Sample records for catalyst precursor anions

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

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    Abotsi, G.M.K.


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

  2. Supported Oxide Catalysts from Chelating Precursors (United States)

    Prieto-Centurion, Dario

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

  3. Catalysts in syntheses of carbon and carbon precursors


    Mochida, Isao; Yoon, Seong-Ho; Qiao, Wenming


    Carbon materials have been applied in different fields because of their unique performances. Naturally, the physical and chemical structures of carbon precursors and carbon materials decide their properties and applications. Catalysts play a very important role in the synthesis of carbon precursors and carbon materials by controlling the molecular and compositional chemistry at the transformation of organic substrates into carbon through carbonaceous intermediates. Carbon materials of high pe...

  4. Effect of Several Anions on Fe-Based Catalyst for Fischer-Tropsch Synthesis

    Institute of Scientific and Technical Information of China (English)

    Jingchang Zhang; Xuehua Guo; Weiliang Cao


    The influence of several anions on Fe-based Fischer-Tropsch catalyst, used in the synthesis of light olefins from synthesis gas, was studied. The results indicated that the addition of anions resulted in the reduction of catalytic activity. When the anion content in the catalyst was 500 ppm, the influence of different anions on the catalysis activity was as follows: S2->Cl->SO42->NO3-. The addition of S2- improved the selectivity of total hydrocarbons in the products, and Cl- reduced this selectivity but increased the olefin content in the total hydrocarbons at the same time. When the contents of S2- and Cl- in the catalyst were less than 50 ppm, their influence could be ignored. The XRD results indicated that the addition of anions reduced the contents of a-Fe and Fe3C, which were the active components in the catalyst.

  5. Transesterification of propylene glycol methyl ether in chromatographic reactors using anion exchange resin as a catalyst. (United States)

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


    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.

  6. Effects of catalyst precursors on carbon nanowires by using ethanol catalytic combustion technique

    Institute of Scientific and Technical Information of China (English)

    CHENG Jin; ZOU Xiao-ping; LI Fei; ZHANG Hong-dan; REN Peng-fei


    Iron nitrate,nickel nitrate and cobalt nitrate were used as catalyst precursors to study their effects on carbon nanowires synthesized by ethanol catalytic combustion (ECC) process. The as-grown carbon nanowires were characterized by means of scanning electron microscopy,transmission electron microscopy and Raman spectroscopy. The results show that relatively uniform nanowires will be formed when the catalyst precursor is iron nitrate:while helical structure or disordered structure will be formed when the catalyst precursor is nickel nitrate or cobalt nitrate.

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

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    Guanlin Zhang


    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.

  8. The precursor phase composition of iron catalyst and discovery of FeO based catalyst for ammonia synthesis

    Institute of Scientific and Technical Information of China (English)

    刘化章; 李小年


    The relationship between the activity and the precursor phase composition of the molten iron catalyst for ammonia synthesis has been studied with high pressure testing equipment and XRD. A humped curve between the activity and Fe2+/Fe3+ has been obtained. It is found that the unicity of the iron oxidate phase in precursor is an essential condition of the high activity of the iron catalyst and that the uniform distribution of the adominant phase and the promoters is the key to preparing a catalyst with better performance The humped curve is interpreted using the ratio f of the phase compositions in precursor. A new idea has been obtained that the activity change of the molten iron catalyst depends essentially on the molecule ratio of the different iron oxidates in precursor under the certain promoters, and it is found that the FeO based catalyst for ammonia synthesis with Wustite phase structure (Fe1-xO, 0.04≤x≤0.10) has the highest activity of all the molten iron catalysts for ammonia synthesis.

  9. Study on the Precursor Phase Composition of Fused Iron Catalyst for Fischer-Tropsch Synthesis

    Institute of Scientific and Technical Information of China (English)


    The effect of the precursor composition of fused iron catalyst on the performance of Fischer-Tropsch synthesis was investigated. XRD, BET and CO2 adsorption experiments were carried out to provide better insight into the relationship therein. The results showed that the selectivity of C5+ hydrocarbon products was dependent on the mole ratio of Fe2+/Fe3+, which was represented by a hump-shaped curve. Catalysts with precursors containing Fe3O4 phase favored the magnetite spinal formation during F-T reaction, while Fe1-xO-based catalysts were more likely to favor the formation and growth of the iron carbide crystals.

  10. Influences of Platinum Precursors and Solution Acidities on REO-Based Catalysts Performances

    Institute of Scientific and Technical Information of China (English)


    Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.

