring anionic clays - might offer novel environmental-friendly solutions for the cost effective removal of organic pollutants. This work presents ZnO/ZnAl2O4, ZnO/Zn2TiO4 and ZnO/ZnCr2O4 as novel photocatalytic formulations for phenol degradation under UV irradiation. They were obtained by the controlled thermal treatment of the layered double hydroxides matrices (LDHs), as precursors materials, type ZnM-LDH (M = Al3+, Cr3+ or Ti4+). The LDHs were synthesized by the co-precipitation method at a constant pH. Controlled calcination at 650°C gives rise to solutions of mixed metal oxides. The structural and nanoarchitectonics characteristics of the studied catalysts were described by: XRD, SEM/TEM and TG/DTG techniques. Results show that in the photocatalytic process of the phenol degradation from aqueous solutions, ZnO/ZnCr2O4 and ZnO/ZnAl2O4 showed the best performance degrading ∼98% of phenol after 3.5 hs and 5 hs, respectively; while ZnO/Zn2TiO4 has degraded almost 80 % after 7.5 hs of UV irradiation. These results open new opportunities in the development of new cost effective photoresponsive formulations able to facilitate the photo-degradation of the organic pollution as “green” solution for removal of dangerous pollutants.

  18. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schoeb, Ann M. [Iowa State Univ., Ames, IA (United States)

    1997-10-17

    The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO2 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/SiO2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO2 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/SiO2, Pt-Ag/SiO2 and Pt-Cu/SiO2 catalysts produced only butyraldehyde. Initial heats of adsorption (~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 1H NMR Knight shift.

  19. Electrocatalytic activity of atomic layer deposited Pt–Ru catalysts onto N-doped carbon nanotubes

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta; Larsen, Jackie Vincent; Verheijen, Marcel A.

    2014-01-01

    (ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), respectively. O2 was used as the reactant in both processes. The composition of the catalysts was easily tuned by varying the Pt-to-Ru ALD cycle ratio. The catalysts were tested toward the CO oxidation and methanol oxidation reaction (MOR) in a three-electrode electrochemical set......Pt–Ru catalysts of various compositions, between 0 and 100at.% of Ru, were deposited onto N-doped multi-walled carbon nanotubes (N-CNTs) by atomic layer deposition (ALD) at 250°C. The Pt and Ru precursors were trimethyl(methylcyclopentadienyl)platinum (MeCpPtMe3) and bis...

  20. Preparation and heat treatment characterization of alumina-based ceramic catalyst supports

    International Nuclear Information System (INIS)

    Che Seman Mahmood; Sarimah Mahat; Che Nor Aiza Jaafar

    2000-01-01

    Physical and chemical properties of support materials are as equally important as the precursor metals to the overall performance and function of the heterogeneous catalyst system. Studies on support properties could lead to development of procedure for production of catalyst designed for a desired functionality. This paper reports on the studies of changes of physical properties of alumina and mullite, that have been synthesized for catalyst support, after undergoing heat treatment. The crystallization has been studied by XRD technique, and the phase transformation was monitored by TGA and DTA methods. The surface area changes were followed by BET nitrogen adsorption method

  1. Anion conductance of the human red cell is carried by a maxi-anion channel

    DEFF Research Database (Denmark)

    Glogowska, Edyta; Dyrda, Agnieszka; Cueff, Anne

    2010-01-01

    Historically, the anion transport through the human red cell membrane has been perceived to be mediated by Band 3, in the two-component concept with the large electroneutral anion exchange accompanied by the conductance proper, which dominated the total membrane conductance. The status of anion...... that the diversity of anionic channel activities recorded in human erythrocytes corresponds to different kinetic modalities of a unique type of maxi-anion channel with multiple conductance levels and probably multiple gating properties and pharmacology, depending on conditions. It demonstrates the role of activator...... played by serum in the recruitment of multiple new conductance levels showing very complex kinetics and gating properties upon serum addition. These channels, which seem to be dormant under normal physiological conditions, are potentially activable and could confer a far higher anion conductance...

  2. Magnetic and dendritic catalysts.

    Science.gov (United States)

    Wang, Dong; Deraedt, Christophe; Ruiz, Jaime; Astruc, Didier

    2015-07-21

    The recovery and reuse of catalysts is a major challenge in the development of sustainable chemical processes. Two methods at the frontier between homogeneous and heterogeneous catalysis have recently emerged for addressing this problem: loading the catalyst onto a dendrimer or onto a magnetic nanoparticle. In this Account, we describe representative examples of these two methods, primarily from our research group, and compare them. We then describe new chemistry that combines the benefits of these two methods of catalysis. Classic dendritic catalysis has involved either attaching the catalyst covalently at the branch termini or within the dendrimer core. We have used chelating pyridyltriazole ligands to insolubilize catalysts at the termini of dendrimers, providing an efficient, recyclable heterogeneous catalysts. With the addition of dendritic unimolecular micelles olefin metathesis reactions catalyzed by commercial Grubbs-type ruthenium-benzylidene complexes in water required unusually low amounts of catalyst. When such dendritic micelles include intradendritic ligands, both the micellar effect and ligand acceleration promote faster catalysis in water. With these types of catalysts, we could carry out azide alkyne cycloaddition ("click") chemistry with only ppm amounts of CuSO4·5H2O and sodium ascorbate under ambient conditions. Alternatively we can attach catalysts to the surface of superparamagnetic iron oxide nanoparticles (SPIONs), essentially magnetite (Fe3O4) or maghemite (γ-Fe2O3), offering the opportunity to recover the catalysts using magnets. Taking advantage of the merits of both of these strategies, we and others have developed a new generation of recyclable catalysts: dendritic magnetically recoverable catalysts. In particular, some of our catalysts with a γ-Fe2O3@SiO2 core and 1,2,3-triazole tethers and loaded with Pd nanoparticles generate strong positive dendritic effects with respect to ligand loading, catalyst loading, catalytic activity and

  3. Catalytic dimerization of propene with a Bis(salicyladiminato)Nic le (II) catalyst using 2,4,6-trichlorophenol for isomerization reactions

    International Nuclear Information System (INIS)

    Alt, H. G.; Schneider, K.J; Gorl, C.

    2009-01-01

    A bis(salicylaldiminato)nic le(II) catalyst was used for dimerization reactions of propene. The catalyst precursor was activated with a triethylaluminum/aluminum trichloride mixture in the presence of phosphines and 2, 4, 6-trichlorophenol. The influence of the various components on the catalytic activity and product distribution is shown.

  4. Innovative sol–gel route in neutral hydroalcoholic condition to obtain antibacterial cotton finishing by zinc precursor

    NARCIS (Netherlands)

    Poli, R.; Colleoni, C.; Calvimontes, A.; Polaskova, H.; Dutschk, Victoria; Rosace, G.

    2015-01-01

    In the present study, a possibility to realize a transparent sol by zinc-based precursors in a neutral medium without acidic or alkaline catalyst was investigated.Moreover, to study the influence of an inorganic–organic hybrid polymer on the proposed antibacterial finishing, the Zn-based sol was

  5. Preparation of superconductor precursor powders

    Science.gov (United States)

    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.

  6. Trending analysis of precursor events

    International Nuclear Information System (INIS)

    Watanabe, Norio

    1998-01-01

    The Accident Sequence Precursor (ASP) Program of United States Nuclear Regulatory Commission (U.S.NRC) identifies and categorizes operational events at nuclear power plants in terms of the potential for core damage. The ASP analysis has been performed on yearly basis and the results have been published in the annual reports. This paper describes the trends in initiating events and dominant sequences for 459 precursors identified in the ASP Program during the 1969-94 period and also discusses a comparison with dominant sequences predicted in the past Probabilistic Risk Assessment (PRA) studies. These trends were examined for three time periods, 1969-81, 1984-87 and 1988-94. Although the different models had been used in the ASP analyses for these three periods, the distribution of precursors by dominant sequences show similar trends to each other. For example, the sequences involving loss of both main and auxiliary feedwater were identified in many PWR events and those involving loss of both high and low coolant injection were found in many BWR events. Also, it was found that these dominant sequences were comparable to those determined to be dominant in the predictions by the past PRAs. As well, a list of the 459 precursors identified are provided in Appendix, indicating initiating event types, unavailable systems, dominant sequences, conditional core damage probabilities, and so on. (author)

  7. Synthesis of labelled ecdysone precursors

    International Nuclear Information System (INIS)

    Haag, T.; Hetru, C.; Nakatani, Y.; Luu, B.; Meister, M.; Pichat, L.; Audinot, M.

    1985-01-01

    High specific activity tritiated 3β,14α-dihydroxy-5β-cholest-7-en-6-one, has been prepared using a precursor which permits rapid and easy labelling. This compound is converted to ecdysone under in vitro conditions by insect prothoracic glands, a well known site of ecdysone biosynthesis. (author)

  8. Synthesis and Characterization of Anionic Polyester-Polyurethane Dispersion as Environmentally-Friendly Waterbased Resins

    Directory of Open Access Journals (Sweden)

    Najaf i F. Manouchehri F., and Shaabanz

    2012-01-01

    Full Text Available Aqueous polyurethane dispersions (PUDs have recently emerged as important alternatives to their solvent-based counterparts for various applications due to increasing health and environmental awareness (green chemistry. Anionic polyester-polyurethane dispersions were synthesized by three steps. In the first step, macromonomer diisocyanate having carboxylic acid was prepared by isophorone diisocyanate (IPDI, dimethylol propionic acid (DMPA in percent of acetone as solvent and dibutyldtin dilaurate (DBTDL as catalyst. Then, carboxylic polyurethane was prepared by reaction macromonomer diisocyanate having carboxylic acid with linear aliphatic polyester (Mw=2000, trifunctional polyester (Mw=2800 and butanediol (BDO as chain extender. The next step involved neutralization and dispersion in water, where acidic polyurethane was neutralized by the addition of triethylamine (TEA.  Factors influencing the synthesis of polyurethane dispersion mainly involve reaction temperature, reaction time, the concentration of catalyst, DMPA content and BDO content, were studied. The polymers have been characterized with DSC and FTIR.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  11. Catalyst component interactions in nickel/alumina catalyst

    Directory of Open Access Journals (Sweden)

    Kiš Erne E.

    2007-01-01

    Full Text Available The influence of nickel loading (5; 10; 20 wt% Ni, temperature of heat treatment (400; 700; 1100°C and way of catalyst preparation on the catalyst component interactions (CCI in the impregnated, mechanical powder mixed and co-precipitated catalyst was investigated. For sample characterization, low temperature nitrogen adsorption (LTNA and X-ray diffraction (XRD were applied. Significant differences were revealed, concerning CCI in dependence of nickel loading, temperature of heat treatment and way of catalyst preparation. The obtained results show that the support metal oxide interactions (SMI in impregnated and co-precipitated catalysts are more intensive than in the mechanical powder mixed catalyst. The degree and intensity of CCI is expressed by the ratio of real and theoretical surface area of the catalyst. This ratio can be used for a quantitative estimation of CCI and it is generally applicable to all types of heterogeneous catalysts.

  12. Supported organoiridium catalysts for alkane dehydrogenation

    Science.gov (United States)

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  13. Optimisation of Ag loading and alumina characteristics to give sulphur-tolerant Ag/Al2O3 catalyst for H2-assisted NH3-SCR of NOx

    DEFF Research Database (Denmark)

    Fogel, Sebastian; Doronkin, Dmitry E.; Gabrielsson, Pär

    2012-01-01

    A series of Ag/Al2O3 catalysts with different alumina precursors and different Ag loadings were tested for H2 assisted NH3-SCR of NO. The catalysts were characterised (BET, XRD, NH3-TPD, ICP-OES, TEM and UV–vis spectroscopy) and tested as fresh catalyst, during long-term cycling tests with SO2...

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

    Energy Technology Data Exchange (ETDEWEB)

    Carja, Gabriela [Department of Physical Chemistry, Faculty of Industrial Chemistry, Technical University of Iasi, 71 Mangeron Boulevard, 700050 Iasi (Romania); Chiriac, Horia [National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050 Iasi (Romania)]. E-mail: hchiriac@phys-iasi.ro; Lupu, Nicoleta [National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050 Iasi (Romania)

    2007-04-15

    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.

  15. Differentiating homogeneous and heterogeneous water oxidation catalysis: confirmation that [Co4(H2O)2(α-PW9O34)2]10- is a molecular water oxidation catalyst.

    Science.gov (United States)

    Vickers, James W; Lv, Hongjin; Sumliner, Jordan M; Zhu, Guibo; Luo, Zhen; Musaev, Djamaladdin G; Geletii, Yurii V; Hill, Craig L

    2013-09-25

    Distinguishing between homogeneous and heterogeneous catalysis is not straightforward. In the case of the water oxidation catalyst (WOC) [Co4(H2O)2(PW9O34)2](10-) (Co4POM), initial reports of an efficient, molecular catalyst have been challenged by studies suggesting that formation of cobalt oxide (CoOx) or other byproducts are responsible for the catalytic activity. Thus, we describe a series of experiments for thorough examination of active species under catalytic conditions and apply them to Co4POM. These provide strong evidence that under the conditions initially reported for water oxidation using Co4POM (Yin et al. Science, 2010, 328, 342), this POM anion functions as a molecular catalyst, not a precursor for CoOx. Specifically, we quantify the amount of Co(2+)(aq) released from Co4POM by two methods (cathodic adsorptive stripping voltammetry and inductively coupled plasma mass spectrometry) and show that this amount of cobalt, whatever speciation state it may exist in, cannot account for the observed water oxidation. We document that catalytic O2 evolution by Co4POM, Co(2+)(aq), and CoOx have different dependences on buffers, pH, and WOC concentration. Extraction of Co4POM, but not Co(2+)(aq) or CoOx into toluene from water, and other experiments further confirm that Co4POM is the dominant WOC. Recent studies showing that Co4POM decomposes to a CoOx WOC under electrochemical bias (Stracke and Finke, J. Am. Chem. Soc., 2011, 133, 14872), or displays an increased ability to reduce [Ru(bpy)3](3+) upon aging (Scandola, et al., Chem. Commun., 2012, 48, 8808) help complete the picture of Co4POM behavior under various conditions but do not affect our central conclusions.

  16. Catalyst, method of making, and reactions using the catalyst

    Science.gov (United States)

    Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

    2002-08-27

    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.

  17. Oxide Nanocrystal Model Catalysts.

    Science.gov (United States)

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified

  18. Fuel cell catalyst degradation

    DEFF Research Database (Denmark)

    Arenz, Matthias; Zana, Alessandro

    2016-01-01

    Fuel cells are an important piece in our quest for a sustainable energy supply. Although there are several different types of fuel cells, the by far most popular is the proton exchange membrane fuel cell (PEMFC). Among its many favorable properties are a short start up time and a high power density...... increasing focus. Activity of the catalyst is important, but stability is essential. In the presented perspective paper, we review recent efforts to investigate fuel cell catalysts ex-situ in electrochemical half-cell measurements. Due to the amount of different studies, this review has no intention to give...

  19. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.

    1986-05-20

    A process is described for preparing a disproportionation catalyst comprising admixing a catalytically effective amount of a calcined and activated catalyst consisting essentially of at least one metal oxide selected from molybdenum oxide and tungsten oxide and a support containing a major proportion of silica or alumina with a promoting amount of a methylating agent selected from the group consisting of dimethyl sulfate, dimethylsulfoxide, trimethyloxonium tetrafluorborate, methyl iodide, and methyl bromide, and subjecting same to inert atmospheric conditions for the methylating agent to promote the activity of the calcined molybdenum and tungsten oxides for the disproportionation of olefins.

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

    Science.gov (United States)

    Serna, Pedro; Gates, Bruce C

    2014-08-19

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

  1. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Daria L. [Department of Chemistry, Yale University, 225; Beltrán-Suito, Rodrigo [Department of Chemistry, Yale University, 225; Thomsen, Julianne M. [Department of Chemistry, Yale University, 225; Hashmi, Sara M. [Department of Chemical and Environmental; Materna, Kelly L. [Department of Chemistry, Yale University, 225; Sheehan, Stafford W. [Catalytic Innovations LLC, 70 Crandall; Mercado, Brandon Q. [Department of Chemistry, Yale University, 225; Brudvig, Gary W. [Department of Chemistry, Yale University, 225; Crabtree, Robert H. [Department of Chemistry, Yale University, 225

    2016-02-05

    This paper introduces IrI(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*IrIII(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 IrIV 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 IrIV 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 1H 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.

  2. Precursor polymer compositions comprising polybenzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    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. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    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

  4. Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon

    2012-02-01

    Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

  5. Nonalloyed carbon-supported PtRu catalysts for PEMFC applications

    NARCIS (Netherlands)

    Papageorgopoulos, D.C.; De Heer, M.P.; Keijzer, M.; Pieterse, J.A.Z.; de Bruijn, F. A.

    2004-01-01

    PtRu(1:1)/C catalysts were prepared by a process that was claimed previously to lead to non-alloyed Pt and Ru particles, using two different precursors, Ru nitrosyl nitrate and Ru chloride hydrate. Both X-ray diffraction and characterization by cyclic voltammetry point toward Pt and Ru being present

  6. Correction of the anion gap for albumin in order to detect occult tissue anions in shock.

    Science.gov (United States)

    Hatherill, M; Waggie, Z; Purves, L; Reynolds, L; Argent, A

    2002-12-01

    It is believed that hypoalbuminaemia confounds interpretation of the anion gap (AG) unless corrected for serum albumin in critically ill children with shock. To compare the ability of the AG and the albumin corrected anion gap (CAG) to detect the presence of occult tissue anions. 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). 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. 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 lactate and other occult tissue anions. We suggest that

  7. Deactivation-resistant catalyst for selective catalyst reduction of NOx

    DEFF Research Database (Denmark)

    2011-01-01

    The present invention relates to a catalyst for selective catalytic reduction of NOx in alkali metal containing flue gas using ammonia as reductant, the catalyst comprising a surface with catalytically active sites, wherein the surface is at least partly coated with a coating comprising at least...... one metal oxide. In another aspect the present invention relates to the use of said catalyst and to a method of producing said catalyst. In addition, the present invention relates to a method of treating an catalyst for conferring thereon an improved resistance to alkali poisoning....