  11. Analysis of coke precursor on catalyst and study on regeneration of catalyst in upgrading of bio-oil

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    Guo, Xiaoya; Zheng, Yong; Zhang, Baohua; Chen, Jinyang [Department of Chemical Engineering, Shanghai University, Shanghai 201800 (China)


    Catalyst HZSM-5 was used in bio-oil catalytic cracking upgrading. The precursor of coke on the catalyst was analyzed by means of TGA, FTIR and C13 NMR. Precursors of coke deposited in the pore of the molecular sieve were mainly aromatic hydrocarbon with the boiling point range from 350 C to 650 C. Those on the outer surface of the pellet precursor were identified as saturated aliphatic hydrocarbons with the boiling point below 200 C. The activity of HZSM-5 was studied after regeneration. In terms of yield of organic distillate and formation rate of coke, results showed that catalytic activity change moderately during the first three times of regeneration. (author)

  12. Preparation of carbon nanotubes by ethanol catalytic combustion technique using nickel salt as catalyst precursor

    Institute of Scientific and Technical Information of China (English)

    LI Fei; ZOU Xiao-ping; CHENG Jin; ZHANG Hong-dan; REN Peng-fei


    A simple growth technique of carbon nanotubes (CNTs) by combustion of ethanol was developed. In the experiment,copper plate was employed as substrate,nickel nitrate (Ni(NO3)2) and nickel chloride (NiCl2) as catalyst precursor,and ethanol as carbon source. The cleaned copper substrate was dipped into catalyst precursor solution for mounting catalyst precursor particles. The dip-coated substrate was then placed into ethanol flame for about 10 min after drying. The black wool-like production grown on copper plate was obtained. This route is called an ethanol catalytic combustion(ECC) process. The black powders were characterized by means of scanning electron microscopy(SEM),transmission electron microscopy(TEM),energy dispersive X-ray spectrometer(EDS) and Raman spectroscopy. The results show that the techique is much simpler and more economical to meet the future broader applications.

  13. Fabrication of CdS nanowires with increasing anionic precursor by SILAR method (United States)

    Dariani, R. S.; Salehi, F.


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

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



    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...


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    Khoirina Dwi Nugrahaningtyas


    Full Text Available The preparation and characterization of bimetallic catalysts using impregnation method with a variation of concentration of precursor sequence Co and Mo metal obtained catalyst K 1 [Co (0.018 M - Mo (0.037 M/USY]. K 2 [Co (0.026 M - Mo (0.055 M/USY], K 3 [Co (0.035 M - Mo (0.074 M/USY], K 4 [Co (0.05 M - Mo (0.11 M /USY] and K 5 [Co (0.107 M - Mo (0.22 M/USY]. Character of the catalyst in terms of crystallinity was analyzed by XRD. The result shows that there is no cristalinity damage of USY after impregnation but the amorphous cristalin structure was obtained. Amount of metal content was analyzed by XRF and the catalyst morphology by SEM-EDS. The result shows that the higher the concentration of Co and Mo so that find the higher content of metal in catalyst of the prepared catalyst increase. K 4 shows the best characteristic of catalysts prepared in this research. Analysis of K 4 is proving that Co and Mo are presented in catalyst.

  16. Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts (United States)

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


    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

  17. Sodium salts of anionic chiral cobalt(III) complexes as catalysts of the enantioselective Povarov reaction. (United States)

    Yu, Jie; Jiang, Hua-Jie; Zhou, Ya; Luo, Shi-Wei; Gong, Liu-Zhu


    The sodium salts of anionic chiral cobalt(III) complexes (CCC(-) Na(+) ) have been found to be efficient catalysts of the asymmetric Povarov reaction of easily accessible dienophiles, such as 2,3-dihydrofuran, ethyl vinyl ether, and an N-protected 2,3-dihydropyrrole, with 2-azadienes. Ring-fused tetrahydroquinolines with up to three contiguous stereogenic centers were thus obtained in high yields, excellent diastereoselectivities (endo/exo up to >20:1), and high enantioselectivities (up to 95:5 e.r.).

  18. Ozone decomposition on ZnO catalysts obtained from different precursors

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    Milenova Katya I.


    Full Text Available Kinetic investigations for ozone conversion on three different series of zinc oxide catalysts, containing pure ZnO and doped with Mn or Cu one with dopant content less than 1 wt.% were carried out. The different samples were obtained from carbonate, nitrate and acetate precursors. The as prepared catalysts were characterized by AAS, XRD, IR, EPR and BET methods. The mean size of the crystallites determined by XRD data is in the range 27÷68 nm. The presence of Mn2+ and Cu2+ ions into the ZnO matrix was established by EPR. The ozone decomposition was investigated for 30÷75°C temperature range. The zinc carbonate precursor samples show highest activity, while the nitrate precursor ones show lowest activity toward reaction decomposition of ozone in the whole temperature range. At 75°C two of the catalyst, obtained from carbonate precursor - ZnO and CuZnO show 100% conversion.