  8. Iron Fischer-Tropsch Catalysts Prepared by Solvent-Deficient Precipitation (SDP: Effects of Washing, Promoter Addition Step, and Drying Temperature

    Directory of Open Access Journals (Sweden)

    Kyle M. Brunner

    2015-07-01

    Full Text Available A novel, solvent-deficient precipitation (SDP method for catalyst preparation in general and for preparation of iron FT catalysts in particular is reported. Eight catalysts using a 23 factorial design of experiments to identify the key preparation variables were prepared. The catalysts were characterized by electron microprobe, N2 adsorption, TEM, XRD, and ICP. Results show that the morphology of the catalysts, i.e., surface area, pore volume, pore size distribution, crystallite sizes, and promoter distribution are significantly influenced by (1 whether or not the precursor catalyst is washed, (2 the promoter addition step, and (3 the drying condition (temperature. Consequently, the activity, selectivity, and stability of the catalysts determined from fixed-bed testing are also affected by these three variables. Unwashed catalysts prepared by a one-step method and dried at 100 °C produced the most active catalysts for FT synthesis. The catalysts of this study prepared by SDP compared favorably in activity, productivity, and stability with Fe FT catalysts reported in the literature. It is believed that this facile SDP approach has promise for development of future FT catalysts, and also offers a potential alternate route for the preparation of other catalysts for various other applications.

  9. Templating Routes to Supported Oxide Catalysts by Design

    Energy Technology Data Exchange (ETDEWEB)

    Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

    2016-09-08

    The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MOx-SiO2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO2-Al2O3 acid catalysts and to control reactant selectivity in Al2O3-TiO2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

  10. Preparation of supported heterogeneous catalysts by pulse impregnation: Application to Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Haukka, M.; Pakkanen, T.A. (Univ. of Joensuu (Finland))

    1994-07-01

    In this paper, the authors introduce pulse impregnation, a method for preparing supported heterogeneous catalysts by successive impregnation cycles. Pulse impregnation is a method for preparing supported heterogeneous catalysts from the liquid phase. In the pulse-impregnation technique the catalyst surface is grown gradually in consecutive cycles, with each cycle consisting of separate deposition and activation steps. During the deposition step, the catalyst precursor or precursors are deposited onto the support from a suitable solvent. The actual chemically bonded catalyst phase is formed during the activation step (e.g., thermal activation). Pulse impregnation was tested in the separate deposition of 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12] onto a silica support, and in the preparation of Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, in a column-type reactor system. Macroscopically uniform deposition was achieved with both 2,2[prime]-bipyridine and Ru[sub 3](CO)[sub 12]. Various solvent systems were used to control the amount of solute adsorbed during deposition. In the preparation of the Ru[sub 3](CO)[sub 12]/2,2[prime]-bipyridine/SiO[sub 2] catalyst, the ruthenium content increased nearly linearly with the number of preparation cycles. The effects of the preparation method on the catalyst activity was also tested in 1-hexane hydroformylation. 31 refs., 7 figs., 1 tab.

  11. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-05-14

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

  12. Hydrogen evolution reaction catalyst

    Science.gov (United States)

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

    2016-02-09

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

  13. Sabatier Catalyst Poisoning Investigation

    Science.gov (United States)

    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.

  14. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

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

    OpenAIRE

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

    2012-01-01

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

  16. A direct ascorbate fuel cell with an anion exchange membrane

    Science.gov (United States)

    Muneeb, Omar; Do, Emily; Tran, Timothy; Boyd, Desiree; Huynh, Michelle; Ghosn, Gregory; Haan, John L.

    2017-05-01

    Ascorbic Acid (Vitamin C) is investigated as a renewable alternative fuel for alkaline direct liquid fuel cells (DLFCs). The environmentally- and biologically-friendly compound, L-ascorbic acid (AA) has been modeled and studied experimentally under acidic fuel cell conditions. In this work, we demonstrate that ascorbic acid is a more efficient fuel in alkaline media than in acidic media. An operating direct ascorbate fuel cell is constructed with the combination of L-ascorbic acid and KOH as the anode fuel, air or oxygen as the oxidant, a polymer anion exchange membrane, metal or carbon black anode materials and metal cathode catalyst. Operation of the fuel cell at 60 °C using 1 M AA and 1 M KOH as the anode fuel and electrolyte, respectively, and oxygen gas at the cathode, produces a maximum power density of 73 mW cm-2, maximum current density of 497 mA cm-2 and an open circuit voltage of 0.90 V. This performance is significantly greater than that of an ascorbic acid fuel cell with a cation exchange membrane, and it is competitive with alkaline DLFCs fueled by alcohols.

  17. Characterization of VPO ammoxidation catalysts by in situ methods

    Energy Technology Data Exchange (ETDEWEB)

    Martin, A.; Luecke, B.; Brueckner, A.; Steinike, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Brzezinka, K.W. [Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin (Germany); Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie

    1998-12-31

    In-situ methods are well known as powerful tools in studying catalyst formation processes, their solid state properties under working conditions and the interaction with the feed, intermediates and products to reveal reaction mechanisms. This paper gives a short overview on results of intense studies using in-situ techniques to reveal VPO catalyst generation processes, interaction of educts, intermediates and products with VPO catalyst surfaces and mechanistic insights. Catalytic data of the ammoxidation of toluene on different VPOs complete these findings. The precursor-catalyst transformation processes were preferently investigated by in-situ XRD, in-situ Raman and in-situ ESR spectroscopy. The interaction of aromatic molecules and intermediates, resp., and VPO solid surfaces was followed by in-situ ESR and in-situ FTIR spectroscopy. Mechanistic information was mainly obtained using in-situ FTIR spectroscopy and the temporal-analysis-of-products (TAP) technique. Catalytic studies were carried out in a fixed-bed microreactor on pure (NH{sub 4}){sub 2}(VO){sub 3}(P{sub 2}O{sub 7}){sub 2}, generated [(NH{sub 4}){sub 2}(VO{sub 3})(P{sub 2}O{sub 7}){sub 2}+V{sub x}O{sub y}] catalysts, having different V{sub x}O{sub y} proportions by use of VOHPO{sub 4} x 1/2H{sub 2}O (V/P=1) and recently studied (VO){sub 3}(PO{sub 4}){sub 2} x 7 H{sub 2}O (V/P=1.5) precursors; the well-known (VO){sub 2}P{sub 2}O{sub 7} was used for comparison. (orig.)

  18. Noble metal ionic catalysts.

    Science.gov (United States)

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

    2009-06-16

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

  19. Catalyst support structure, catalyst including the structure, reactor including a catalyst, and methods of forming same

    Science.gov (United States)

    Van Norman, Staci A.; Aston, Victoria J.; Weimer, Alan W.

    2017-05-09

    Structures, catalysts, and reactors suitable for use for a variety of applications, including gas-to-liquid and coal-to-liquid processes and methods of forming the structures, catalysts, and reactors are disclosed. The catalyst material can be deposited onto an inner wall of a microtubular reactor and/or onto porous tungsten support structures using atomic layer deposition techniques.

  20. New borohydride anion B6H7-

    International Nuclear Information System (INIS)

    Kuznetsov, I.Yu.; Vinitskij, D.M.; Solntsev, K.A.

    1985-01-01

    The [Ni(Bipy) 3 ] (B 6 H 7 ) 2 , (Ph 4 P)B 6 H 7 , [Ni(Phen) 3 ](B 6 H 7 ) 2 crystals (where Bipy = bipyridine, Phen = phenathroline, Ph = phenyl) are obtained via the exchange reaction with a subsequent recrystallization from aqua-acetonic and acetonic solutions. The structure is studied of a new borohydride anion B 6 H 7 - possessing a four-valence bond unique for polyhedral borohydride anions. A triangular face of boride skeleton coordinating a hydrogen atom is considerably larger than other faces, and the electron density on this hydrogen atom is evidently much higher than at the end hydride hydrogen atoms. The trend of B 6 H 7 - anion to form statistically disordered structurs testifies to a rather slight effect of the seventh hydrogen atom position on the structure pattern of the ionic crystal lattice

  1. Photoemission from tin and lead cluster anions

    International Nuclear Information System (INIS)

    Gantefoer, G.; Gausa, M.; Meiwes-Broer, K.H.; Lutz, H.O.

    1989-01-01

    Photoelectrons from mass-identified jet-cooled tin and lead cluster anions (Sn n - , Pb n - ) are detached by ultraviolet laser light (hν=3.68 eV). The photoelectron energy spectra give the detachment energies of ground state cluster anions (electron affinities) as well as excitation energies of neutral clusters in the geometry of the anions. The energy spectra for Sn n - are dominated by flat thresholds with an n-dependence similar to that of other group IV clusters. In contrast, for Pb n - we find pronounced narrow lines close to threshold, generally followed by a 0.3-1.4 eV gap which indicates closed-shell behaviour of Pb n - for nearly all n. (orig.)

  2. Effects of Cationic Pendant Groups on Ionic Conductivity for Anion Exchange Membranes: Structure Conductivity Relationships

    Science.gov (United States)

    Kim, Sojeong; Choi, Soo-Hyung; Lee, Won Bo

    Anion exchange membranes(AEMs) have been widely studied due to their various applications, especially for Fuel cells. Previous proton exchange membranes(PEMs), such as Nafions® have better conductivity than AEMs so far. However, technical limitations such as slow electrode kinetics, carbon monoxide (CO) poisoning of metal catalysts, high methanol crossover and high cost of Pt-based catalyst detered further usages. AEMs have advantages to supplement its drawbacks. AEMs are environmentally friendly and cost-efficient. Based on the well-defined block copolymer, self-assembled morphology is expected to have some relationship with its ionic conductivity. Recently AEMs based on various cations, including ammonium, phosphonium, guanidinium, imidazolium, metal cation, and benzimidazolium cations have been developed and extensively studied with the aim to prepare high- performance AEMs. But more fundamental approach, such as relationships between nanostructure and conductivity is needed. We use well-defined block copolymer Poly(styrene-block-isoprene) as a backbone which is synthesized by anionic polymerization. Then we graft various cationic functional groups and analysis the relation between morphology and conductivity. Theoretical and computational soft matter lab.

  3. Revealing the Formation of Copper Nanoparticles from a Homogeneous Solid Precursor by Electron Microscopy

    DEFF Research Database (Denmark)

    van den Berg, Roy; Elkjær, Christian Fink; Gommes, Cedric J.

    2016-01-01

    nucleation. The combination of a uniform size of precursor particles and the autocatalytic reduction thus offers means to synthesize nanoparticles with well-defined sizes in large amounts. In this way, in situ observations made by electron microscopy provide mechanistic and kinetic insights......The understanding of processes leading to the formation of nanometer-sized particles is important for tailoring of their size, shape and location. The growth mechanisms and kinetics of nanoparticles from solid precursors are, however, often poorly described. Here we employ transmission electron...... microscopy (TEM) to examine the formation of copper nanoparticles on a silica support during the reduction by H2 of homogeneous copper phyllosilicate platelets, as a prototype precursor for a coprecipitated catalyst. Specifically, time-lapsed TEM image series acquired of the material during the reduction...

  4. Clinical acid-base pathophysiology: disorders of plasma anion gap.

    Science.gov (United States)

    Moe, Orson W; Fuster, Daniel

    2003-12-01

    The plasma anion gap is a frequently used parameter in the clinical diagnosis of a variety of conditions. The commonest application of the anion gap is to classify cases of metabolic acidosis into those that do and those that do not leave unmeasured anions in the plasma. While this algorithm is useful in streamlining the diagnostic process, it should not be used solely in this fashion. The anion gap measures the difference between the unmeasured anions and unmeasured cations and thus conveys much more information to the clinician than just quantifying anions of strong acids. In this chapter, the significance of the anion gap is emphasized and several examples are given to illustrate a more analytic approach to using the clinical anion gap; these include disorders of low anion gap, respiratory alkalosis and pyroglutamic acidosis.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Preparation and Characterization of Sugar Based Catalyst on Various Supports

    Directory of Open Access Journals (Sweden)

    Jidon Adrian Janaun

    2017-04-01

    Full Text Available A novel structured carbon-based acid catalyst was prepared by depositing the carbon precursor onto glass, ceramic and aluminum supports via dip-coating method, followed by carbonization process for converting the d-glucose layer into black carbon char in an inert nitrogen environment at 400 °C. Then, the –SO3H group was introduced into the framework of the carbon char by multiple vapor phase sulfonation. Four different carbonization methods were carried out (dry pyrolysis and hydrothermal carbonization with or without pressurized in the catalyst preparation while among the carbonization methods, the samples which prepared from dry pyrolysis without pressurized process showed the strong acidity due to highest adsorption of acid group in the catalyst surface although the catalyst attached onto the support was the least compared to other preparation methods. Among the catalysts, the sulfonated carbon-base catalyst that is attached on the ceramic support exhibited the highest aci-dity (1.327 mmol/g followed by the catalyst deposited on the glass (0.917 mmol/g and aluminum (0.321 mmol/g supports. The porous structure of ceramic surface, allowed a better interaction between reactants and –SO3H site in the carbon. Through the FT-IR analysis, it was observed that the functional groups –COOH, –OH, and –SO3H were present in the active sites of the catalysts. The surface areas of  glass (Si–SC, ceramic (Ce–SC and aluminum (Al–SC catalysts were larger than 1 m2/g, whereas the pore size belongs to macroporous as the average pore size is more than 50 nm. It is also stable within the temperature of 400 °C as there was less than 10% weight loss revealed from the TGA analysis. Copyright © 2017 BCREC GROUP. All rights reserved Received: 20th April 2016; Revised: 14th October 2016; Accepted: 17th October 2016 How to Cite: Janaun, J.A., Mey, T.J., Bono, A., Krishnaiah, D. (2017. Preparation and Characterization of Sugar Based Catalyst on Various

  7. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  8. Organic superconductors with an incommensurate anion structure

    OpenAIRE

    Kawamoto, Tadashi; Takimiya, Kazuo

    2009-01-01

    Superconducting incommensurate organic composite crystals based on the methylenedithio-tetraselenafulvalene (MDT-TSF) series donors, where the energy band filling deviates from the usual 3/4-filled, are reviewed. The incommensurate anion potential reconstructs the Fermi surface for both (MDT-TSF)(AuI2)0.436 and (MDT-ST)(I3)0.417 neither by the fundamental anion periodicity q nor by 2q, but by 3q, where MDT-ST is 5H-2-(1,3-dithiol-2-ylidene)-1,3-diselena-4,6-dithiapentalene, and q is the recip...

  9. Recognition, Sensing and Separation of Anions

    Indian Academy of Sciences (India)

    Dr Pradyut Ghosh

    2016-11-05

    Nov 5, 2016 ... Arsenate Recognition in Aqueous Medium. Anion log K log Ka log Kb. HAsO4. 2-. 4.42. 4.35. -. H2PO4. -. 3.62. 3.62. 5.52. SO4. 2-. 3.48. 3.36. 4.73. CO3. 2-. 2.68. -. 4.04. Table 1. Association constant value of L in DMSO-d6/D2O (9:1, v/v) with different anion in DMSO-d6/D2O (1.1:1, v/v) at 298 K a: log K ...

  10. ANION GAP NO SANGUE VENOSO EM EQUINOS

    Directory of Open Access Journals (Sweden)

    Luís Carlos Ribeiro Fan

    1994-01-01

    Full Text Available RESUMO A influência do sangue venoso na determinação do anion gap foi estudada em 50 equinos adultos clinicamente sadios no município de Santa Maria, RS. Os resultados obtidos em mEq/1 foram: sódio 140 ± 2,0; potássio 4,2 ± 0,5; cloreto 102 ± 12 e bicarbonato 26,9 ± 2,0. Conclui-se que o sangue venoso pode substituir o arterial na determinação do anion gap em equinos.

  11. Hydrogen Production from a Methanol-Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions.

    Science.gov (United States)

    Fujita, Ken-ichi; Kawahara, Ryoko; Aikawa, Takuya; Yamaguchi, Ryohei

    2015-07-27

    An efficient catalytic system for the production of hydrogen from a methanol-water solution has been developed using a new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. This system can be operated under mild conditions [weakly basic solution (0.046 mol L(-1) NaOH) below 100 °C] without the use of an additional organic solvent. Long-term continuous hydrogen production from a methanol-water solution catalyzed by the anionic iridium complex was also achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Nanostructured nonprecious metal catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Wu, Gang; Zelenay, Piotr

    2013-08-20

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

  13. Catalytic etherification of glycerol to produce biofuels over novel spherical silica supported Hyflon® catalysts.

    Science.gov (United States)

    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 (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. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. One-step routes from di- and triblock copolymer precursors to hydrophilic nanoporous poly(acrylic acid)-b-polystyrene

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Schulte, Lars

    2008-01-01

    Nanoporous polystyrene with hydrophilic pores was prepared from di- and triblock copolymer precursors. The precursor material was either a poly(tert-butyl acryl ate)-b-polystyrene (PtBA-b-PS) diblock copolymer synthesized by atom transfer radical polymerization (ATRP) or a polydimethylsiloxane......-b-poly(tertbutyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer synthesized by a combination of living anionic polymerization and ATRP. In the latter copolymer, PS was the matrix and mechanically stable component, PtBA was converted by acidic deprotection to hydrophilic poly(acrylic acid) (PAA) providing...

  15. Alkaline earth metal catalysts for asymmetric reactions.

    Science.gov (United States)

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

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

  16. Role of Precursor-Conversion Chemistry in the Crystal-Phase Control of Catalytically Grown Colloidal Semiconductor Quantum Wires.

    Science.gov (United States)

    Wang, Fudong; Buhro, William E

    2017-12-26

    Crystal-phase control is one of the most challenging problems in nanowire growth. We demonstrate that, in the solution-phase catalyzed growth of colloidal cadmium telluride (CdTe) quantum wires (QWs), the crystal phase can be controlled by manipulating the reaction chemistry of the Cd precursors and tri-n-octylphosphine telluride (TOPTe) to favor the production of either a CdTe solute or Te, which consequently determines the composition and (liquid or solid) state of the Bi x Cd y Te z catalyst nanoparticles. Growth of single-phase (e.g., wurtzite) QWs is achieved only from solid catalysts (y ≪ z) that enable the solution-solid-solid growth of the QWs, whereas the liquid catalysts (y ≈ z) fulfill the solution-liquid-solid growth of the polytypic QWs. Factors that affect the precursor-conversion chemistry are systematically accounted for, which are correlated with a kinetic study of the composition and state of the catalyst nanoparticles to understand the mechanism. This work reveals the role of the precursor-reaction chemistry in the crystal-phase control of catalytically grown colloidal QWs, opening the possibility of growing phase-pure QWs of other compositions.

  17. Sulfate radicals enable a non-enzymatic Krebs cycle precursor.

    Science.gov (United States)

    Keller, Markus A; Kampjut, Domen; Harrison, Stuart A; Ralser, Markus

    2017-03-13

    The evolutionary origins of the tricarboxylic acid cycle (TCA), or Krebs cycle, are so far unclear. Despite a few years ago, the existence of a simple non-enzymatic Krebs-cycle catalyst has been dismissed 'as an appeal to magic', citrate and other intermediates have meanwhile been discovered on a carbonaceous meteorite and do interconvert non-enzymatically. To identify the non-enzymatic Krebs cycle catalyst, we used combinatorial, quantitative high-throughput metabolomics to systematically screen iron and sulfate reaction milieus that orient on Archean sediment constituents. TCA cycle intermediates are found stable in water and in the presence of most iron and sulfate species, including simple iron-sulfate minerals. However, we report that TCA intermediates undergo 24 interconversion reactions in the presence of sulfate radicals that form from peroxydisulfate. The non-enzymatic reactions critically cover a topology as present in the Krebs cycle, the glyoxylate shunt and the succinic semialdehyde pathways. Assembled in a chemical network, the reactions achieve more than ninety percent carbon recovery. Our results show that a non-enzymatic precursor for the Krebs cycle is biologically sensible, efficient, and forms spontaneously in the presence of sulfate radicals.

  18. The liquid phase hydrogenation of nitrobenzene over supported copper catalysts

    International Nuclear Information System (INIS)

    Anderson, David Scott

    1999-01-01

    A series of silica-supported copper catalysts have been prepared, characterised and used for the hydrogenation of nitrobenzene. The catalysts were prepared using a wet impregnation technique, with three different metal salts (copper nitrate, copper acetate and copper carbonate) deposited onto two different forms of silica (Cab-O-Sil and C-10), with nominal metal loadings of approximately 10 wt%. Although different pretreatments were applied to produce derivatives of the catalyst precursors, the four principal substrates used are referred to as Cu(N)/Cab, Cu(A)/Cab, Cu(C)/Cab and Cu(N)/C-10. The catalysts have been the subject of numerous characterisation techniques including atomic absorption spectroscopy, BET surface area determination, thermal gravimetric analysis, temperature programmed reduction and nitrous oxide decomposition; with the latter technique used to measure the metal surface areas of the active catalysts. Selected samples were also analysed using differential scanning calorimetry, variable temperature x-ray diffraction and electron microscopy. The characterisation experiments provided insight into the nature of the catalysts. The choice of metal salt used in the preparation, rather than the choice of support material, was found to be the major factor affecting catalyst performance. The activation procedure applied to the catalysts was optimised with respect to metal surface area. The apparatus and experimental protocol for liquid phase nitrobenzene hydrogenation over copper/silica catalysts was developed. A batch slurry reactor was found to be preferable over a bubble-phase vessel. Catalyst activation was conducted in situ, whilst the design allowed control over a range of variables, e.g. mass of catalyst, concentration of reactant, reaction temperature, etc. The choice of solvent for the reaction was not trivial, and the suitability of various solvents was assessed. The use of an alcohol solvent led to the formation of unwanted by-products, arising

  19. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts.

    Science.gov (United States)

    Park, Hyun Ju; Park, Sung Hoon; Sohn, Jung Min; Park, Junhong; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Young-Kwon

    2010-01-01

    The steam reforming of benzene as a model compound of biomass gasification tar was carried out over various Ni/metal oxide catalysts. The effects of the support, temperature, Ni-precursor, Ni loading and reaction time were examined, and their catalytic performance was compared with that of a commercial Ni catalyst. Among the Ni/metal oxide catalysts used, 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) showed the highest catalytic performance owing to its greater redox characteristics and increased surface area, irrespective of the reaction temperature. The catalytic activity of 15 wt% Ni/CeO(2)(75%)-ZrO(2)(25%) was higher than that of the commercial Ni catalyst. Moreover, the catalyst activity was retained due to its excellent resistance to coke deposition even after 5h. The Ni-precursor played a critical role in the catalytic activity. With the exception of nickel nitrate, all the Ni-precursors (chloride and sulfate) caused deactivation of the catalyst.

  20. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.

    2005-01-01

    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  1. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  2. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    Transmission electron microscopy (TEM) is extensively used in catalysis research. Recent developments in aberration correction allows imaging surface structures with unprecedented resolution. Using these correctors in conjunction with environmental TEM (ETEM), where imaging of materials can be done...... under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...... and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...

  3. Mesoporous molecular sieve catalysts

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane

    This thesis deals with a very specific class of molecular sieves known as zeolites. Zeolites are a class of crystalline aluminosilicates characterised by pores or cavities of molecular dimensions as part of their crystal structure. In this work zeolites were modified for the use and understanding...... of different catalytic applications. Primarily the zeolites were modified regarding the porosity and the introduction of metals to the framework. The obtained materials were used as solid acid catalysts, as an inert matrix for stabilising metal nanoparticles and as an anchoring material for molecular metal....... Furthermore, preliminary work was done using mesoporous ZSM-5 zeolites as support material for anchoring molecular CoMo6 species for the application as potential bi-functional catalyst in simultaneous hydrodesulfurisation (HDS) and hydrocracking. HDS activity tests revealed that the anchoring improved...

  4. Photo catalyst; Ko shokubai

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-07-01

    While titanium oxide is excited by the light, electrons of titanium oxide are taken away by the light energy to form positive holes. Water will be decomposed into hydrogen ion and hydroxy radical (OH) by these positive holes. This hydroxy radical is a strong reactive substance called active oxygen, it decomposes organisms. Besides this photo- catalyst function, the titanium oxide can also make surface of a substance superhydrophilic. The super hydrophilicity results in not forming water drops on the glass surface but spreading all over the surface to prevent a covering of fog on the glass surface. The published patents concerning the photo catalysts were 593 from Jan. 1998 to Jan. 1999. The applicant order is the first TOTO 143, the second Daikin Industry 19, the third Toshiba Raitech, Nitto Denko, Hitachi 17 respectively. (NEDO)

  5. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kongkanand, Anusorn [General Motors LLC, Pontiac, MI (United States)

    2014-09-30

    Reduction of costly Pt usage in proton exchange membrane fuel cell electrodes is one of the major challenges towards development and commercialization of fuel cell vehicles. Although few have met the initial-kinetic activity requirements in a realistic fuel cell device, no catalyst material has ever met the demanding fuel cell durability targets set by DOE. In this project, a team of 4 universities and 2 companies came together to investigate a concept that appeared promising in preliminary non-fuel cell tests then to further develop the catalyst to a mature level ready for vehicle implementation. The team consists of academia with technical leadership in their respective areas, a catalyst supplier, and a fuel cell system integrator.The tightly collaborative project enabled development of a highly active and durable catalyst with performance that significantly exceeds that of previous catalysts and meets the DOE targets for the first time (Figure 1A). The catalyst was then further evaluated in full-active-area stack in a realistic vehicle operating condition (Figure 1B). This is the first public demonstration that one can realize the performance benefit and Pt cost reduction over a conventional pure Pt catalyst in a long-term realistic PEMFC system. Furthermore, systematic analyses of a range of catalysts with different performance after fuel cell testing allowed for correlation between catalyst microstructure and its electrocatalytic activity and durability. This will in turn aid future catalyst development.

  6. Deactivation of Oxidation Catalysts

    Science.gov (United States)

    1991-05-01

    been observed to decrease CO oxidation even at 500TC ( Farrauto and Wedding, 1973, p. 254) by a sulfate formation mechanism, it is likely that the...sulfated CoO, in the study of Farrauto and Wedding (1973) and that no deactivation was observed in the previously discussed study by Pope et al...This is attributed to the adsorption of HO on the catalyst surface which competes with the adsorption of ethanol. Farrauto and Wedding (1973) studied

  7. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-03-12

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disporoportionation reaction.

  8. Catalyst in Basic Oleochemicals

    OpenAIRE

    Eva Suyenty; Herlina Sentosa; Mariani Agustine; Sandy Anwar; Abun Lie; Erwin Sutanto

    2007-01-01

    Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemic...

  9. Catalyst component interactions in nickel/alumina catalyst

    OpenAIRE

    Kiš Erne E.; Lazić Matilda M.; Bošković Goran C.

    2007-01-01

    The influence of nickel loading (5; 10; 20 wt% Ni), temperature of heat treatment (400; 700; 1100°C) and way of catalyst preparation on the catalyst component interactions (CCI) in the impregnated, mechanical powder mixed and co-precipitated catalyst was investigated. For sample characterization, low temperature nitrogen adsorption (LTNA) and X-ray diffraction (XRD) were applied. Significant differences were revealed, concerning CCI in dependence of nickel loading, temperature of heat treatme...

  10. Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor.

    Science.gov (United States)

    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.

  11. Modelling the transport of carbonic acid anions through anion-exchange membranes

    International Nuclear Information System (INIS)

    Nikonenko, V.; Lebedev, K.; Manzanares, J.A.; Pourcelly, G.

    2003-01-01

    Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO 3 - and CO 3 2- anions through the membrane which takes into account Donnan exclusion of H + ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed

  12. Chiral pyrrolidinium salts derived from menthol as precursor – synthesis and properties

    Directory of Open Access Journals (Sweden)

    Janus Ewa

    2017-09-01

    Full Text Available Six new chiral pyrolidinium salts with chiral substituent at quaternary nitrogen atom were synthesized with high overall yields from (--menthol as cheap chiral precursor and were identified by NMR and HRMS spectroscopy. It was shown that anion type had the effect on chemical shift of protons adjacent to quaternary nitrogen atom and physical properties of these salts. Salts with NTf2 or NPf2 were in a liquid state at room temperature and characterized with the highest thermal stability among others. Furthermore, chiral ionic liquid with NTf2 anion was used as solvent in Diels-Alder reaction and gave higher yield and stereoselectivity than in ionic liquids with achiral cations. Synthesized chiral salts have the potential as chiral solvents in synthesis and auxiliaries in analytical methods to improve chiral recognition.

  13. Experimental Detection of the Pentazole Anion, N5(-)

    National Research Council Canada - National Science Library

    Vij, Ashwani

    2002-01-01

    .... Whereas at low collision voltages the para-phenoxypentazole anion undergoes stepwise N2 elimination generating the corresponding azide and nitrene, at high collision voltages the N5(-) anion is formed...

  14. Advances in anion supramolecular chemistry: from recognition to chemical applications.

    Science.gov (United States)

    Evans, Nicholas H; Beer, Paul D

    2014-10-27

    Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under-exploited anion-π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion-templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research. The supramolecular chemistry of anions has also found real practical use in a variety of applications such as catalysis, ion extraction, and the use of anions as stimuli for responsive chemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Use of Pillared Clay-Based Catalysts for Wastewater Treatment Through Fenton-Like Processes

    Science.gov (United States)

    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).

  16. Study on the poisoning effect-of non-vanadium catalysts by potassium

    Science.gov (United States)

    Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

    2018-02-01

    The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.

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

    Science.gov (United States)

    Zelenay, Piotr; Wu, Gang

    2014-04-29

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

  18. Development and characterization of direct ethanol fuel cells using alkaline anion-exchange membranes

    Science.gov (United States)

    Lim, Peck Cheng

    2009-08-01

    Alkaline membrane fuel cell (AMFC) is a relatively new fuel cell technology that is generating considerable interests. It offers the electrocatalytic advantages of conventional alkaline fuel cells, and the manufacturing and cost advantages of solid polymer electrolyte fuel cells. This project was carried out to develop and characterize high performance membrane electrode assemblies (MEAs) for all-solid-state AMFCs. The primary fuel of interests is ethanol, but hydrogen was used in the development stages to facilitate the diagnostic and evaluation of the fuel cell performance. In the preliminary investigation, AMFC was assembled using off-the-shelf electrodes and anion-exchange membrane (AEM). It was found that the performance of AMFC operating on ethanol fuel was limited by a large high-frequency resistance (HFR) value. The advantage of using non-toxic ethanol fuel was also compromised by the need to add hydrazine and potassium hydroxide to the fuel blend. Subsequently, a high performance MEA was developed for an all-solid-state AMFC, in which liquid electrolyte or other additives were not required during the operation of the fuel cell. Ionomer was incorporated in the formulation of catalyst ink, and the catalyst ink was directly coated on the anion-exchange membrane (AEM). An ionomer content of 20 wt.% was found to be the optimum amount required in the catalyst layers. It was demonstrated that the AMFC generated a maximum power density of 365 mW/cm2 and 213 mW/cm 2 with the use of hydrogen/oxygen and hydrogen/pure air, respectively. The performance of the AMFC was also found to be influenced by exposure to carbon dioxide in the air. Hence, the CCMs were pre-treated in potassium hydroxide solution and pure oxygen was used to condition the fuel cell to maximize the power output from the AMFCs. Although satisfactory performance was demonstrated in the AMFC, its stability during cell operation remains a major issue. The poor stability was attributed to degradation of

  19. Dispersion enhanced metal/zeolite catalysts

    Science.gov (United States)

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

    1987-01-01

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

  20. Non-PGM cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

    2017-09-27

    A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

  1. Hyperfine interactions in metallic catalysts

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  2. Production of Biofuel via Catalytic Hydrocracking of Kapuk (Ceiba pentandra) Seed Oil with NiMo/HZSM-5 Catalyst

    OpenAIRE

    Parahita I Gede Andy Andika; Mirzayanti Yustia Wulandari; Gunardi Ignatius; Roesyadi Achmad; Prajitno Danawati Hari

    2018-01-01

    Biofuel is one of alternative energy that is being developed today to solve the problem of limited fossil fuel as an energy source. The goal of this study is to produce biofuel from kapuk (Ceiba pentandra) seed oil (KSO) through catalytic hydrocracking process using NiMo/HZSM-5 catalyst. NiMo/HZSM-5 catalyst was obtained by impregnation of nickel and molybdenum as metallic precursors on HZSM-5 catalyst as support using incipient wetness impregnation method. It was found that the surface area ...

  3. Catalytic cracking of iso-hexene over sapo-34 catalyst

    International Nuclear Information System (INIS)

    Nawaz, Z.; Shu, Q.

    2009-01-01

    The catalytic cracking of model feed compound, iso-hexene (2-methyl-1-pentene) was experimentally studied over 100% pure SAPO-34 zeolite catalyst. The critical focus was given to obtain maximum propylene selectivity. The product distributions were analyzed at temperature between 450-600 degree C. time-on-stream (TOS) from 1 to 5 min. and at WHSV = 7.9 h/sub -1/ The reaction behavior was quantified on both direct and indirect carbenium ion mechanisms owing to catalyst's small pore diameter with respect to 2-methyl-l-pentene kinetic diameter. The propylene yield and selectivity obtained was 41.2% and 43.1% respectively. with higher overall olefins selectivity 90.3%. The small pore size and week surface acid sites of 1000 percent pure SAPO-34 catalyst were found to be suitable for light olefins production and eliminate chances of bimolecular reactions. It was observed that both conversion and selectivity were strongly effected by TOS, as coke precursors become dominant and deactivate catalyst at higher TOS. (author)

  4. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States); Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ γ-Al2O3, and Pt/ γ-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module.

  5. Oxygen-reducing catalyst layer

    Science.gov (United States)

    O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  6. Catalyst systems and uses thereof

    Science.gov (United States)

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

    2012-07-24

    A method of carbon monoxide (CO) removal comprises providing an oxidation catalyst comprising cobalt supported on an inorganic oxide. The method further comprises feeding a gaseous stream comprising CO, and oxygen (O.sub.2) to the catalyst system, and removing CO from the gaseous stream by oxidizing the CO to carbon dioxide (CO.sub.2) in the presence of the oxidation catalyst at a temperature between about 20 to about 200.degree. C.

  7. High Throughput In Situ XAFS Screening of Catalysts

    International Nuclear Information System (INIS)

    Tsapatsaris, Nikolaos; Beesley, Angela M.; Weiher, Norbert; Tatton, Helen; Schroeder, Sven L. M.; Dent, Andy J.; Mosselmans, Frederick J. W.; Tromp, Moniek; Russu, Sergio; Evans, John; Harvey, Ian; Hayama, Shu

    2007-01-01

    We outline and demonstrate the feasibility of high-throughput (HT) in situ XAFS for synchrotron radiation studies. An XAS data acquisition and control system for the analysis of dynamic materials libraries under control of temperature and gaseous environments has been developed. The system is compatible with the 96-well industry standard and coupled to multi-stream quadrupole mass spectrometry (QMS) analysis of reactor effluents. An automated analytical workflow generates data quickly compared to traditional individual spectrum acquisition and analyses them in quasi-real time using an HT data analysis tool based on IFFEFIT. The system was used for the automated characterization of a library of 91 catalyst precursors containing ternary combinations of Cu, Pt, and Au on γ-Al2O3, and for the in situ characterization of Au catalysts supported on Al2O3 and TiO2

  8. Ultrasound assisted synthesis of iron doped TiO2 catalyst.

    Science.gov (United States)

    Ambati, Rohini; Gogate, Parag R

    2018-01-01

    The present work deals with synthesis of Fe (III) doped TiO 2 catalyst using the ultrasound assisted approach and conventional sol-gel approach with an objective of establishing the process intensification benefits. Effect of operating parameters such as Fe doping, type of solvent, solvent to precursor ratio and initial temperature has been investigated to get the best catalyst with minimum particle size. Comparison of the catalysts obtained using the conventional and ultrasound assisted approach under the optimized conditions has been performed using the characterization techniques like DLS, XRD, BET, SEM, EDS, TEM, FTIR and UV-Vis band gap analysis. It was established that catalyst synthesized by ultrasound assisted approach under optimized conditions of 0.4mol% doping, irradiation time of 60min, propan-2-ol as the solvent with the solvent to precursor ratio as 10 and initial temperature of 30°C was the best one with minimum particle size as 99nm and surface area as 49.41m 2 /g. SEM analysis, XRD analysis as well as the TEM analysis also confirmed the superiority of the catalyst obtained using ultrasound assisted approach as compared to the conventional approach. EDS analysis also confirmed the presence of 4.05mol% of Fe element in the sample of 0.4mol% iron doped TiO 2 . UV-Vis band gap results showed the reduction in band gap from 3.2eV to 2.9eV. Photocatalytic experiments performed to check the activity also confirmed that ultrasonically synthesized Fe doped TiO 2 catalyst resulted in a higher degradation of Acid Blue 80 as 38% while the conventionally synthesized catalyst resulted in a degradation of 31.1%. Overall, the work has clearly established importance of ultrasound in giving better catalyst characteristics as well as activity for degradation of the Acid Blue 80 dye. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Premarital precursors of marital infidelity.