  19. Lanthanide amidinates and guanidinates: from laboratory curiosities to efficient homogeneous catalysts and precursors for rare-earth oxide thin films. (United States)

    Edelmann, Frank T


    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.

  20. Synthesis of silicon carbide nanorods by catalyst-assisted pyrolysis of polymeric precursor (United States)

    Yang, Weiyou; Miao, Hezhuo; Xie, Zhipeng; Zhang, Ligong; An, Linan


    In this Letter, we report the synthesis of β-SiC nanorods by the pyrolysis of a polysilazane polymeric precursor in the presence of 3 wt% FeCl 2 as a catalyst. The precursor is completely converted to the nanorods after heat-treated at 1700 °C for 2 h, accompanied by ˜50% weight loss. Electron microscopy study reveals that the nanorods preferentially grow along [1 1 1] direction; and the diameters of the nanorods range from 80 to 200 nm and lengths are ˜4 μm. A solid-liquid-solid growth mechanism is proposed.

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

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    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)


    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.)

  2. Bridging complexes of rare earth and cobalt cluster as catalyst precursors for Fischer-Tropsch synthesis

    Institute of Scientific and Technical Information of China (English)

    ZENG Shanghong; DU Dongping; BAI Fenghua; SU Haiquan


    Three new bridging complexes of rare earth and cobalt cluster were synthesized and characterized via ICP, IR and TG techniques.The structure of the complexes was speculated as: two rare earth atoms were bridged with four CF3COO-, and rare earth atoms were coordinated with cobalt carbonyl clusters to form a steady structure. Application of the complexes as the catalyst precursors was explored for Fischer-Tropsch synthesis. The study showed that the bridging complexes of rare earth and cobalt cluster had large molecular size and were difficult to enter pore path of γ-Al2O3, so they were dispersed on the surface of γ-A12O3 support. In addition, the performance of Co(Ce)/γ-Al2O3 was the best among the catalysts with complex as precursor and maintained 77.7% CO conversion at 220 ℃ for 80 operation hours.

  3. Improved and selective platinum recovery from spent alpha-alumina supported catalysts using pretreated anionic ion exchange resin. (United States)

    Shams, K; Goodarzi, F


    Improved and selective recovery of platinum from a spent dehydrogenation platinum alpha-alumina supported catalyst using a strong basic ion exchange resin is reported. Platinum and other precious metal group (PMG) complexes are leached using concentrated hydrochloric acid along with about 0.20 vol.% nitric acid as an oxidizing agent from de-coked and crushed spent catalyst. Effects of hydrochloric acid concentration, time, and temperature in leaching stage are investigated. The strong basic anionic resin is treated by sodium hydroxide solution to replace chloride anion by hydroxyl group ion. The supernatant of the leaching process is passed through a fixed column of hydroxylated strong base anionic resin. The treated resin on which the platinum complex is adsorbed is dried and burned in an oxidizing atmosphere at 750-800 degrees C. The recovered gray metallic powder is mainly platinum. Results compared with those obtained from untreated anionic resin show that adsorption of platinum complexes onto the treated anionic resin is more selective and the yield of separation is considerably improved. The breakthrough curves of the pretreated anion exchanger and that of untreated exchange resin reveals that the capacity of the hyroxilated resin is decreased by about 14%. These breakthrough curves can be used for calculation of height of a practical exchange plate (HPEP) for design purposes.

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

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    Le eXin


    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.

  5. Study on Sulifdation Degree and Morphology of MoS2 Catalyst Derived from Various Molybdate Precursors

    Institute of Scientific and Technical Information of China (English)

    Zhang Le; Li Mingfeng; Nie Hong


    The MoS2 catalysts were prepared from various molybdate precursors including inorganic and organic molybdate compounds. The sulifdation degree and morphology of active phases of MoS2 activated by various molybdate precursors in H2S/H2 stream at different temperatures were studied by X-ray photoelectron spectroscopy (XPS) and high-resolution trans-mission electron microscopy (HRTEM). The organic molybdate precursors lead to MoS2 catalysts with higher sulifdation degree and smaller active phases to demonstrate higher catalytic activity during hydrodesulfurizaiton (HDS) of 4,6-DMDBT.

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

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    Eftichia Papadopoulou


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

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

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    Britta Kämpken


    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.

  8. Biogas reforming on La-promoted NiMgAl catalysts derived from hydrotalcite-like precursors (United States)

    Serrano-Lotina, A.; Rodríguez, L.; Muñoz, G.; Daza, L.

    Hydrotalcite-like precursors have been synthesized in order to study the influence of lanthanum on the structure and the properties of the precursors, as well as on the catalytic activity and stability of their derived catalyst on biogas reforming. From XRD, and TPO characterization, we confirmed that hydrotalcite-like precursors where obtained. After calcination at 750 °C, Mg(Ni,Al)O solid solution was detected. High surface areas have been obtained finding the highest surface area on the catalyst without lanthanum. TPR experiments were performed in order to study the reducibility of the catalysts. One reduction peak was found in the catalyst without lanthanum while two peaks were observed in the catalysts with lanthanum. A reduction peak at 900 °C was observed over the sample without Ni and La. Catalytic tests, at 700 °C with a feed of CH 4:CO 2 1:1, were performed after appropriate reduction during 50 h. While a decrease on catalytic activity was observed with the addition and the increase of La content, an enhancement in the stability was observed. No sign of deactivation of the catalyst and no carbon deposition were found on the catalysts doped with lanthanum.

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

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    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.


    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.

  10. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction. (United States)

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


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

  11. Synthesis and Structure of Solvated Protons Incorporating Weakly Coordinating Anions. Precursors of Superacids

    Institute of Scientific and Technical Information of China (English)

    TSANG,Chi-Wing(曾志荣); YANG,Qing-Chuan(杨清传); MAK,Thomas C.W.(麦松威); XIE,Zuo-Wei(谢作伟)


    Six new solvated proton salts of highly halogenated carborane anions, [H(solvent)n] [carborane] (carborane = 1-R-CB11-Y5X-6 (R= H, Me; X, Y= Cl, Br, I), 1-H-CB9Br-9 ) were preparrf from the salt metathesis reaction of Ag(carborane)and HCl in high yields. Single-crystal X-ray analyses show that they are all discrete molecules in the solid-state. Tne mumher of the solvated molecules surrounding H+ ion can not be determined with the knowledge of the size and substituents of the carborane anions. Thnese salts provide convenient weighable sources of Brφnsted acid reagents having a wide range of acidities and good thermal stabilities. TGA results ubducate that the solvated molecules (water or organic molecules) in the catiobs [H(solvent)n]+ can be renoved under high temperature and high vacuum conditions to give superacidic mterials H(carborane) which can protonate olefin.

  12. Effective VTeO/SBA-15 Catalyst Prepared by Precursor Method for the Selective Oxidation of Propane to Acrolein

    Institute of Scientific and Technical Information of China (English)

    FENG Mao-ying; HUANG Chuan-jing; WENG Wei-zheng; WAN Hui-lin; XU Qin; ZHOU Zhao-hui


    Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein.The catalyst shows a better performance compared with those prepared by conventional impregnant method.A yield of 9.3% of acrolein was achieved with 2% V Ioadings at 500℃.XRD,N2-adsorption,H2-TPR,Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.

  13. Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic clay for Friedel-Crafts type benzylation reactions

    Indian Academy of Sciences (India)

    Vasant R Choudhary; Rani Jha; Pankaj A Choudhari


    Fe-Mg-hydrotalcite (Mg/Fe = 3) anionic clay with or without calcination (at 200-800°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, particularly after its use in the benzylation reaction, and the catalyst derived from it by its calcination at 200-800°C show high catalytic activity for the benzylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the chlorides and oxides of iron on the catalyst surface.

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

  15. Synthesis of Nitrogen-Doped Carbon Nanocoils with Adjustable Morphology using Ni–Fe Layered Double Hydroxides as Catalyst Precursors

    Directory of Open Access Journals (Sweden)

    Tomohiro Iwasaki


    Full Text Available Nitrogen-doped carbon nanocoils (CNCs with adjusted morphologies were synthesized in a one-step catalytic chemical vapour deposition (CVD process using acetoni‐ trile as the carbon and nitrogen source. The nickel iron oxide/nickel oxide nanocomposites, which were derived from nickel–iron layered double hydroxide (LDH precur‐ sors, were employed as catalysts for the synthesis of CNCs. In this method, precursor-to-catalyst transformation, catalyst activation, formation of CNCs, and nitrogen doping were all performed in situ in a single process. The morphology (coil diameter, coil pitch, and fibre diameter and nitrogen content of the synthesized CNCs was indi‐ vidually adjusted by modulation of the catalyst composi‐ tion and CVD reaction temperature, respectively. The adjustable ranges of the coil diameter, coil pitch, fibre diameter, and nitrogen content were confirmed to be approximately 500±100 nm, 600±100 nm, 100±20 nm, and 1.1±0.3 atom%, respectively.