    Science.gov (United States)

    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.

  10. Modelling the Effects of Competing Anions on Fluoride Removal by ...

    African Journals Online (AJOL)

    NICOLAAS

    ... the physico-chemical properties of anions and their interaction with the adsorbent surface.16. Properties of anions such as the solubility, ionic radius, hydration energy and bulk diffusion coefficient are of great importance for the selective adsorption of anions.17 In our earlier study the equilibrium and thermodynamics of ...

  11. Reuse of Hydrotreating Spent Catalyst

    International Nuclear Information System (INIS)

    Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

    2004-01-01

    All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

  12. Mixed Alcohol Synthesis Catalyst Screening

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Mark A.; White, James F.; Stevens, Don J.

    2007-09-03

    National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

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

    Science.gov (United States)

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

    2018-01-01

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

  14. Three dimensional metal/N-doped nanoplate carbon catalysts for oxygen reduction, the reason for using a layered nanoreactor.

    Science.gov (United States)

    Yeganeh Ghotbi, Mohammad; Javanmard, Arash; Soleimani, Hassan

    2018-02-21

    A layered nanoreactor (zinc hydroxide gallate/nitrate nanohybrid) has been designed as a nano-vessel to confine the gallate/nitrate reaction inside zinc hydroxide layers for production of metal/nitrogen-doped carbon catalysts. Metals (Fe 2+ , Co 2+ and Ni 2+ ) doped and bare zinc hydroxide nitrates (ZHN) were synthesized as the α-phase hydroxide hosts. By an incomplete ion-exchange process, nitrate anions between the layers of the hosts were then partially replaced by the gallate anions to produce the layered nanoreactors. Under heat-treatment, the reaction between the remaining un-exchanged nitrate anions and the organic moiety inside the basal spacing of each nanohybrid plate resulted in obtaining highly porous 3D metal/nitrogen-doped carbon nanosheets. These catalysts were then used as extremely efficient electrocatalysts for catalyzing oxygen reduction reaction (ORR). This study is intended to show the way to get maximum electrocatalytic activity of the metal/N-doped carbon catalysts toward the ORR. This exceptionally high ORR performance originates from the increased available surface, the best pore size range and the uniform distribution of the active sites in the produced catalysts, all provided by the use of new idea of the layered nanoreactor.

  15. Polysulfone-based anion exchange polymers for catalyst binders in alkaline electrolyzers

    Czech Academy of Sciences Publication Activity Database

    Schauer, Jan; Žitka, Jan; Pientka, Zbyněk; Křivčík, J.; Hnát, J.; Bouzek, K.

    2015-01-01

    Roč. 132, č. 40 (2015), 42581_1-42581_7 ISSN 0021-8995 Institutional support: RVO:61389013 Keywords : degradation * electrochemistry * membranes Subject RIV: JI - Composite Materials Impact factor: 1.866, year: 2015

  16. Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic ...

    Indian Academy of Sciences (India)

    800°C) has been used for the benzylation of toluene and other aromatic compounds by benzyl chloride. Hydrotalcite before and after its calcination was characterized for surface area, crystalline phases and basicity. Both the hydrotalcite ...

  17. 1994 Accident sequence precursor program results

    International Nuclear Information System (INIS)

    Belles, R.J.; Cletcher, J.W.; Copinger, D.A.

    1996-01-01

    The Accident Sequence Precursor (ASP) Program involves the systematic review and evaluation of operational events that have occurred at light-water reactors to identify and categorize precursors to potential severe core damage accident sequences. The results of the ASP Program are published in an annual report. The most recent report, which contains the analyses of the precursors for 1994, is NUREG/CR-4674, Vols. 21 and 22, Precursors to Potential Severe Core Damage Accidents: 1994, A Status Report, published in December 1995. This article provides an overview of the ASP review and evaluation process and a summary of the results for 1994. 12 refs., 2 figs., 4 tabs

  18. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    Science.gov (United States)

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan

    1998-01-01

    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

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

    Science.gov (United States)

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

    2017-09-01

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

  20. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Dongyan, E-mail: xdy0156@sina.com; Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: • SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. • Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. • The hydration of ZS is vital to the acidic property and catalytic performance. • The ZS/SAPO-34 catalyst treated at 200 °C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 °C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  1. High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

    2009-01-01

    A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

  2. Preparation of porous silicon carbide from molecular precursors; Preparation de carbure de silicium poreux a partir de precurseurs moleculaires

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, J

    2008-02-15

    The preparation of Porous Silicon Carbide (SiC) from molecular precursors is described in this work. Firstly, poly-silane and poly-carbo-silane were synthesised from targeted molecular precursors TSCH and TCDSCB. The pyrolysis of these polymers under inert conditions gave the SiC. Secondly, the preparation of functional poly-silane was explored. It was shown that Cp{sub 2}Ti(OPh){sub 2} was a suitable catalyst for the preparation of such functional poly-silane in a one-pot process. Finally, macroporous SiC were prepared from hard templating method by using a commercial silica. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-04-01

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

  4. Effect of Support Materials on Catalytic Activity of Nano Ruthenium Catalyst in Hydrogenolysis of Glycerol

    International Nuclear Information System (INIS)

    Noraini Hamzah; Mohd Ambar Yarmo

    2016-01-01

    A series of heterogenous catalysts based on supported ruthenium were prepared from RuCl 3 precursor by impregnation method. The effect of support materials (bentonite, TiO 2 , Al 2 O 3 and SiO 2 ) on catalytic activity of Ru catalyst for hydrogenolysis of glycerol were investigated under mild reaction condition of 150 degree Celsius and 20 bar initial hydrogen pressure for 7 hours reaction time and glycerol concentration was 20 % (wt). It was found that the type of support material have significant effects on the activity and selectivity of glycerol hydrogenolysis. The order of Ru catalyst activity was Ru/ bentonite > Ru /Al 2 O 3 ≅ Ru/ TiO 2 > Ru/ SiO 2 . This study showed that bentonite supported Ru catalyst was the most active with glycerol conversion reaching 62.5 % compared to other supports. All the tested catalyst exhibited high selectivity to 1,2-propanediol with more than 80 %. Characterization of the catalysts was carried out using BET, XPS, FESEM-EDX and TEM to obtain the physicochemical properties of the catalysts. (author)

  5. Enhancement of microbial fuel cell performance by introducing a nano-composite cathode catalyst.

    Science.gov (United States)

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

    2018-03-01

    Iron aminoantipyrine (Fe-AAPyr), graphene nanosheets (GNSs) derived catalysts and their physical mixture Fe-AAPyr-GNS were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR) with the activated carbon (AC) as a baseline. Fe-AAPyr catalyst was prepared by Sacrificial Support Method (SSM) with silica as a template and aminoantipyrine (AAPyr) as the organic precursor. 3D-GNS was prepared using modified Hummers method technique. The Oxygen Reduction Reaction (ORR) activity of these catalysts at different loadings was investigated by using rotating ring disk (RRDE) electrode setup in the neutral electrolyte. The performance of the catalysts integrated into air-breathing cathode was also investigated. The co-presence of GNS (2 mg cm -2 ) and Fe-AAPyr (2 mg cm -2 ) catalyst within the air-breathing cathode resulted in the higher power generation recorded in MFC of 235 ± 1 μW cm -2 . Fe-AAPyr catalyst itself showed high performance (217 ± 1 μW cm -2 ), higher compared to GNS (150 ± 5 μW cm -2 ) while AC generated power of roughly 104 μW cm -2 .

  6. Co-Liquefaction of Elbistan Lignite with Manure Biomass; Part 1. Effect of Catalyst Concentration

    Science.gov (United States)

    Koyunoglu, Cemil; Karaca, Hüseyin

    2017-12-01

    The hydrogenation of coal by molecular hydrogen has not been appreciable unless a catalyst has been used, especially at temperatures below 500 °C. Conversion under these conditions is essentially the result of the pyrolysis of coal, although hydrogen increases the yield of conversion due to the stabilization of radicals and other reactive species. Curtis and his co-workers has shown that highly effective and accessible catalyst are required to achieve high levels of oil production from the coprocessing of coal and heavy residua. In their work, powdered hydrotreating catalyst at high loadings an oil-soluble metal salts of organic acids as catalyst precursors achieved the highest levels of activity for coal conversion and oil production. Red mud which is iron-based catalysed has been used in several co-processing studies. It was used as an inexpensive sulphur sink for the H2S evolved to convert Fe into pyrrohotite during coal liquefaction. In this study, Elbistan Lignite (EL) processed with manure using red mud as a catalyst with the range of concentration from 3% to 12%. The main point of using red mud catalyst is to enhance oil products yield of coal liquefaction, which deals with its catalytic activity. On the other hand, red mud acts on EL liquefaction with manure as a catalyst and represents an environmental option to produce lower sulphur content oil products as well.

  7. CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

    Directory of Open Access Journals (Sweden)

    Didik Prasetyoko

    2010-07-01

    Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

  8. REACTOR FILLED WITH CATALYST MATERIAL, AND CATALYST THEREFOR

    NARCIS (Netherlands)

    Sie, S.T.

    1995-01-01

    Abstract of WO 9521691 (A1) Described is a reactor (1) at least partially filled with catalyst granules (11), which is intended for catalytically reacting at least one gas and at least one liquid with each other. According to the invention the catalyst granules (11) are collected in agglomerates

  9. Interactions between anions and soil constituents

    International Nuclear Information System (INIS)

    Bolt, G.H.; Haan, F.A.M. de

    1965-01-01

    Clay mineral crystals are characterized by a non-isotropic structure, in which a pattern is recognized. It is known that the planar sides are negatively charged (as a result of the isomorphic replacement of Si 4+ by Al 3+ and/or Al 3+ by Mg 2+ ). Under certain conditions the exposed alumina groups at the edges are charged positively. The different types of interaction between ions and clay crystals may be listed as follows: (a) Cations: positive adsorption on planar side (electrostatic interaction modified by -- non-electrostatic -- specific factors); and possibly negative adsorption at positively charged edges (electrostatic effect). (b) Anions: negative adsorption (exclusion) on planar side (electrostatic effect); and positive adsorption on the edges -- in part electrostatic, if edge positively charged; furthermore chemisorption of certain anions, as e.g. PO 4 , SiO 4

  10. An intracellular anion channel critical for pigmentation.

    Science.gov (United States)

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-12-16

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation.

  11. Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Tikkanen

    2006-12-31

    The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replaced by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.

  12. Politseiuuringud kooskõlastamisele / Liivia Anion

    Index Scriptorium Estoniae

    Anion, Liivia

    2003-01-01

    1. aprillil 2003. a. moodustatud uurimistööde kooskõlastamise komisjoni tegevuse eesmärk on saada ülevaade kõrgkoolides õppivate töötajate poolt politseis korraldatavatest uurimustest, kasutada saadud infot politsei kasuks ja vältida teenistujate tööd segavate uurimuste tegemist. Komisjoni liige Liivia Anion teeb ülevaate komisjoni otsustuspädevuse valdkondadest ja töökorraldusest

  13. Sequence anatomy of mitochondrial anion carriers

    Czech Academy of Sciences Publication Activity Database

    Ježek, Petr; Ježek, Jan

    2003-01-01

    Roč. 534, 1-3 (2003), s. 15-25 ISSN 0014-5793 R&D Projects: GA AV ČR IAA5011106; GA ČR GA301/02/1215; GA MŠk ME 389 Institutional research plan: CEZ:AV0Z5011922 Keywords : mitochondrial anion carriers * carrier genomics * bioinformatics Subject RIV: CE - Biochemistry Impact factor: 3.609, year: 2003

  14. Molecular basis of claudin-17 anion selectivity.

    Science.gov (United States)

    Conrad, Marcel P; Piontek, Jörg; Günzel, Dorothee; Fromm, Michael; Krug, Susanne M

    2016-01-01

    Claudin-17 is a paracellular channel-forming tight junction protein. Unlike the cation channels claudin-2 and -15, claudin-17 forms a distinct anion-selective channel. Aim of this study was to determine the molecular basis of channel formation and charge selectivity of this protein. To achieve this, residues located in the extracellular loops (ECL) 1 and 2 of claudin-17 were substituted, preferably those whose charges differed in claudin-17 and in claudin-2 or -15. The respective mutants were stably expressed in MDCK C7 cells and their ability to form charge-selective channels was analyzed by measuring ion permeabilities and transepithelial electrical resistance. The functional data were combined with homology modeling of the claudin-17 protomer using the structure of claudin-15 as template. In ECL1, K65, R31, E48, and E44 were found to be stronger involved in Cldn17 channel function than the clustered R45, R56, R59, and R61. For K65, not only charge but also stereochemical properties were crucial for formation of the anion-selective channel. In ECL2, both Y149 and H154 were found to contribute to constitution of the anion channel in a distinct manner. In conclusion, we provide insight into the molecular mechanism of the formation of charge- and size-selective paracellular ion channels. In detail, we propose a hydrophilic furrow in the claudin-17 protomer spanning from a gap between the ends of TM2 and TM3 along R31, E48, and Y67 to a gap between K65 and S68 lining the anion channel.

  15. Novel Reforming Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pfefferle, Lisa D; Haller, Gary L

    2012-10-16

    Aqueous phase reforming is useful for processing oxygenated hydrocarbons to hydrogen and other more useful products. Current processing is hampered by the fact that oxide based catalysts are not stable under high temperature hydrothermal conditions. Silica in the form of structured MCM-41 is thermally a more stable support for Co and Ni than conventional high surface area amorphous silica but hydrothermal stability is not demonstrated. Carbon nanotube supports, in contrast, are highly stable under hydrothermal reaction conditions. In this project we show that carbon nanotubes are stable high activity/selectivity supports for the conversion of ethylene glycol to hydrogen.

  16. A Catalyst for Change

    DEFF Research Database (Denmark)

    Lønsmann, Dorte

    2017-01-01

    into in a process that hinges on new members functioning as tools for management to bring about the desired change. The article shows that while the newcomer is used as a catalyst for increased use of English and for the creation of a 'global mindset,' she is at the same time socialized into the existing Danish...... for changing language practices toward more English, with the ultimate aim of creating a 'global mindset' in the organization. Language socialization in a transient multilingual setting is shown to focus on and assign positive value to new linguistic norms that experienced members are socialized...

  17. In-situ characterization of heterogeneous catalysts

    CERN Document Server

    Rodriguez, Jose A; Chupas, Peter J

    2013-01-01

    Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

  18. Recyclable Aggregates of Mesoporous Titania Synthesized by Thermal Treatment of Amorphous or Peptized Precursors

    Directory of Open Access Journals (Sweden)

    Maria Cristina Mascolo

    2018-03-01

    Full Text Available Recyclable aggregates of mesoporous titania with different anatase–rutile ratios have been prepared by thermal treatments of either amorphous or peptized precursors. These last two have been obtained by hydrolysis of either Ti(OC2H54 or of Ti(OC2H54 in mixture with 5 mol % Zr(OC3H74 at room temperature in the presence of NH4OH as a catalyzing agent. The anatase–rutile ratio, the recyclable aggregates of the nano-sized particles, the mesoporosity, the surface area and the crystallinity of the resulting crystallized products of titania can be controlled by the synthesis parameters including: concentration of ammonia catalyst, stirring time and concentration of the peptizing HNO3, drying method of peptized precursors, calcination temperature, and finally the ramp rate up to the titania crystallization temperature. A broad range of synthesis parameters control the crystal sizes of titania particles produced. This allows catalyst preparation with very different crystal size, surface area, anatase to rutile crystal ratio and various mesoporous structures. Drying by lyophilization of precursors reduce the aggregation of the primary particles giving micro-/macroporous structures.

  19. Revisiting the Anionic Polymerization of Methyl Ethacrylate

    Energy Technology Data Exchange (ETDEWEB)

    Kennemur, Justin G. [Department of Chemistry and Biochemistry, Florida State University, Tallahassee FL 32306-4390 USA; Bates, Frank S. [Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis MN 55455-0431 USA; Hillmyer, Marc A. [Department of Chemistry, University of Minnesota, Minneapolis MN 55455-0431 USA

    2017-09-26

    Synthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at -78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol-1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer-to-initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene-block-PMEA, (PS-PMEA), and poly(4-tert-butylstyrene)-block-PMEA, (PtBS-PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed by small-angle X-ray scattering (SAXS) for symmetric PS-PMEA at relatively high molar mass (39 kg mol-1) suggests an effective interaction parameter (χeff) that is smaller than for PS-block-poly(methyl methacrylate). On the other hand, PtBS-PMEA block polymers form a well-ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.

  20. Impacts of anions on the oxygen reduction reaction kinetics on platinum and palladium surfaces in alkaline solutions.

    Science.gov (United States)

    Zhu, Shangqian; Hu, Xiaomeng; Shao, Minhua

    2017-03-15

    The fundamental understanding of the impacts induced by anions on oxygen reduction reaction (ORR) in alkaline media is of great importance in the design of more advanced catalysts for alkaline fuel cells (AFC). In this study, the specific adsorption of F - , Cl - , ClO 4 - , CO 3 2- , SO 4 2- , and citrate anions on Pt/C and Pd/C catalysts, and their impacts on the ORR kinetics in alkaline solutions were systematically studied. It was found that F - , Cl - and ClO 4 - did not specifically adsorb on Pt or Pd surfaces and had no poisoning effect on ORR. CO 3 2- and SO 4 2- had significant effects on Pt/C and lowered the activity even at a very low concentration. On the other hand, their impacts on Pd/C were negligible. Self-dissociation of citrate anions was found to occur on both Pt/C and Pd/C in the H adsorption/desorption and double layer regions. For the first time, surface enhanced infrared absorption spectroscopy (SEIRAS) with the attenuated total reflection (ATR) technique was used to investigate the self-dissociation of citrate on Pt and Pd thin film electrodes. The breaking of carboxylic groups and the carbon backbone was proposed as a possible dissociation pathway for citrate. The adsorbed species have a negligible effect on ORR activity on Pt/C as they are removed by oxidation before 0.75 V. In contrast, their oxidation on Pd/C surfaces is not completed until 0.91 V, which causes a lower ORR activity observed in rotating disk electrode measurements. The findings in this paper emphasize the importance of specific adsorption of anions and double-layer interfacial effects on the ORR activity measurement in alkaline solutions.

  1. Catalysts for low temperature oxidation

    Science.gov (United States)

    Toops, Todd J.; Parks, III, James E.; Bauer, John C.

    2016-03-01

    The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

  2. Ion-selective electrode and anion gap range: What should the anion gap be?

    Science.gov (United States)

    Sadjadi, Seyed-Ali; Manalo, Rendell; Jaipaul, Navin; McMillan, James

    2013-01-01

    Using flame photometry technique in the 1970s, the normal value of anion gap (AG) was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE), the anion gap value has fallen to lower levels. A retrospective study of US veterans from a single medical center was performed to determine the value of the anion gap in subjects with normal renal function and normal serum albumin and in patients with lactic acidosis and end-stage renal disease on dialysis. In 409 patients with an estimated glomerular filtration rate ≥60 mL/min/1.73 m(2) body surface area and serum albumin ≥4 g/dL, the mean AG was 7.2 ± 2 (range 3-11) meq/L. In 299 patients with lactic acidosis (lactate level ≥4 meq/L) and 68 patients with endstage renal disease on dialysis, the mean AG was 12.5 meq/L and 12.4 meq/L, respectively. A value anion gap and a possible clue to drug intoxication and paraproteinemic disorders. With the advent of ISE for measurement of analytes, the value of the anion gap has fallen. Physicians need to be aware of the normal AG value in their respective institutions, and laboratories need to have an established value for AG based on the type of instrument they are using.

  3. nanoparticles synthesized by citrate precursor m

    African Journals Online (AJOL)

    user

    Abstract. Ni0.5M0.5Fe2O4 (M = Co, Cu) ferrite nanoparticles were synthesized using citrate precursor method. The citrate precursor was annealed at temperatures 400oC, 450oC, 500oC and 550oC. The annealed powders were characterized using X-ray diffractometer. (XRD) and vibrating sample magnetometer (VSM).

  4. Rapid synthesis of macrocycles from diol precursors

    DEFF Research Database (Denmark)

    Wingstrand, Magnus; Madsen, Charlotte Marie; Clausen, Mads Hartvig

    2009-01-01

    A method for the formation of synthetic macrocycles with different ring sizes from diols is presented. Reacting a simple diol precursor with electrophilic reagents leads to a cyclic carbonate, sulfite or phosphate in a single step in 25-60% yield. Converting the cyclization precursor to a bis-ele...

  5. Synthesis of Carbon Nano tubes Using Anadara Granosa Shells as Catalyst Support

    International Nuclear Information System (INIS)

    Mohd Zobir Hussein; Mohd Zobir Hussein; Salwani Asyikin Zakarya; Siti Halimah Sarijo

    2011-01-01

    The synthesis of carbon nano tubes (CNTs) by chemical vapor deposition (CVD) method using natural calcite prepared from Anadara granosa shells (CS), as metal catalyst support was studied. Hexane and iron were used as carbon precursor and catalyst, respectively. The as synthesised CNTs was characterized using XRD, TEM and FESEM. From the XRD patterns the CNTs peak can be seen more incisive after purification process and from the FESEM micrographs the CNTs can be seen as a bunch of rope-like structures. (author)

  6. Arsenate stabilized Cu₂O nanoparticle catalyst for one-electron transfer reversible reaction.

    Science.gov (United States)

    Sahoo, Ramkrishna; Dutta, Soumen; Pradhan, Mukul; Ray, Chaiti; Roy, Anindita; Pal, Tarasankar; Pal, Anjali

    2014-05-14

    The befitting capping capabilities of AsO4(3-) provide a stable Cu2O nanocatalyst from a galvanic reaction between a Cu(II) precursor salt and As(0) nanoparticles. This stable Cu2O hydrosol appears to be a suitable catalyst for the one-electron transfer reversible redox reaction between Eosin Y and NaBH4. The progress of the reaction relates to three different kinetic stages. In the presence of the new catalyst the reversible redox reaction of Eosin Y in air shows a periodic color change providing a new crowd-pleasing demonstration, i.e. a "clock reaction".

  7. Ring opening metathesis polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H.; Johnson, L.K.; Novak, B.M.; Hillmyer, M.; Benedicto, A.; France, M.; Nguyen, S.T. [California Institute of Technology, Pasadena, CA (United States)

    1993-12-31

    Over the past eight years, a number of new catalysts for the ring opening metathesis polymerization of cyclic olefins have been developed. These catalysts are simple organometallic complexes containing metal carbon multiple bonds that in most cases polymerize olefins by a living process. These catalysts have been used to prepare a family of near monodispersed and structurally homogeneous polymers, a series of telechelic polymers with controlled molecular weight and functionality and triblock polymers with segments with potentially interesting electronic properties. A series of new group VIII catalysts are being developed that allow a wide range of functionality to be incorporated into the polymer side chains. The same catalysts can also be used in the synthesis of fine chemicals.

  8. Supported molten-metal catalysts

    Science.gov (United States)

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

    2001-01-01

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

  9. Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    (FDA), a possible plastics precursor. The novel catalyst systems were characterized by nitrogen physisorption, XRPD, TEM and EDS analysis, and applied for the oxidation with no added base at moderate to high pressures of dioxygen and elevated temperatures. The effects of support, temperature...... and oxidant pressure were studied and optimized to allow a quantitative yield of FDA to be obtained....

  10. Structural and elemental influence from various MOFs on the performance of Fe@C catalysts for Fischer-Tropsch synthesis

    NARCIS (Netherlands)

    Wezendonk, T.A.; Warringa, Quirinus S E; Santos, Vera P.; Chojecki, Adam; Ruitenbeek, Matthijs; Meima, Garry; Makkee, M.; Kapteijn, F.; Gascon Sabate, J.

    2017-01-01

    The structure and elementary composition of various commercial Fe-based MOFs used as precursors for Fischer-Tropsch synthesis (FTS) catalysts have a large influence on the high-temperature FTS activity and selectivity of the resulting Fe on carbon composites. The selected Fe-MOF topologies

  11. The interrelationships of mathematical precursors in kindergarten.

    Science.gov (United States)

    Cirino, Paul T

    2011-04-01

    This study evaluated the interrelations among cognitive precursors across quantitative, linguistic, and spatial attention domains that have been implicated for math achievement in young children. The dimensionality of the quantity precursors was evaluated in 286 kindergarteners via latent variable techniques, and the contribution of precursors from each domain was established for small sums addition. Results showed a five-factor structure for the quantity precursors, with the major distinction being between nonsymbolic and symbolic tasks. The overall model demonstrated good fit and strong predictive power (R(2)=55%) for addition number combinations. Linguistic and spatial attention domains showed indirect relationships with outcomes, with their effects mediated by symbolic quantity measures. These results have implications for the measurement of mathematical precursors and yield promise for predicting future math performance. Copyright © 2010 Elsevier Inc. All rights reserved.

  12. Rapid evaluation of catalysts and MAO activators by kinetics: what controls polymer molecular weight and activity in metallocene/MAO catalysts?

    Science.gov (United States)

    Ghiotto, Fabio; Pateraki, Chrysoula; Severn, John R; Friederichs, Nic; Bochmann, Manfred

    2013-07-07

    The influence of methylaluminoxane (MAO) catalyst activators of different concentrations and preparative histories on the performance of 1-hexene polymerisations was investigated by kinetic methods, using rac-Me2Si(2-Me-Benz[e]Ind)2ZrCl2 as the standard catalyst precursor. Fast sampling and analysis allow the time dependence of monomer conversion and the growth of the number-average polymer molecular weight to be determined at a sufficiently short timescale to make this a feasible method for routine catalyst evaluation. Differences in productivity, polymer molecular weight and active species count are shown to be primarily a linear function of the trimethylaluminium concentration. The results in toluene and heptane as solvents are compared; the data show that the inferior performance in heptane is due to a substantially lower active species concentration.

  13. Improved Low-Temperature Activity of V2O5-WO3/TiO2 for Denitration Using Different Vanadium Precursors

    Directory of Open Access Journals (Sweden)

    Lina Gan

    2016-02-01

    Full Text Available This work tested two V2O5-WO3/TiO2 catalysts with different vanadium precursors for selective catalytic reduction (SCR of flue gas NO using NH3 at 150–450 °C. While catalyst A was prepared using ammonium metavanadate (NH4VO3 through incipient impregnation, catalyst B was made according to the solvothermal method using vanadyl acetylacetonate (VO(acac2 as the vanadium precursor. The catalytic evaluation for denitration was in a laboratory fixed bed reactor using simulated flue gas under conditions of a gas hourly space velocity (GHSV of 40,000 h−1 and an NH3/NO molar ratio of 0.8. Without SO2 and water vapor in the flue gas at 200 °C, the realized NO conversion was 56% for catalyst A but 80% for B. The presence of 350 ppm SO2 and 10 vol. % water vapor in the flue gas slightly reduced the NO conversion over catalyst B, and its activity was stable in a 108-h continuous test at temperatures varying from 450 °C to 220 °C. Via fourier transformation infrared spectroscopy (FT-IR and thermogravimetric (TG analysis, it was shown that over catalyst B a dynamic balance between the formation and decomposition of ammonium sulfite or sulfate is built possibly at temperatures as low as 220 °C. For this catalyst there was a higher surface atomic concentration of vanadium and a higher ratio of V4+/(V4+ + V5+, while the NH3 adsorption test revealed more acidic sites on catalyst B. The study discloses a potentially new approach to prepare a V2O5-WO3/TiO2 catalyst with good performance for SCR of flue gas NO at 220–300 °C.

  14. CO{sub 2} REFORMING OF METHANE TO SYNGAS OVER HYDROTALCITES DERRIVED CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Z. Abdelssadek; F. Touahra; A. Saadi; O. Cherifi; D. Halliche [Laboratoire de Chimie du Gaz Naturel, Faculte de Chimie, El-Alia, Alger (Algeria); K. Bachari [Centre de recherches scientifiques et techniques en analyses physico-chimiques, Alger (Algeria)

    2008-09-30

    Considerable attention has been paid to the catalytic reforming of CH4 with CO2 to synthesis gas (CH4 + CO2 - 2CO + 2H2 ) in recent years. This reaction has very important environmental implications since both CH4 and CO2 contribute to the green house effect. They are also two of the most important abundant carbon-containing materials. Therefore, converting these two gases into a valuable synthesis gas may not only reduce atmospheric emissions of CO2 and CH4 , but also satisfy the requirement of many synthesis processes. In addition, the synthesis gas produced by this reaction has a high CO content, it is more suitable for the synthesis of valuable oxygenated chemicals then that produced by conventional steam reforming. Great efforts have been focused on the development of catalysts which show high activity and stability. Layered double hydroxides (LDH), are a class of synthetic two-dimensional nanostructured anionic clays catalysts. The catalysts obtained are characterized by ICP method, DRX, FTIR and BET methods. The data obtained from chemical analysis of the calcined catalysts confirmed that the n (M2+) / n(M3+) ratio is close to the intended value of 2. Room temperature FT-IR spectra were recorded in the range 4000 - 400 cm-1 , on a Perkin Elmer spectrometer. Catalysts stability were carried out at 650 C and a 1:1 CO2 / CH4 feed ratio. It was found that performances of catalysts after 6 h in reaction indicates that within this period nor or little deactivation takes place over them: At 650 C, the NiMgAL-HDL, NiMgLa-LDH catalysts reach respectively 54.0%, 69.0%, of methane conversion versus 75.0% 79.3% respectively of CO2 conversion. However, Co- catalysts did not show any catalytic activity in these experiments conditions.

  15. Near-fatal persistent anion- and osmolal-gap acidosis due to massive gamma-butyrolactone/ethanol intoxication.

    Science.gov (United States)

    Heytens, Luc; Neels, Hugo; Van Regenmortel, Niels; van den Brink, Wim; Henckes, Manu; Schouwers, Sofie; Dockx, Greet; Crunelle, Cleo L

    2015-03-01

    We report a case of an ethanol and massive gamma-butyrolactone (GBL) intoxication, the precursor of the recreational drug gamma-hydroxybutyric acid (GHB), resulting in life-threatening metabolic acidosis (pH 6.5) with a highly increased anion- and osmolal gap. Rapid analysis using gas chromatography revealed a GHB plasma concentration of 4400 mg/L, far above the upper limit concentration of 1000 mg/L found in adult fatalities attributed to GBL. Full recovery was established following supportive treatment including haemodialysis. This is the first report of a combined ethanol/GBL intoxication as a cause of high serum anion- and osmolal-gap metabolic acidosis. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

  16. Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy.

    Science.gov (United States)

    Eilert, André; Roberts, F Sloan; Friebel, Daniel; Nilsson, Anders

    2016-04-21

    Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO2RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO2RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)-carbonate/hydroxide is also reported. This study highlights the importance of using oxidized copper precursors for constructing selective CO2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.

  17. Ion-selective electrode and anion gap range: What should the anion gap be?

    OpenAIRE

    Sadjadi,; Manalo,Rendell; Jaipaul,Navin; McMillan,James

    2013-01-01

    Seyed-Ali Sadjadi, Rendell Manalo, Navin Jaipaul, James McMillan Jerry L Pettis Memorial Veterans Medical Center, Loma Linda University School of Medicine, Loma Linda, CA, USA Background: Using flame photometry technique in the 1970s, the normal value of anion gap (AG) was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE), the anion gap value has fallen to lower levels. Methods: A retrospective study of US veteran...

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

    KAUST Repository

    Widger, Peter C. B.

    2011-07-26

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

  19. Synthesis of N-hydroxysuccinimide from succinic acid and hydroxylammonium chloride using Amberlyst A21 as reusable solid base catalyst

    Science.gov (United States)

    Le, Son Dinh; Nishimura, Shun; Ebitani, Kohki

    2018-01-01

    Solid base catalysts were studied for the first time to synthesize N-hydroxysuccinimide (NHS) through the reaction of succinic acid with hydroxylammonium chloride. The highest yield of 42% (±3%) with 65% (±4%) selectivity toward NHS production was achieved by using Amberlyst A21, which is a weak base anion-exchange resin. The present catalyst could be recycled during five runs without significant decreases in activity. Also, efficacy for the Amberlyst A21 mediated reaction was also explored with other dicarboxylic acids such as phthalic acid, glutaric acid, and maleic acid.

  20. Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Shirazi, Yaser; Tofighy, Maryam Ahmadzadeh [Research Centre for Membrane Separation Processes, Faculty of Chemical Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran (Iran, Islamic Republic of); Mohammadi, Toraj, E-mail: torajmohammadi@iust.ac.ir [Research Centre for Membrane Separation Processes, Faculty of Chemical Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran (Iran, Islamic Republic of); Pak, Afshin [Research Centre for Membrane Separation Processes, Faculty of Chemical Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran (Iran, Islamic Republic of)

    2011-06-01

    Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 deg. C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO{sub 3}/H{sub 2}SO{sub 4} (1/3 or 1/1), 8 M HCl or 8 M HNO{sub 3} was carried out. The results showed that 8 M HNO{sub 3} could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO{sub 3}/H{sub 2}SO{sub 4} (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.

  1. Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

    Science.gov (United States)

    Shirazi, Yaser; Tofighy, Maryam Ahmadzadeh; Mohammadi, Toraj; Pak, Afshin

    2011-06-01

    Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO 3/H 2SO 4 (1/3 or 1/1), 8 M HCl or 8 M HNO 3 was carried out. The results showed that 8 M HNO 3 could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO 3/H 2SO 4 (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.

  2. Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

    International Nuclear Information System (INIS)

    Shirazi, Yaser; Tofighy, Maryam Ahmadzadeh; Mohammadi, Toraj; Pak, Afshin

    2011-01-01

    Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 deg. C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO 3 /H 2 SO 4 (1/3 or 1/1), 8 M HCl or 8 M HNO 3 was carried out. The results showed that 8 M HNO 3 could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO 3 /H 2 SO 4 (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.

  3. Graphene-coated polymeric anion exchangers for ion chromatography

    International Nuclear Information System (INIS)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan; Wu, Shuchao; Zhang, Peimin; Zhi, Mingyu; Zhu, Yan

    2017-01-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  4. Graphene-coated polymeric anion exchangers for ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  5. Electron-beam-induced cyclization to obtain C-fiber precursors from polyacrylonitrile homopolymers

    International Nuclear Information System (INIS)

    Dietrich, J.; Hirt, P.; Herlinger, H.

    1996-01-01

    Alkyl radicals were produced and proved to be present (ESR) in polyacrylonitrile fibres which had been exposed to electron beams. By giving the irradiated fibres thermal treatment, it was possible to achieve a radical cyclisation of the PAN fibres. The mechanical textile characteristics of the fibres were determined; they were found to be suitable precursors for carbon fibres. In contrast to conventional cyclisation methods, the convenient high-energy method of irradiation does not need any external or internal catalysts (e.g. PAN copolymers), and it leads to reduced cyclisation times. (UK)

  6. Preparation of multilayer carbon microspheres by using graphitic carbon nitride as precursor

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xuefei, E-mail: wuxt12@mails.jlu.edu.cn; Wu, Xingtong

    2015-11-15

    Multilayer carbon microspheres were synthesized by using graphitic Carbon Nitride as precursor. The result of SEM and TEM showed that micrometer-sized multilayer spherical carbon structure had been prepared without the designed addition of any catalyst or template. The composition of the sample indicated that the sample was pure carbon materials. The result of XRD and Raman revealed low graphitization degree of carbon microspheres. FTIR and the analysis of theoretical spectra calculated by using GAUSSIAN 03 program indicated carbon microspheres structure model consisted of many five-member carbon rings. It also can be the cause of the low graphitized degree.