  16. CO2 Reforming of CH4 over Nickel and Cobalt Catalysts Prepared from La-Based Perovskite Precursors

    Institute of Scientific and Technical Information of China (English)

    Jianjun Guo; Hui Lou; Yinghong Zhu; Xiaoming Zheng


    Four perovskite-type complex oxides (LaNiO3, La2NiO4, LaCoO3 and La2CoO4) were suc-cessfully prepared using two sol-gel methods, the Pechini method (PC) and the citric acid complexingmethod (CC). The catalysts were characterized by XRD and TPR. After reduction, the activity of thecatalysts in the CO2 reforming of methane was tested. Ni-based catalysts from La2NiO4 precursors werethe most active and stable catalyst after calcination above 850 ℃, which gave a methane conversion of0.025 mmol/(g@s) for those prepared by the PC method and 0.020 mmol/(g.s) by the CC method. Itwas proposed that the well-defined structure and lower reducibility is responsible for the unusual catalyticbehavior observed over the pre-reduced La2NiO4 catalyst.

  17. 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


    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.

  18. Influence of different palladium precursors on the properties of solution-combustion-synthesized palladium/ceria catalysts for methane combustion


    Colussi, Sara; Gayen, Arup; Boaro, Marta; Llorca Piqué, Jordi; Trovarelli, Alessandro


    A series of Pd/CeO2 catalysts was prepared by solution combustion synthesis (SCS) using different Pd precursors. The powders were characterized by complementary techniques such as BET surface area measurements, X-Ray diffraction analysis, X-Ray photoelectron spectroscopy, temperature-programmed reduction, temperature-programmed oxidation, and high-resolution TEM. The results obtained evidenced the formation of a Pd-Ce solid solution on all SCS samples. This solid solution is in the form of an...

  19. A microstructural investigation of gas atomized Raney type Al-27.5 at.% Ni catalyst precursor alloys

    Energy Technology Data Exchange (ETDEWEB)

    Mullis, A.M., E-mail: [Institute for Materials Research, University of Leeds, Leeds LS2 9JT (United Kingdom); Bigg, T.D., E-mail: [Institute for Materials Research, University of Leeds, Leeds LS2 9JT (United Kingdom); Adkins, N.J., E-mail: [IRC in Materials Processing, University of Birmingham, Edgbaston, Birmingham B15-2TT (United Kingdom)


    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 such catalysts, including the necessity for post-production crushing of gas atomized powders. Models are proposed to account for both variations. - Highlights: • The phase composition of powder Raney-Ni catalysts has been investigated. • Image analysis is used to quantify differences between and within particles. • Phase composition can vary by up to 10% between the particle surface and centre. • Differences of up to 10% in the mean composition are also found between particles.

  20. Anionic liposome template synthesis of raspberry-like hollow silica particle under ambient conditions with basic catalyst. (United States)

    Ishii, Haruyuki; Sato, Kumi; Nagao, Daisuke; Konno, Mikio


    Hollow silica particle was obtained with a vesicle template synthesis in water under ambient conditions in the presence of ammonia. Biomimetic vesicles, liposomes were used, which consisted of a zwitterionic phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), and a tiny amount of charged amphiphiles, hexadecylamine (HDA) or dicetylphosphate (DCP). Aggregation of silica occurred for DPPC or cationic DPPC/HDA liposome, whereas well-dispersed hollow silica particle could be obtained for anionic DPPC/DCP liposome. The hollow particle synthesized with the anionic liposome had single-layered and raspberry-like structures. Electrostatic repulsion between anionic vesicles maintained stable dispersion of the as-synthesized particles during the reaction. Formation of the raspberry-like morphology is explained by silica particle precipitation selectively induced around the liposomes under basic conditions due to affinity of silica precursors for the liposomes. Synthesis of well-dispersed hollow silica particle with a raspberry-like morphology is the first report in vesicle template syntheses.

  1. Catalytic synthesis of nitrogen-doped multi-walled carbon nanotubes using layered double hydroxides as catalyst precursors

    Indian Academy of Sciences (India)

    Yong Cao; Yun Zhao; Qingxia Li; Qingze Jiao


    The nitrogen (N)-doped carbon (CN) nanotubes were synthesized by pyrolysis of ethylenediamine with Ni1.07Mg1.01AlO3.58, Ni1.99Mg0.29AlO3.78, and Ni2.31Mg0.08AlO3.89 mixed oxides as catalysts at 650°C. Those mixed oxides were obtained by calcination of corresponding layered double hydroxide precursors (LDHs). Structure and composition of LDHs and mixed oxides were characterized by X-ray diffraction (XRD) and Inductively coupled plasma spectrum. X-ray photoelectron spectroscopy and transmission electron microscope were used to characterize the N content, proportion of pyridine-like N structure and morphology of CN nanotubes. The results showed that the tubes grown with Ni2.31Mg0.08AlO3.89 as catalysts had more obvious bamboo-like structure, larger diameter than those grown with Ni1.07Mg1.01AlO3.58 and Ni1.99Mg0.29AlO3.78. The N content and proportion of graphitic-like N structures increased with the content of Ni2+ increasing in LDH precursors. The morphology, N content and pyridine-like N structures for CN nanotubes can be controlled to a certain extent by varying the content of Ni2+ in LDH precursors.

  2. Helix-Sense-Selective Polymerization of N,N-Diphenyl(Meth)acrylamide by Anionic Catalysts

    Institute of Scientific and Technical Information of China (English)


    In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diphenyl methacrylamide(DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too.It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

  3. Porous structure and particle size of silica and hydrotalcite catalyst precursors

    NARCIS (Netherlands)

    Titulaer, M.K.


    The subject of this thesis is the control of the porous structure of catalyst bodies. The first part deals with silica, that can be utilized as catalyst support with many industrially important catalytic reactions. The second part of the thesis deals with the preparation and characterization of soli

  4. Influence of hydrogen on chemical vapour synthesis of different carbon nanostructures using propane as precursor and nickel as catalyst

    Indian Academy of Sciences (India)

    R K Sahoo; H Mamgain; C Jacob


    The role of hydrogen in the catalytic chemical vapour deposition of carbon nanotubes using sputtered nickel thin film as a catalyst is explained in this work. The growth of different carbon nanostructures with the variation in the precursor gas content was studied by keeping all other process parameters constant and using sputtered Ni thin film as a catalyst. The catalyst granule size, its external morphology and the resulting products were analysed. Carbon nanotubes (CNTs), carbon nanofibres (CNFs) and carbon nanoribbons (CNRs) were observed under different growth conditions. The different conditions of growth leading to form tubes, fibres or ribbons were analysed by varying the flow ratio of propane and hydrogen gas during the high temperature growth. Scanning and transmission electron microscopies confirmed the above structures under different growth conditions. The role of hydrogen on the surface passivation behaviour of the Ni catalyst and its correlative effect on the growth of carbon nanostructures is analysed. This direct approach can, in principle, be used to synthesize different types of carbon nanostructures by tailoring the hydrogen concentration.

  5. Steam reforming of methane over Ni catalysts prepared from hydrotalcite-type precursors:Catalytic activity and reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    Yang Qi; Zhenmin Cheng; Zhiming Zhou


    Ni/Mg–Al catalysts derived from hydrotalcite-type precursors were prepared by a co-precipitation technique and applied to steam reforming of methane. By comparison with Ni/γ-Al2O3 and Ni/α-Al2O3 catalysts prepared by in-cipient wetness impregnation, the Ni/Mg–Al catalyst presented much higher activity as a result of higher specific surface area and better Ni dispersion. The Ni/Mg–Al catalyst with a Ni/Mg/Al molar ratio of 0.5:2.5:1 exhibited the highest activity for steam methane reforming and was selected for kinetic investigation. With external and inter-nal diffusion limitations eliminated, kinetic experiments were carried out at atmospheric pressure and over a temperature range of 823–973 K. The results demonstrated that the overal conversion of CH4 and the conversion of CH4 to CO2 were strongly influenced by reaction temperature, residence time of reactants as wel as molar ratio of steam to methane. A classical Langmuir–Hinshelwood kinetic model proposed by Xu and Froment (1989) fitted the experimental data with excellent agreement. The estimated adsorption parameters were consistent thermodynamical y.

  6. Nickel-carbon nanocomposites prepared using castor oil as precursor: A novel catalyst for ethanol steam reforming (United States)

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

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

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

    DEFF Research Database (Denmark)

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


    and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS...

  8. Salt anions promote the conversion of HypF-N into amyloid-like oligomers and modulate the structure of the oligomers and the monomeric precursor state. (United States)

    Campioni, Silvia; Mannini, Benedetta; López-Alonso, Jorge P; Shalova, Irina N; Penco, Amanda; Mulvihill, Estefania; Laurents, Douglas V; Relini, Annalisa; Chiti, Fabrizio


    An understanding of the solution factors contributing to the rate of aggregation of a protein into amyloid oligomers, to the modulation of the conformational state populated prior to aggregation and to the structure/morphology of the resulting oligomers is one of the goals of present research in this field. We have studied the influence of six different salts on the conversion of the N-terminal domain of Escherichiacoli HypF (HypF-N) into amyloid-like oligomers under conditions of acidic pH. Our results show that salts having different anions (NaCl, NaClO(4), NaI, Na(2)SO(4)) accelerate oligomerization with an efficacy that follows the electroselectivity series of the anions (SO(4)(2-)≥ ClO(4)(-)>I(-)>Cl(-)). By contrast, salts with different cations (NaCl, LiCl, KCl) have similar effects. We also investigated the effect of salts on the structure of the final and initial states of HypF-N aggregation. The electroselectivity series does not apply to the effect of anions on the structure of the oligomers. By contrast, it applies to their effect on the content of secondary structure and on the exposure of hydrophobic clusters of the monomeric precursor state. The results therefore indicate that the binding of anions to the positively charged residues of HypF-N at low pH is the mechanism by which salts modulate the rate of oligomerization and the structure of the monomeric precursor state but not the structure of the resulting oligomers. Overall, the data contribute to rationalize the effect of salts on amyloid-like oligomer formation and to explain the role of charged biological macromolecules in protein aggregation processes.