  7. Sulfonic-based precursors (SAPs for silica mesostructures: Advances in synthesis and applications

    Directory of Open Access Journals (Sweden)

    Sadegh Rostamnia*

    2016-01-01

    Full Text Available Sulfonic acid-based precursors (SAP play an important role in tailoring mesoporous silica’s and convert them to a solid acid catalyst with a Bronsted-type nature. These kinds of solid acids contribute to sustainable and green chemistry by their heterogeneous, recyclable, and high efficiency features. Therefore, knowing the properties and reactivity of SAPs can guide us to manufacture a sulfonated mesostructures compatible with reaction type and conditions. In the present review, some of the important SAPs, their reactivity and mechanism of functionalization are discussed.

  8. Development of GREET Catalyst Module

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhichao [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division; Cronauer, Donald C. [Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division

    2014-09-01

    Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.

  9. Designing Catalysts for Clean Technology, Green Chemistry, and Sustainable Development

    Science.gov (United States)

    Meurig Thomas, John; Raja, Robert

    2005-08-01

    There is a pressing need for cleaner fuels (free or aromatics and of minimal sulfur content) or ones that convert chemical energy directly to electricity, silently and without production of noxious oxides and particulates; chemical, petrochemical and pharmaceutical processes that may be conducted in a one-step, solvent-free manner and that use air as the preferred oxidant; and industrial processes that minimize consumption of energy, production of waste, or the use of corrosive, explosive, volatile, and nonbiodegradable materials. All these needs and other desiderata, such as the in situ production and containment of aggressive and hazardous reagents, and the avoidance of use of ecologically harmful elements, may be achieved by designing the appropriate heterogeneous inorganic catalyst, which ideally should be cheap, readily preparable and fully characterizable, preferably under in situ reaction conditions. A range of nanoporous and nanoparticle catalysts that meet most of the stringent demands of sustainable development and responsible (clean) technology is described. Specific examples that are highlighted include the production of adipic acid (precursor of polyamides and urethanes) without the use of concentrated nitric acid nor the production of greenhouse gases such as nitrous oxide; the production of caprolactam (precursor of nylon) without the use of oleum and hydroxylamine sulfate; and the terminal oxyfunctionalization of linear alkanes in air. The topic of biocatalysis and sustainable development is also briefly discussed for the epoxidation of terpenes and fatty acid methyl esters; for the generation of polymers, polylactides, and polyesters; and for the production of 1,3-propanediol from corn.

  10. Probes for anionic cell surface detection

    Science.gov (United States)

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  11. Recognition and sensing of fluoride anion.

    Science.gov (United States)

    Cametti, Massimo; Rissanen, Kari

    2009-05-28

    Fluoride anion recognition is attracting a mounting interest in the scientific community due to its duplicitous nature. It is a useful chemical for many industrial applications, and it has been used in human diet, but, recently it has been accused for several human pathologies. Here we describe the ample panorama of different approaches the chemists world-wide have employed to face the challenge of fluoride binding, and we outline some of the research which in our view can contribute to the development of this field, especially when fluoride binding has to be achieved in highly competitive protic solvents and water.

  12. Facile synthesis of highly aligned multiwalled carbon nanotubes from polymer precursors.

    Energy Technology Data Exchange (ETDEWEB)

    Han, C. Y.; Xiao, Z.-L.; Wang, H. H.; Lin, X.-M.; Trasobares, S.; Cook, R. E.; Richard J. Daley Coll.; Northern Illinois Univ.; Univ. de Cadiz

    2009-01-01

    We report a facile one-step approach which involves no flammable gas, no catalyst, and no in situ polymerization for the preparation of well-aligned carbon nanotube array. A polymer precursor is placed on top of an anodized aluminum oxide (AAO) membrane containing regular nanopore arrays, and slow heating under Ar flow allows the molten polymer to wet the template through adhesive force. The polymer spread into the nanopores of the template to form polymer nanotubes. Upon carbonization the resulting multi-walled carbon nanotubes duplicate the nanopores morphology precisely. The process is demonstrated for 230, 50, and 20 nm pore membranes. The synthesized carbon nanotubes are characterized with scanning/transmission electron microscopies, Raman spectroscopy, and resistive measurements. Convenient functionalization of the nanotubes with this method is demonstrated through premixing CoPt nanoparticles in the polymer precursors.

  13. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.

    2007-01-01

    Full Text Available Zirconium-hydroxide precursor samples are synthesized from Zr-hydroxide, Zr-nitrate, and Zr-alkoxide, by precipitation/impregnation, as well as by a modified sol-gel method. Precursor samples are further sulphated for the intended SO4 2- content of 4 wt.%, and calcined at 500-700oC. Differences in precursors’ origin and calcination temperature induce the incorporation of SO4 2- groups into ZrO2 matrices by various mechanisms. As a result, different amounts of residual sulphates are coupled with other structural, as well as surface properties, resulting in various catalytic activities of sulphated zirconia samples. Catalyst activity and selectivity are a complex synergistic function of tetragonal phase fraction, sulphates contents, textural and surface characteristics. Superior activity of SZ of alkoxide origin can be explained by a beneficial effect of meso-pores owing to a better accommodation of coke deposits.

  14. Facile Synthesis of Highly Aligned Multiwalled Carbon Nanotubes from Polymer Precursors

    Directory of Open Access Journals (Sweden)

    Catherine Y. Han

    2009-01-01

    Full Text Available We report a facile one-step approach which involves no flammable gas, no catalyst, and no in situ polymerization for the preparation of well-aligned carbon nanotube array. A polymer precursor is placed on top of an anodized aluminum oxide (AAO membrane containing regular nanopore arrays, and slow heating under Ar flow allows the molten polymer to wet the template through adhesive force. The polymer spread into the nanopores of the template to form polymer nanotubes. Upon carbonization the resulting multi-walled carbon nanotubes duplicate the nanopores morphology precisely. The process is demonstrated for 230, 50, and 20 nm pore membranes. The synthesized carbon nanotubes are characterized with scanning/transmission electron microscopies, Raman spectroscopy, and resistive measurements. Convenient functionalization of the nanotubes with this method is demonstrated through premixing CoPt nanoparticles in the polymer precursors.

  15. Chalcogen catalysts for polymer electrolyte fuel cell

    Science.gov (United States)

    Alonso-Vante, Nicolas [Buxerolles, FR; Zelenay, Piotr [Los Alamos, NM; Choi, Jong-Ho [Los Alamos, NM; Wieckowski, Andrzej [Champaign, IL; Cao, Dianxue [Urbana, IL

    2009-09-15

    A methanol-tolerant cathode catalyst and a membrane electrode assembly for fuel cells that includes such a cathode catalyst. The cathode catalyst includes a support having at least one transition metal in elemental form and a chalcogen disposed on the support. Methods of making the cathode catalyst and membrane electrode assembly are also described.

  16. Increasing the lifetime of fuel cell catalysts

    NARCIS (Netherlands)

    Latsuzbaia, R.

    2015-01-01

    In this thesis, I discuss a novel idea of fuel cell catalyst regeneration to increase lifetime of the PEM fuel cell electrode/catalyst operation and, therefore, reduce the catalyst costs. As many of the catalyst degradation mechanisms are difficult to avoid, the regeneration is alternative option to

  17. Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

    Science.gov (United States)

    Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

    2017-09-01

    Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

  18. Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

    Directory of Open Access Journals (Sweden)

    Ernő E. Kiss

    2012-12-01

    Full Text Available Impeded chemical reactions and impeded polymorphous transformation in materials are discussed, as desired effects, for stabilization of ceramic catalyst supports and ceramic based catalysts. This paper gives a short overview about the possibilities of slowing down the aging processes in ceramic catalyst supports and catalysts. Special attention is given to alumina and titania based catalysts.

  19. Synthesis and structures of metal chalcogenide precursors

    Science.gov (United States)

    Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

    1990-01-01

    The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

  20. NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

    Directory of Open Access Journals (Sweden)

    María Juliana Maccarrone

    2016-01-01

    Full Text Available Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+ species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z -3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a the electronic effects, related to the high charge of W (+6, causing an intensive dipole moment in the hydrogen molecule (van der Waals forces and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K. The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z -3-hexene (94% at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst

  1. Hydrophobic catalyst applications in the nuclear field and in environmental studies

    International Nuclear Information System (INIS)

    Ionita, Gheorghe; Popescu, Irina; Stefanescu, Ioan; Varlam, Carmen

    2002-01-01

    The paper presents methods of preparation and applications of hydrophobic platinum catalysts in nuclear field and environmental protection. These catalysts allow the transport of gaseous reactants and reaction products to and from catalytic active centers since the pore blocking by water is avoided. Hence the activity and stability of the catalysts increase and isotopic exchange columns with simpler internal structure can be achieved. The aim of the paper is: 1. to give a data base regarding the preparation methods of the optimal catalyst type; 2. to indicate the utilization and operation procedures of hydrophobic catalysts with mixed and simple packings; 3. to evaluate the performances and applications of hydrophobic catalysts. Over one hundred of hydrophobic catalysts of the active metal/support type were prepared in our laboratory. Hydrophobic features were obtained by different methods like these: - coating a hydrophilic conventional catalyst with a hydrophobic agent such as silicone or teflon; - supporting the active metal directly into the pores of a hydrophobic support; - mixing the teflon powder with a hydrophilic conventional catalyst; coating the support with teflon followed by the impregnation with the precursor of the active metal. The most important application of these catalysts is detritiation of the heavy water used as moderator and coolant in CANDU type reactors. Build-up of tritium in heavy water following the neutron capture by deuterium leads to a reduction in the moderating properties and at the same time leads to a contamination hazard for both operation personnel and environment. Tritium recovery leads this way to both improving the moderating qualities of the heavy water and obtaining valuable pure tritium of high importance in fusion research and other laboratory studies. One gram of tritium costs about USD 10,000. The physical chemical process is water-hydrogen catalyzed isotopic exchange. Also discussed in the paper is the separation of

  2. DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst

    KAUST Repository

    Pasha, Farhan Ahmad

    2015-01-26

    A computational study within the framework of density functional theory is presented on the oligomerization of ethylene to yield 1-hexene using [(η5-C5H4CMe2C6H5)]TiCl3/MAO] catalyst. This study explicitly takes into account a methylaluminoxane (MAO) cocatalyst model, where the MAO cluster has become an anionic species after having abstracted one chloride anion, yielding a cationic activated catalyst. Hence, the reaction profile was calculated using the zwitterionic system, and the potential energy surface has been compared to the cationic catalytic system. Modest differences were found between the two free energy profiles. However, we show for the first time that the use of a realistic zwitterionic model is required to obtain a Brønsted-Evans-Polanyi relationship between the energy barriers and reaction energies.

  3. Aerosol Ions and Their Gaseous Precursors over North America and their Sensitivity to Nitrogen Emissions

    Science.gov (United States)

    Tang, Y.; Carmichael, G. R.; Thongboonchoo, N.; Horowitz, L. W.; Dabdub, D.; Sandu, A.; Weber, R. J.; Heckel, A.

    2004-12-01

    During the ITCT-2K2 and ICARTT-2k4 experiments, a regional chemical transport model, STEM-2K3, was applied to study developed to study the aerosol ions, their precursors, and photochemistry. The major anions: sulfate and nitrate, show obvious geographic distribution from west to east coasts: nitrate is the dominant anion in west coast, and sulfate is the major anion in east coast. It reflects the distribution of NOx and SO2 sources and the influence of prevailing wind directions. The model also reveals that sulfate is the major component of aerosol extinction coefficients in Eastern and Southeastern USA during the ICARTT experiment. Ammonia emissions play an important role on controlling the ratio of nitrate versus HNO3 over inland states. Sea salt is the one of major influence factors in the coast regions. Our three-dimensional model revealed the procedure of aerosol secondary uptake when airmasses move from west to east. Using modeled regional tracers to identify the airmass sources, the aerosols also show source-related distributions. The SO2 industrial emissions, such as power plants, are the major sources of sulfate. The sulfate formation illustrates the non-local effect associated with transport and diffusion. Simulated carbonaceous concentrations are also discussed with equilibrium assumption. The consideration of aerosol secondary partition is important not only for aerosol prediction, but also for gaseous chemistry. The sensitivity studies with and without nitrate aerosol formation revealed its influence on gaseous HNO3, NOy concentrations and photochemical products.

  4. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    Proposed in theory and confirmed to exist, 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, intrinsic anion–π interaction strengths that are free from complications of condensed phases’ 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 SO₄²⁻). The binding energies of the resultant gaseous 1:1 complexes (1•Cl⁻,1•Br⁻, 1•I⁻, 1•SCN⁻, 1•NO₃⁻, 1•IO₃⁻ and 1•SO₄²⁻) 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, but only about 40% of that between 1 and SO₄²⁻. Quantum chemical calculations reveal that all anions reside in the center of the cavity of 1 with 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 natural bond orbital charge distribution analysis 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

  5. Improved electrochemical performance of Fe-N-C catalysts through ionic liquid modification in alkaline media

    Science.gov (United States)

    Martinaiou, Ioanna; Wolker, Thomas; Shahraei, Ali; Zhang, Gui-Rong; Janßen, Arne; Wagner, Stephan; Weidler, Natascha; Stark, Robert W.; Etzold, Bastian J. M.; Kramm, Ulrike I.

    2018-01-01

    It is well known that Fe-N-C catalysts reach a significantly better ORR activity in alkaline compared to acidic electrolyte. This advantage makes the material of interest for application in alkaline fuel cells. Beside this, for Pt/C catalyst it is known that the performance in acid can be significantly enhanced through ionic liquid modification following the Solid Catalysts with Ionic Liquid Layer (SCILL) concept. In our current study we combine both advantages and investigate for two Fe-N-C catalysts prepared either with or without sulfur in the precursor mixture the effect of IL modification. The unmodified catalysts are characterized using X-ray induced photoelectron spectroscopy (XPS), 57Fe Mößbauer and Raman spectroscopy as well as N2 sorption. The electrochemical behavior of the unmodified catalyst and with different pore-filling degrees of ionic liquid (IL) is analysed with respect to double layer capacitance, ORR activity and stability in accelerated stress tests mimicking the load-cycle conditions.

  6. A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration.

    Science.gov (United States)

    Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop

    2014-08-01

    Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Characterization of a surface modified carbon cryogel and a carbon supported Pt catalyst

    Directory of Open Access Journals (Sweden)

    BILJANA M. BABIĆ

    2007-08-01

    Full Text Available A carbon cryogel, synthesized by carbonization of a resorcinol/formaldehyde cryogel and oxidized in nitric acid, was used as catalyst support for Pt nano-particles. The Pt/C catalyst was prepared by a modified polyol synthesis method in an ethylene glycol (EG solution. Characterization by nitrogen adsorption showed that the carbon cryogel support and the Pt/C catalyst were mesoporous materials with high specific surface areas (SBET > 400 m2 g-1 and large mesoporous volumes. X-Ray diffraction of the catalyst demonstrated the successful reduction of the Pt precursor to metallic form. TEM Images of the Pt/C catalyst and Pt particle size distribution showed that the mean Pt particle size was about 3.3 nm. Cyclic voltammetry (CV experiments at various scan rates (from 2 to 200 mV s-1 were performed in 0.5 mol dm-3 HClO4 solution. The large capacitance of the oxidized carbon cryogel electrode, which arises from a combination of the double-layer capacitance and pseudocapacitance, associated with the participation of surface redox-type reactions was demonstrated. For the oxidized carbon cryogel, the total specific capacitance determined by 1/C vs. ν0.5 extrapolation method was found to be 386 F g-1. The hydrogen oxidation reaction at the investigated Pt/C catalyst proceeded as an electrochemically reversible, two-electron direct discharge reaction.

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

    Science.gov (United States)

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

    2016-01-01

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

  9. The quantum structure of anionic hydrogen clusters

    Science.gov (United States)

    Calvo, F.; Yurtsever, E.

    2018-03-01

    A flexible and polarizable interatomic potential has been developed to model hydrogen clusters interacting with one hydrogen anion, (H2)nH-, in a broad range of sizes n = 1-54 and parametrized against coupled cluster quantum chemical calculations. Using path-integral molecular dynamics simulations at 1 K initiated from the putative classical global minima, the equilibrium structures are found to generally rely on icosahedral shells with the hydrogen molecules pointing toward the anion, producing geometric magic numbers at sizes n = 12, 32, and 44 that are in agreement with recent mass spectrometry measurements. The energetic stability of the clusters is also connected with the extent of vibrational delocalization, measured here by the fluctuations among inherent structures hidden in the vibrational wave function. As the clusters grow, the outer molecules become increasingly free to rotate, and strong finite size effects are also found between magic numbers, associated with more prominent vibrational delocalization. The effective icosahedral structure of the 44-molecule cluster is found to originate from quantum nuclear effects as well, the classical structure showing no particular symmetry.

  10. An intracellular anion channel critical for pigmentation

    Science.gov (United States)

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-01-01

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation. DOI: http://dx.doi.org/10.7554/eLife.04543.001 PMID:25513726

  11. Isobar Separator for Anions: Current status

    International Nuclear Information System (INIS)

    Alary, Jean-François; Javahery, Gholamreza; Kieser, William; Zhao, Xiao-Lei; Litherland, Albert; Cousins, Lisa; Charles, Christopher

    2015-01-01

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of 36 S from 36 Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion–molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  12. Isobar Separator for Anions: Current status

    Energy Technology Data Exchange (ETDEWEB)

    Alary, Jean-François, E-mail: alaryjf@isobarex.ca [Isobarex Corp., 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Javahery, Gholamreza [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Kieser, William; Zhao, Xiao-Lei [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada); Litherland, Albert [IsoTrace Laboratory, Department of Physics, University of Toronto, 60 St. George Street, Toronto, ON M5S 3B1 (Canada); Cousins, Lisa [IONICS Mass Spectrometry, 32 Nixon Road Unit #1, Bolton, ON L7E 1W2 (Canada); Charles, Christopher [Andre E. Lalonde Accelerator Mass Spectrometry Laboratory, Advanced Research Complex, University of Ottawa, 25 Templeton Street, Ottawa, ON K1N 6N5 (Canada)

    2015-10-15

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of {sup 36}S from {sup 36}Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion–molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  13. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (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 C2H and C4H. Other radicals studied include NCN and I3. 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 I3 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.