  9. 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


    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.

  10. Development of a New Combinatorial Approach to Multifunctional Catalysts: Metal Silsesquioxanes as Precursors to Microporous Metallosilicates

    Institute of Scientific and Technical Information of China (English)

    MAXIM, Nicolae


    Microporous, silica-supported netal oxides with a very narrow pore size distribution around 0.6 nm diameter, typicalsurface areas ranging from 350 to 700 m2/g, and loadings of well-dispersed metal oxide (up to w=10% of metal) result from thecontrolled calcination of silsesquioxane metal complexes. A versatile new methodology is envisioned that, in a combinatorial fashion, enables catalyst preparation with control over metal content and dispersity, together with adjustable Lewis and Bronsted acidity, In addition, the method is suitable for the preparation of bi-andmultifunctional catalysts containing different metals.

  11. Influence of Aging Time on the Properties of Precursors of CuO/ZnO Catalysts for Methanol Synthesis

    Institute of Scientific and Technical Information of China (English)

    Deren Fang; Zhongmin Liu; Shuanghe Meng; Ligang Wang; Lei Xu; Hua Wang


    The aging process of pure copper precursors and copper-zinc binary precursors were studied by XRD, TG-DTG and TPR techniques. The catalytic activity and stability of CuO/ZnO were tested using fixed-bed flow reactor, and the physical properties of the catalysts and Cu species were characterized with N2 adsorption and N2O passivation method, respectively. For the Cu-Zn binary system prepared at the precipitating condition of pH=8.0 and temperature=80 ℃, the initial phase was a mixture of copper nitrate hydroxide Cu2(NO3)(OH)3, georgeite and hydrozincite Zn5(CO3)2(OH)6. By increasing the duration of its aging time, the phase of Cu2(NO3)(OH)2 first transited to georgeite, and then interdiffused into Zn5(CO3)2(OH)6 and resulted in two new phases: rosasite (Cu,Zn)2CO3(OH)2 and aurichalcite (Zn,Cu)5(CO3)2(OH)6. The former phase was much easier to be formed than the latter one,while the latter phase was more responsible for the activity of methanol synthesis than the former one. It is found that the composition and structure of the precursors altered obviously after the colour transition point. The experimental results showed that methanol synthesis is a structure-sensitive catalytic reaction.

  12. CO-free hydrogen from steam-reforming of bioethanol over ZnO-supported cobalt catalysts. Effect of the metallic precursor

    Energy Technology Data Exchange (ETDEWEB)

    Llorca, Jordi; De la Piscina, Pilar Ramirez; Sales, Joaquim; Homs, Narcis [Departament de Quimica Inorganica, Universitat de Barcelona, c/Marti i Franques 1-11, 08028 Barcelona (Spain); Dalmon, Jean-Alain [Institut de Recherches sur la Catalyse-CNRS, 2 Avenue Albert Einstein, 69626 Villeurbanne (France)


    The ethanol steam-reforming reaction was studied over ZnO-supported cobalt catalysts (10wt.% Co). Catalysts were prepared by impregnation of nitrate and carbonyl cobalt precursors. Characterization was accomplished by transmission electron microscopy (TEM), Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), and in situ techniques: magnetic measurements, and diffuse reflectance infrared spectroscopy (DRIFT) coupled to mass spectrometry. The use of Co{sub 2}(CO){sub 8} as precursor produced a catalyst that was highly stable and selective for the production of CO-free hydrogen at reaction temperature as low as 623K. The only by-product was methane and selectivity of 73% to H{sub 2} and 25% to CO{sub 2} was obtained. Under reaction conditions, the catalyst showed 92% of reduced cobalt, mainly as small particles.

  13. Permanganic acid: a novel precursor for the preparation of manganese oxide catalysts

    NARCIS (Netherlands)

    C. Kappenstein; T. Wahdan; D. Duprez; M.I. Zaki; D. Brands; E. Poels; A. Bliek


    Unsupported and ψ-alumina supported MnOx catalysts (1-10 wt-% Mn) were preparedfrom aqueous solutions of HMnO4 and compared with nitrate based samples. They were characterized by XRD, XPS, BET area, oxygen storage capacity and by their catalytic behaviour versus ammonia DeNOx reaction. The unsupport

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


    Sufang He; Lei Zhang; Suyun He; Liuye Mo; Xiaoming Zheng; Hua Wang; Yongming Luo


    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...