  14. Rare earth metals for automotive exhaust catalysts

    International Nuclear Information System (INIS)

    Shinjoh, Hirohumi

    2006-01-01

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

  15. Ion-selective electrode and anion gap range: What should the anion gap be?

    Directory of Open Access Journals (Sweden)

    Sadjadi SA

    2013-06-01

    Full Text Available Seyed-Ali Sadjadi, Rendell Manalo, Navin Jaipaul, James McMillan Jerry L Pettis Memorial Veterans Medical Center, Loma Linda University School of Medicine, Loma Linda, CA, USA Background: Using flame photometry technique in the 1970s, the normal value of anion gap (AG was determined to be 12 ± 4 meq/L. However, with introduction of the autoanalyzers using an ion-selective electrode (ISE, the anion gap value has fallen to lower levels. Methods: A retrospective study of US veterans from a single medical center was performed to determine the value of the anion gap in subjects with normal renal function and normal serum albumin and in patients with lactic acidosis and end-stage renal disease on dialysis. Results: In 409 patients with an estimated glomerular filtration rate ≥60 mL/min/1.73 m2 body surface area and serum albumin ≥4 g/dL, the mean AG was 7.2 ± 2 (range 3–11 meq/L. In 299 patients with lactic acidosis (lactate level ≥4 meq/L and 68 patients with end-stage renal disease on dialysis, the mean AG was 12.5 meq/L and 12.4 meq/L, respectively. A value <2 meq/L should be considered a low anion gap and a possible clue to drug intoxication and paraproteinemic disorders. Conclusion: With the advent of ISE for measurement of analytes, the value of the anion gap has fallen. Physicians need to be aware of the normal AG value in their respective institutions, and laboratories need to have an established value for AG based on the type of instrument they are using. Keywords: acidosis, electrolytes, ESRD

  16. Tailoring Synthesis Conditions of Carbon Xerogels towards Their Utilization as Pt-Catalyst Supports for Oxygen Reduction Reaction (ORR

    Directory of Open Access Journals (Sweden)

    María Jesús Lázaro

    2012-10-01

    Full Text Available Carbon xerogels characterized by different textural, structural and chemical properties were synthesized and used as supports for Pt catalysts for the application in polymer electrolyte fuel cells. Synthesis conditions were varied in order to synthesize carbon xerogels following the sol-gel method. These included the reactants ratio (precursor/formaldehyde, the catalyst concentration (precursor/catalyst ratio and type (basic and acid, the precursor type (resorcinol and pyrogallol and the solvent (aqueous or acetone based. Stoichiometric mixtures of resorcinol and formaldehyde yielded well polymerized gels and highly developed structures. Slow gelation, favored by the presence of acetone as solvent in the sol and low catalyst concentration, resulted in higher polymerization extent with a highly mesoporous or even macroporous texture and more ordered structure, as evidenced by XPS and Raman spectroscopy. Small Pt particles of ca. 3.5 nm were obtained by using carbon xerogels characterized by an ordered surface structure. The specific activity towards the oxygen reduction reaction, i.e., the limiting catalytic process in low temperature fuel cells, is significantly favored by highly ordered carbon xerogels due to a metal-support enhanced interaction. Nevertheless, surface defects favor the distribution of the metallic particles on the surface of carbon, which in the end influences the effectiveness of the catalyst. Accelerated degradation tests were conducted to evaluate catalyst stability under potential cycling conditions. The observed decay of performance was considerably lower for the catalysts based on ordered carbon xerogels stabilizing Pt particles in a higher extent than the other xerogels and the commercial carbon black support.

  17. Synthesis of Magnetic Carbon Supported Manganese Catalysts for Phenol Oxidation by Activation of Peroxymonosulfate

    OpenAIRE

    Yuxian Wang; Yongbing Xie; Chunmao Chen; Xiaoguang Duan; Hongqi Sun; Shaobin Wang

    2016-01-01

    Magnetic core/shell nanospheres (MCS) were synthesized by a novel and facile one-step hydrothermal method. Supported manganese oxide nanoparticles (Fe3O4/C/Mn) were obtained from various methods (including redox, hydrothermal and impregnation) using MCS as the support material and potassium permanganate as the precursor of manganese oxide. The Mn/MCS catalysts were characterized by a variety of characterization techniques and the catalytic performances of Fe3O4/C/Mn nanoparticles were tested ...

  18. How nitric oxide affects the decomposition of supported nickel nitrate to arrive at highly dispersed catalysts

    NARCIS (Netherlands)

    Sietsma, J.R.A.; Friedrich, H.; Broersma, A.; Versluijs-Helder, M.; van Dillen, A.J.; de Jongh, P.E.; de Jong, K.P.

    2008-01-01

    An explanation is put forward for the beneficial effect of thermal decomposition of supported Ni3(NO3)2(OH)4 in NO/He flow (0.1–1 vol%) that enables preparation of well-dispersed (3–5 nm particles) 24 wt% Ni-catalysts via impregnation and drying using aqueous [Ni(OH2)6](NO3)2 precursor solution.

  19. CO and Soot Oxidation over Ce-Zr-Pr Oxide Catalysts.

    Science.gov (United States)

    Andana, Tahrizi; Piumetti, Marco; Bensaid, Samir; Russo, Nunzio; Fino, Debora; Pirone, Raffaele

    2016-12-01

    A set of ceria, ceria-zirconia (Ce 80 at.%, Zr 20 at.%), ceria-praseodymia (Ce 80 at.%, Pr 20 at.%) and ceria-zirconia-praseodymia (Ce 80 at.%, Zr 10 at.% and Pr 10 at.%) catalysts has been prepared by the solution combustion synthesis (SCS). The effects of Zr and Pr as dopants on ceria have been studied in CO and soot oxidation reactions. All the prepared catalysts have been characterized by complementary techniques, including XRD, FESEM, N2 physisorption at -196 °C, H2-temperature-programmed reduction, and X-ray photoelectron spectroscopy to investigate the relationships between the structure and composition of materials and their catalytic performance. Better results for CO oxidation have been obtained with mixed oxides (performance scale, Ce80Zr10Pr10 > Ce80Zr20 > Ce80Pr20) rather than pure ceria, thus confirming the beneficial role of multicomponent catalysts for this prototypical reaction. Since CO oxidation occurs via a Mars-van Krevelen (MvK)-type mechanism over ceria-based catalysts, it appears that the presence of both Zr and Pr species into the ceria framework improves the oxidation activity, via collective properties, such as electrical conductivity and surface or bulk oxygen anion mobility. On the other hand, this positive effect becomes less prominent in soot oxidation, since the effect of catalyst morphology prevails.

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

    KAUST Repository

    Ahmed, Syud M.

    2013-12-18

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

  1. Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction.

    Science.gov (United States)

    Kibsgaard, Jakob; Jaramillo, Thomas F

    2014-12-22

    Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst.

    Science.gov (United States)

    Jaya, N; Selvan, B Karpanai; Vennison, S John

    2015-11-01

    Biodiesel is a clean-burning renewable substitute fuel for petroleum. Biodiesel could be effectively produced by transesterification reaction of triglycerides of vegetable oils with short-chain alcohols in the presence of homogeneous or heterogeneous catalysts. Conventionally, biodiesel manufacturing processes employ strong acids or bases as catalysts. But, separation of the catalyst and the by-product glycerol from the product ester is too expensive to justify the product use as an automobile fuel. Hence heterogeneous catalysts are preferred. In this study, transesterification of pongamia oil with ethanol was performed using a solid ion-exchange resin catalyst. It is a macro porous strongly basic anion exchange resin. The process parameters affecting the ethyl ester yield were investigated. The reaction conditions were optimized for the maximum yield of fatty acid ethyl ester (FAEE) of pongamia oil. The properties of FAEE were compared with accepted standards of biodiesel. Engine performance was also studied with pongamia oil diesel blend and engine emission characteristics were observed. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Inhibition of nuclear waste solutions containing multiple aggressive anions

    International Nuclear Information System (INIS)

    Congdon, J.W.

    1987-01-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10 refs., 5 figs., 2 tabs

  4. Photoinduced Dynamics of Neutral, Cationic, and Anionic Species

    DEFF Research Database (Denmark)

    Stephansen, Anne Boutrup

    electrons and subsequently transition from dipole to valence-bound anions in different energy regimes. The investigations indicate that dipole-bound anion formation depends strongly on the magnitude of the molecular dipole moment, while the formation and stability of valence-bound anions depends on ring....... Nucleobase anions are posited to be involved in DNA damage, where the molecular dipole moment of a nucleobase acts as electron-antenna and gateway for low-energy electrons to access the valence system of DNA. The investigations presented herein explore the abilities of adenine, thymine, and uracil to capture...

  5. Photoelectron Spectroscopy of 4-Bromochlorobenzene Dimer and Trimer Anions

    International Nuclear Information System (INIS)

    Kim, Namdoo

    2013-01-01

    I investigated the electron attachment to 4-BCB dimer and trimer anions using anion photoelectron spectroscopy and theoretical calculations. I found that an excess electron can be delocalized to these clusters through extended π-network. However, the nature of the ion core is different for the dimer and trimer. For the heterodimer anions, the geometry is determined by the differences in electronegativity of the molecules. Dimer anions with a large electronegativity difference have T-shaped geometries and those with a small electronegativity difference have PD geometries

  6. Biomass processing over gold catalysts

    CERN Document Server

    Simakova, Olga A; Murzin, Dmitry Yu

    2014-01-01

    The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are pre...

  7. Efficient Air Desulfurization Catalysts Derived from Pig Manure Liquefaction Char

    Directory of Open Access Journals (Sweden)

    Rajiv Wallace

    2017-11-01

    Full Text Available Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2 was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H2S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H2S removal can be obtained from pig manure liquefaction wastes.

  8. Biochemical Removal of HAP Precursors From Coal

    Energy Technology Data Exchange (ETDEWEB)

    Olson, G.; Tucker, L.; Richards, J.

    1997-07-01

    This project addresses DOE`s interest in advanced concepts for controlling emissions of air toxics from coal-fired utility boilers. We are determining the feasibility of developing a biochemical process for the precombustion removal of substantial percentages of 13 inorganic hazardous air pollutant (HAP) precursors from coal. These HAP precursors are Sb, As, Be, Cd, Cr, Cl, Co, F, Pb, Hg, Mn, Ni, and Se. Although rapid physical coal cleaning is done routinely in preparation plants, biochemical processes for removal of HAP precursors from coal potentially offer advantages of deeper cleaning, more specificity, and less coal loss. Compared to chemical processes for coal cleaning, biochemical processes potentially offer lower costs and milder process conditions. Pyrite oxidizing bacteria, most notably Thiobacillusferrooxidans, are being evaluated in this project for their ability to remove HAP precursors from U.S. coals.

  9. Precursor Parameter Identification for IGBT Prognostics

    Data.gov (United States)

    National Aeronautics and Space Administration — Precursor parameters have been identified to enable development of a prognostic approach for insulated gate bipolar transistors (IGBT). The IGBT were subjected to...

  10. Probabilistic precursor analysis - an application of PSA

    International Nuclear Information System (INIS)

    Hari Prasad, M.; Gopika, V.; Sanyasi Rao, V.V.S.; Vaze, K.K.

    2011-01-01

    Incidents are inevitably part of the operational life of any complex industrial facility, and it is hard to predict how various contributing factors combine to cause the outcome. However, it should be possible to detect the existence of latent conditions that, together with the triggering failure(s), result in abnormal events. These incidents are called precursors. Precursor study, by definition, focuses on how a particular event might have adversely developed. This paper focuses on the events which can be analyzed to assess their potential to develop into core damage situation and looks into extending Probabilistic Safety Assessment techniques to precursor studies and explains the benefits through a typical case study. A preliminary probabilistic precursor analysis has been carried out for a typical NPP. The major advantages of this approach are the strong potential for augmenting event analysis which is currently carried out purely on deterministic basis. (author)

  11. Biochemical Removal of HAP Precursors From Coal

    International Nuclear Information System (INIS)

    Olson, G.; Tucker, L.; Richards, J.

    1997-07-01

    This project addresses DOE's interest in advanced concepts for controlling emissions of air toxics from coal-fired utility boilers. We are determining the feasibility of developing a biochemical process for the precombustion removal of substantial percentages of 13 inorganic hazardous air pollutant (HAP) precursors from coal. These HAP precursors are Sb, As, Be, Cd, Cr, Cl, Co, F, Pb, Hg, Mn, Ni, and Se. Although rapid physical coal cleaning is done routinely in preparation plants, biochemical processes for removal of HAP precursors from coal potentially offer advantages of deeper cleaning, more specificity, and less coal loss. Compared to chemical processes for coal cleaning, biochemical processes potentially offer lower costs and milder process conditions. Pyrite oxidizing bacteria, most notably Thiobacillusferrooxidans, are being evaluated in this project for their ability to remove HAP precursors from U.S. coals

  12. Precursor analyses for German nuclear power plants

    International Nuclear Information System (INIS)

    Babst, Siegfried; Gaenssmantel, Gerhard; Stueck, Reinhard

    2009-01-01

    Precursor analysis is an internationally recognized method for quantifying the safety-relevance of operational events in nuclear power plants. Precursors are operational events in nuclear power plants which had no serious impact, but which could have led to serious impacts, if additional malfunctions had occurred. Examples of such operational events are component failures or transients, for example, the loss of main feedwater. On the basis of the probabilities for the occurrence of additional malfunctions or initiating events precursor analyses determine the probability with which these additional malfunctions during the event occurred would have led to core damage. This conditional probability is a measure for the safety relevance of the operational event occurred. Events, for which the probability of core damages is > 10 -6 , are internationally classified as ''precursor''. (orig.)

  13. Synthesis and characterization of La{sub 0,8}Ca{sub 0,2}MO{sub 3} (M = Co ou Mn) perovskite by using gelatin as organic precursor; Sintese e caracterizacao de perovsquita do tipo La{sub 0,8}Ca{sub 0,2}MO{sub 3} (M = Co ou Mn) usando a gelatina como precursor organico

    Energy Technology Data Exchange (ETDEWEB)

    Wanderley, J.B.M.; Borges, F.M.M. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Escola de Ciencias e Tecnologia; Ribeiro, J.P.; Pimentel, P.M.; Melo, D.M.A., E-mail: brunomoura@daect.com.br [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Departamento de Quimica

    2011-07-01

    Materials with perovskite structure are potential catalysts to prevent the emission of pollutants into the environment, various methods have been proposed for the synthesis of these materials, to produce homogeneous materials with nanoscale particle size. In this work, lanthanum manganate systems and lanthanum cobaltate systems with partial substitution of calcium were synthesized using gelatin as a precursor agent, aiming its use as automotive catalysts. This synthesis method, using gelatin as organic precursor, was used because it allows the synthesis of crystalline phases with powders homogeneous and porous. The powders obtained at 300 ° C, were calcined at temperatures of 700 and 900 ° C for 4h, and were characterized by means of thermogravimetric analysis, X-ray diffraction and scanning electron microscopy. The perovskite were single phase, nanometric, and porous. These features make the powders potential catalysts for automotive combustion. (author)

  14. Planar half-cell shaped precursor body

    DEFF Research Database (Denmark)

    2015-01-01

    The invention relates to a half-cell shaped precursor body of either anode type or cathode type, the half-cell shaped precursor body being prepared to be free sintered to form a sintered or pre-sintered half-cell being adapted to be stacked in a solid oxide fuel cell stack. The obtained half......-cell has an improved planar shape, which remains planar also after a sintering process and during temperature fluctuations....

  15. Polyamide from lactams by reactive rotational molding via anionic ring-opening polymerization: Optimization of processing parameters

    Directory of Open Access Journals (Sweden)

    N. Barhoumi

    2013-01-01

    Full Text Available A reactive rotational molding (RRM process was developed to obtain a PA6 by activated anionic ring-opening polymerization of epsilon-caprolactam (APA6. Sodium caprolactamate (C10 and caprolactam magnesium bromide (C1 were employed as catalysts, and difunctional hexamethylene-1,6-dicarbamoylcaprolactam (C20 was used as an activator. The kinetics of the anionic polymerization of !-caprolactam into polyamide 6 was monitored through dynamic rheology and differential scanning calorimetry measurements. The effect of the processing parameters, such as the polymerization temperature, different catalyst/activator combinations and concentrations, on the kinetics of polymerization is discussed. A temperature of 150°C was demonstrated to be the most appropriate. It was also found that crystallization may occur during PA6 polymerization and that the combination C1/C20 was well suited as it permitted a suitable induction time. Isoviscosity curves were drawn in order to determine the available processing window for RRM. The properties of the obtained APA6 were compared with those of a conventionally rotomolded PA6. Results pointed at lower cycle times and increased tensile properties at weak deformation.

  16. Synthesis of cubic Ia-3d mesoporous silica in anionic surfactant templating system with the aid of acetate.

    Science.gov (United States)

    Deng, Shao-Xin; Xu, Xue-Yan; He, Wen-Chao; Wang, Jin-Gui; Chen, Tie-Hong

    2014-08-01

    Mesoporous silica with three-dimensional (3D) bicontinuous cubic Ia-3d structure and fascinating caterpillar-like morphology was synthesized by using anionic surfactant N-lauroylsarcosine sodium (Sar-Na) as the template and 3-amionpropyltrimethoxysilane (APS) as the co-structure-directing agent (CSDA) with the aid of acetate. A phase transformation from high interfacial curvature 2D hexagonal to low interfacial curvature 3D cubic Ia-3d occurred in the presence of a proper amount of acetate. Other species of salts (excluding acetate) had the ability to induce the caterpillar-like morphology, but failed to induce the cubic Ia-3d mesostructure. Furthermore, [3-(2-aminoethyl)-aminopropyl]trimethoxysilane (DAPS) was also used as the CSDA to synthesize Ia-3d mesostructured silica under the aid of sodium acetate. After extraction of the anionic surfactants, amino and di-amine functionalized 3D bicontinuous cubic Ia-3d mesoporous silicas were obtained and used as supports to immobilize Pd nanoparticles for supported catalysts. The catalytic activity of the catalysts was tested by catalytic hydrogenation of allyl alcohol. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Characterization of Cr/SiO 2 catalysts and ethylene polymerization by XPS

    Science.gov (United States)

    Gaspar, A. B.; Perez, C. A. C.; Dieguez, L. C.

    2005-11-01

    Cr/SiO 2 catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr 6+ and Cr 3+ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr 6+ to Cr 3+ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO 3 and Cr 2O 3 standards did not reveal variation in the binding energy of Cr 2p 3/2, but a physical mixture of CrO 3 with SiO 2 presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.

  18. Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

    International Nuclear Information System (INIS)

    Gaspar, A.B.; Perez, C.A.C.; Dieguez, L.C.

    2005-01-01

    Cr/SiO 2 catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr 6+ and Cr 3+ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr 6+ to Cr 3+ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO 3 and Cr 2 O 3 standards did not reveal variation in the binding energy of Cr 2p 3/2 , but a physical mixture of CrO 3 with SiO 2 presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed

  19. Effect of the functional groups of carbon on the surface and catalytic properties of Ru/C catalysts for hydrogenolysis of glycerol

    International Nuclear Information System (INIS)

    Gallegos-Suarez, E.; Pérez-Cadenas, M.; Guerrero-Ruiz, A.; Rodriguez-Ramos, I.; Arcoya, A.

    2013-01-01

    Ruthenium catalysts supported on activated carbons, original (AC) and treated with nitric acid (AC-Ox) were prepared by incipient wetness impregnation from either chloride (Cl) or nitroxyl nitrate (n) precursors. These catalysts were characterized by TG, XPS, TEM, TPD-MS and CO adsorption microcalorimetry and evaluated in the hydrogenolysis of glycerol in the liquid phase, at 453 K and 8 MPa. Studies by TEM show that ruthenium particles supported on AC-Ox are larger than on AC, without any effect of the nature of the metal precursor. However, adsorption of CO on the ex-chloride catalysts is inhibited in comparison with that of the ex-nitroxyl nitrate catalysts. Catalysts characterization by TG, TPD-MS and XPS reveals that the nitric acid treatment and the nitroxyl nitrate precursor generate oxygenated groups on the carbon surface, which provide acid properties to the catalysts, although they are partly destroyed during the reduction treatment applied to the catalysts. The sequence of the overall TOF, Ru(Cl)/AC < Ru(n)/AC < Ru(Cl)/AC-Ox ≈ Ru(n)/AC-Ox, reasonably parallels the population increase of surface acid groups. Participation of the -COOH groups in the transformation of glycerol into 1,2-propanediol is verified by using the admixture Ru(Cl)/AC+AC-Ox as catalyst. In this case, since AC-Ox was not thermally treated and no loss of oxygenated groups occurred, TOF and selectivity toward 1,2-propanediol improve in comparison with those of the more active catalysts.

  20. Effect of the functional groups of carbon on the surface and catalytic properties of Ru/C catalysts for hydrogenolysis of glycerol

    Energy Technology Data Exchange (ETDEWEB)

    Gallegos-Suarez, E. [Departamento de Química Inorgánica y Técnica, Facultad de Ciencias, UNED, Paseo Senda del Rey n° 9, 28040 Madrid (Spain); Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie n° 2, L-10, 28049 Madrid (Spain); Pérez-Cadenas, M. [Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie n° 2, L-10, 28049 Madrid (Spain); Guerrero-Ruiz, A. [Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie n° 2, L-10, 28049 Madrid (Spain); Unidad Asociada UNED ICP-CSIC, Group Design and Applied Heterogeneous Catalysis (Spain); Rodriguez-Ramos, I. [Departamento de Química Inorgánica y Técnica, Facultad de Ciencias, UNED, Paseo Senda del Rey n° 9, 28040 Madrid (Spain); Unidad Asociada UNED ICP-CSIC, Group Design and Applied Heterogeneous Catalysis (Spain); Arcoya, A., E-mail: aarcoya@icp.csic.es [Departamento de Química Inorgánica y Técnica, Facultad de Ciencias, UNED, Paseo Senda del Rey n° 9, 28040 Madrid (Spain); Unidad Asociada UNED ICP-CSIC, Group Design and Applied Heterogeneous Catalysis (Spain)

    2013-12-15

    Ruthenium catalysts supported on activated carbons, original (AC) and treated with nitric acid (AC-Ox) were prepared by incipient wetness impregnation from either chloride (Cl) or nitroxyl nitrate (n) precursors. These catalysts were characterized by TG, XPS, TEM, TPD-MS and CO adsorption microcalorimetry and evaluated in the hydrogenolysis of glycerol in the liquid phase, at 453 K and 8 MPa. Studies by TEM show that ruthenium particles supported on AC-Ox are larger than on AC, without any effect of the nature of the metal precursor. However, adsorption of CO on the ex-chloride catalysts is inhibited in comparison with that of the ex-nitroxyl nitrate catalysts. Catalysts characterization by TG, TPD-MS and XPS reveals that the nitric acid treatment and the nitroxyl nitrate precursor generate oxygenated groups on the carbon surface, which provide acid properties to the catalysts, although they are partly destroyed during the reduction treatment applied to the catalysts. The sequence of the overall TOF, Ru(Cl)/AC < Ru(n)/AC < Ru(Cl)/AC-Ox ≈ Ru(n)/AC-Ox, reasonably parallels the population increase of surface acid groups. Participation of the -COOH groups in the transformation of glycerol into 1,2-propanediol is verified by using the admixture Ru(Cl)/AC+AC-Ox as catalyst. In this case, since AC-Ox was not thermally treated and no loss of oxygenated groups occurred, TOF and selectivity toward 1,2-propanediol improve in comparison with those of the more active catalysts.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-09-26

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

  2. Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

    Energy Technology Data Exchange (ETDEWEB)

    Aragao, Isaias Barbosa; Ro, Insoo; Liu, Yifei; Ball, Madelyn; Huber, George W.; Zanchet, Daniela; Dumesic, James A.

    2018-03-01

    FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. The catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H2O activation on FeOx species at or near the Pt surface, mostly in the (II) oxidation state.

  3. Dispersed catalysts for transforming extra heavy crude oil into transportable upgraded crude: phase identification

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, S.; Canizales, E.; Machin, I. [Gerencia Depttal de Investigacion Estrategica en Refinacion PDVSA Intevep (Venezuela); Segovia, X.; Rivas, A.; Lopez, E.; Pena, J.P.; Rojas, J.D.; Sardella, R. [Gerencia Depttal de Infraestructura y Mejoramiento en Faja Petrolifera PDVSA Intevep (Venezuela)

    2011-07-01

    A new technology to convert extra heavy crude oil into transportable upgraded crude has been developed. A water/oil emulsion composed of steam and catalyst precursors is introduced in the feed which then generates unsupported dispersed catalyst in situ under thermal decomposition. The aim of this paper is to characterize the particles. The study was conducted in a laboratory and on a pilot scale on three different vacuum residues using high resolution transmission electron microscopy and a transmission electron microscope. Results showed that the particles were formed by oxides and inorganic sulphur based in transition metals and their sizes ranged between 5 and 120 nm; in addition, good dispersion was observed. This study demonstrated that the process involved in the generation of dispersed catalyst is extremely complex and showed that further work with heavy crude oils and its residua is required to understand the mechanisms involved.

  4. An effective low Pd-loading catalyst for hydrogen generation from formic acid

    DEFF Research Database (Denmark)

    Huang, Yunjie; Xu, Junlei; Ma, Xin

    2017-01-01

    ) and a functional support (nitrogen modified reduced graphene oxide, N-rGO) were applied to prepare Pd catalyst. It was found that the Ag atoms facilitated the formation of Pd-rich surface in the preparation strategy, in which the reductive N-rGO and a two-step feeding process of metal precursors played important...... roles. In addition, Ag additive was found to benefit catalyst stability. Most interestingly, the obtained low Pd-loading Pd1Ag6/N-rGO catalyst showed a specific Pd loading turnover frequency of 171 mol Pd−1 h−1 and a specific metal cost turnover frequency of 64.2 $−1 h−1, which were predominant among...

  5. Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

    Science.gov (United States)

    Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

    2018-03-01

    The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal–air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

  6. Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

    Science.gov (United States)

    Gogoi, Satyabrat; Karak, Niranjan

    2017-10-01

    Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

  7. The difference between critical care initiation anion gap and prehospital admission anion gap is predictive of mortality in critical illness.

    Science.gov (United States)

    Lipnick, Michael S; Braun, Andrea B; Cheung, Joyce Ting-Wai; Gibbons, Fiona K; Christopher, Kenneth B

    2013-01-01

    We hypothesized that the delta anion gap defined as difference between critical care initiation standard anion gap and prehospital admission standard anion gap is associated with all cause mortality in the critically ill. Observational cohort study. Two hundred nine medical and surgical intensive care beds in two hospitals in Boston, MA. Eighteen thousand nine hundred eighty-five patients, age ≥18 yrs, who received critical care between 1997 and 2007. The exposure of interest was delta anion gap and categorized a priori as 10 mEq/L. Logistic regression examined death by days 30, 90, and 365 postcritical care initiation and in-hospital mortality. Adjusted odds ratios were estimated by multivariable logistic regression models. The discrimination of delta anion gap for 30-day mortality was evaluated using receiver operator characteristic curves performed for a subset of patients with all laboratory data required to analyze the data via physical chemical principles (n = 664). None. Delta anion gap was a particularly strong predictor of 30-day mortality with a significant risk gradient across delta anion gap quartiles following multivariable adjustment: delta anion gap anion gap 5-10 mEq/L odds ratio 1.56 (95% confidence interval 1.35-1.81; p anion gap >10 mEq/L odds ratio 2.18 (95% confidence interval 1.76-2.71; p anion gap 0-5 mEq/L. Similar significant robust associations post multivariable adjustments are seen with death by days 90 and 365 as well as in-hospital mortality. Correcting for albumin or limiting the cohort to patients with standard anion gap at critical care initiation of 10-18 mEq/L did not materially change the delta anion gap-mortality association. Delta anion gap has similarly moderate discriminative ability for 30-day mortality in comparison to standard base excess and strong ion gap. An increase in standard anion gap at critical care initiation relative to prehospital admission standard anion gap is a predictor of the risk of all cause patient

  8. Effect of different nickel precursors on capacitive behavior of electrodeposited NiO thin films

    Science.gov (United States)

    Kore, R. M.; Ghadge, T. S.; Ambare, R. C.; Lokhande, B. J.

    2016-04-01

    In the present study, the effect of nickel precursors containing different anions like nitrate, chloride and sulphate on the morphology and pseudocapacitance behavior of NiO is investigated. The NiO samples were prepared by using a potentiondynamic electrodeposition technique in the three electrode cell. Cyclic voltammetry technique was exploited for potentiodynamic deposition of the films. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), etc. The XRD reveals the cubic crystal structure for all samples. The SEM micrograph shows nanoflakelike, up grown nanoflakes and honeycomb like nanostructured morphologies for nitrate, chloride and sulphate precursors respectively. The capacitive behavior of these samples was recorded using cyclic voltammetry (CV), charge-discharge and electrochemical impedance spectroscopy (EIS) in 1 M KOH electrolyte. The specific capacitance values of NiO samples obtained using CV for nitrate, chloride and sulphate precursors were 136, 214 and 893 Fg-1 respectively, at the scan rate of 5 mVs-1. The charge discharge study shows high specific energy for the sample obtained from sulphate (23.98 Whkg-1) as compared to chloride (9.67 Whkg-1) and nitrate (4.9 Whkg-1), whereas samples of cholride (13.9 kWkg-1 and nitrate (10.5 kWkg-1) shows comparatively more specific power than samples obtained from sulphate (7.6 kWkg-1). The equivalent series resistance of NiO samples observed from EIS study are 1.34, 1.29 and 1.27 Ω respectively for nitrate, chloride and sulphate precursors. These results emphasizes that the samples obtained from sulphate precursors provides very low impedance through honeycomb like nanostructured morphology which supports good capacitive behavior of NiO.

  9. The innovation catalysts.

    Science.gov (United States)

    Martin, Roger L

    2011-06-01

    A few years ago the software development company Intuit realized that it needed a new approach to galvanizing customers. The company's Net Promoter Score was faltering, and customer recommendations of new products were especially disappointing. Intuit decided to hold a two-day, off-site meeting for the company's top 300 managers with a focus on the role of design in innovation. One of the days was dedicated to a program called Design for Delight. The centerpiece of the day was a PowerPoint presentation by Intuit founder Scott Cook, who realized midway through that he was no Steve Jobs: The managers listened dutifully, but there was little energy in the room. By contrast, a subsequent exercise in which the participants worked through a design challenge by creating prototypes, getting feedback, iterating, and refining, had them mesmerized. The eventual result was the creation of a team of nine design-thinking coaches--"innovation catalysts"--from across Intuit who were made available to help any work group create prototypes, run experiments, and learn from customers. The process includes a "painstorm" (to determine the customer's greatest pain point), a "soljam" (to generate and then winnow possible solutions), and a "code-jam" (to write code "good enough" to take to customers within two weeks). Design for Delight has enabled employees throughout Intuit to move from satisfying customers to delighting them.

  10. Discovery and optimization of new chromium catalysts for ethylene oligomerization and polymerization aided by high-throughput screening.

    Science.gov (United States)

    Jones, David J; Gibson, Vernon C; Green, Simon M; Maddox, Peter J; White, Andrew J P; Williams, David J

    2005-08-10

    High throughput screening (HTS) of a 205 member Schiff base salicylaldimine ligand library derived from salicylaldehydes bearing bulky ortho-substituents, i.e., 9-anthracenyl, 1,4,5,8-tetramethylanthracenyl or triptycenyl, reacted in-situ with (p-tolyl)CrCl2(thf)3, identified two new classes of highly active chromium based systems for the oligomerization and polymerization of ethylene, respectively. The polymerization system comprises bidentate ortho-substituted anthracenyl Schiff bases bearing small primary or secondary alkyl imine substituents. The oligomerization catalysts are based upon tridentate ortho-triptycenyl-substituted Schiff bases with pyridylmethyl or quinolyl substituents. Validation tests confirmed polymerization productivities of up to 3000 g x mmol(-1)h(-1)bar(-1) for the polymerization catalyst systems while the oligomerization catalysts gave productivities up to 10 000 g x mmol(-1)h(-1)bar(-1). Key catalyst precursors have been characterized by X-ray crystallography.

  11. A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

    Science.gov (United States)

    Workman, Michael J., Jr.

    Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of

  12. Nanostructured catalysts for organic transformations.

    Science.gov (United States)

    Chng, Leng Leng; Erathodiyil, Nandanan; Ying, Jackie Y

    2013-08-20

    The development of green, sustainable and economical chemical processes is one of the major challenges in chemistry. Besides the traditional need for efficient and selective catalytic reactions that will transform raw materials into valuable chemicals, pharmaceuticals and fuels, green chemistry also strives for waste reduction, atomic efficiency and high rates of catalyst recovery. Nanostructured materials are attractive candidates as heterogeneous catalysts for various organic transformations, especially because they meet the goals of green chemistry. Researchers have made significant advances in the synthesis of well-defined nanostructured materials in recent years. Among these are novel approaches that have permitted the rational design and synthesis of highly active and selective nanostructured catalysts by controlling the structure and composition of the active nanoparticles (NPs) and by manipulating the interaction between the catalytically active NP species and their support. The ease of isolation and separation of the heterogeneous catalysts from the desired organic product and the recovery and reuse of these NPs further enhance their attractiveness as green and sustainable catalysts. This Account reviews recent advances in the use of nanostructured materials for catalytic organic transformations. We present a broad overview of nanostructured catalysts used in different types of organic transformations including chemoselective oxidations and reductions, asymmetric hydrogenations, coupling reactions, C-H activations, oxidative aminations, domino and tandem reactions, and more. We focus on recent research efforts towards the development of the following nanostructured materials: (i) nanostructured catalysts with controlled morphologies, (ii) magnetic nanocomposites, (iii) semiconductor-metal nanocomposites, and (iv) hybrid nanostructured catalysts. Selected examples showcase principles of nanoparticle design such as the enhancement of reactivity, selectivity

  13. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    KAUST Repository

    Balasamy, Rabindran J.

    2010-12-20

    A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

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

    Science.gov (United States)

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

    2017-10-31

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

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

    Science.gov (United States)

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

    1994-01-01

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

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

    International Nuclear Information System (INIS)

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

    1997-01-01

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

  17. Inverse H/D isotope effects in benzene activation by cationic and anionic cobalt clusters.

    Science.gov (United States)

    Tombers, Matthias; Barzen, Lars; Niedner-Schatteburg, Gereon

    2013-02-14

    Reactions under single collision conditions with benzene C(6)H(6) and with benzene-d(6) C(6)D(6) of size selected cationic cobalt clusters Co(n)(+) and of anionic cobalt clusters Co(n)(-) in the cluster size range n = 3-28 revealed that dehydrogenation by cationic clusters is sparse, whereas it is ubiquitous in reactions by anionic clusters. Kinetic isotope effects (KIE) in total reaction rates are inverse and, in part, large. Dehydrogenation isotope effects (DIE) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate unravels a possible origin of the inverse KIE: Single step C-H bond activation is swift (no KIE in forward direction) and largely reversible (normal KIE backward) whereas H/D tunneling is likely to contribute (backward). DFT calculations of the structures and energetics along the reaction path in [Co(13)C(6)H(6)](+) lend support to the proposed multistep model. The observed effects on rates and KIEs of cluster charges and of cluster sizes are noted to elucidate further.

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

    International Nuclear Information System (INIS)

    Fu Tingjun; Huang Chengdu; Lv Jing; Li Zhenhua

    2014-01-01

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

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  20. Once upon Anion: A Tale of Photodetachment

    Science.gov (United States)

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!