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

    Energy Technology Data Exchange (ETDEWEB)

    Palacio, L.A. [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia, A.A. 1226 - Medellin (Colombia); Silva, E.R.; Catalao, R. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Silva, J.M. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Instituto Superior Engenharia de Lisboa, Departamento de Engenharia Quimica. Av. Cons. Emidio Navarro, 1959-007 Lisboa (Portugal); Hoyos, D.A. [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia, A.A. 1226 - Medellin (Colombia); Ribeiro, F.R. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Ribeiro, M.F. [IBB-Institute for Biotechnology and Bioengineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa (Portugal)], E-mail:


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

  16. Nickel ferrite spinel as catalyst precursor in the dry reforming of methane:Synthesis, characterization and catalytic properties

    Institute of Scientific and Technical Information of China (English)

    Rafik Benrabaa; Hamza Boukhlouf; Axel L(o)fberg; Annick Rubbens; Rose-N(o)elle Vannier; Elisabeth Bordes-Richard; Akila Barama


    Dry reforming of methane by CO2 using nickel ferrite as precursor of catalysts was investigated.Nickel ferrite crystalline particles were prepared by coprecipitation of nitrates with NaOH or ammonia followed by calcination,or by hydrothermal synthesis without calcination step.The textural and structural properties were determined by a number of analysis methods,including X-ray diffraction (XRD),Raman spectroscopy and X-ray photoelectron spectroscopy (XPS),among which X-ray diffraction (XRD) was at room and variable temperatures.All synthesized oxides showed the presence of micro or nanoparticles of NiFe2O4 inverse spinel,but Fe2O3 (hematite) was also present when ammonia was used for coprecipitation.The reducibility by hydrogen was studied by temperature-programmed reduction (TPR) and in situ XRD,which showed the influence of the preparation method.The surface area (BET),particle size (Rietveld refinement),as well as surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied according to the synthesis method.The catalytic reactivity was investigated using isopropanol decomposition to determine the acid/base properties.The catalytic performance of methane reforming with CO2 was measured with and without the pre-treatment of catalysts under H2 in 650-800 ℃ range.The catalytic conversions of methane and CO2 were quite low but they increased when the catalysts were pre-reduced.A significant contribution of reverse water gas shift reaction accounted for the low values of H2/CO ratio.No coking was observed as shown by the reoxidation step performed after the catalytic reactions.The possible formation of nickel-iron alloy observed during the study of reducibility by hydrogen was invoked to account for the catalytic behavior.

  17. 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


    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.

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

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


    Nanostructured CuxZn1-xAl2O4 with a Cu : Zn ratio of ¼ : ¾ has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al2O3-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m2 g-1). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen and the accessible metallic Cu(0) surface area of the reduced catalyst was 8 m2 g-1. The catalytic performance of the material in CO2 hydrogenation and methanol steam reforming was compared with conventionally prepared Cu/ZnO/Al2O3 reference catalysts. The observed lower performance of the spinel-based samples is attributed to a lack of synergetic interaction of the Cu nanoparticles with ZnO due to the incorporation of Zn2+ in the stable spinel lattice. Despite its lower performance, however, the nanostructured nature of the spinel catalyst was stable after thermal treatment up to 500 °C in contrast to other Cu-based catalysts. Furthermore, a large fraction of the re-oxidized copper migrates back into the spinel upon calcination of the reduced catalyst, thereby enabling a regeneration of sintered catalysts after prolonged usage at high temperatures. Similarly prepared samples with Ga instead of Al exhibit a more crystalline catalyst with a spinel particle size around 20 nm. The slightly decreased Cu(0) surface area of 3.2 m2 g-1 due to less copper incorporation is not a significant drawback for the methanol steam reforming.Nanostructured CuxZn1-xAl2O4 with a Cu : Zn ratio of ¼ : ¾ has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al2O3-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m2 g-1). Cu nanoparticles of an average size of 3.3 nm can be formed by reduction of the spinel precursor in hydrogen

  19. Catalytic performance for CO{sub 2} conversion to methanol of gallium-promoted copper-based catalysts. Influence of metallic precursors

    Energy Technology Data Exchange (ETDEWEB)

    Toyir, Jamil; Ramirez de la Piscina, Pilar; Homs, Narcis [Departament de Quimica Inorganica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Fierro, Jose Luis G. [Instituto de Catalisis y Petroleoquimica, C.S.I.C., Cantoblanco, 28049 Madrid (Spain)


    This study reports new gallium-promoted copper-based catalysts prepared by co-impregnation of methoxide-acetylacetonate (acac) precursors from methanolic solutions onto silica and zinc oxide supports. Catalyst performance in the CO{sub 2} hydrogenation to methanol was investigated at 2MPa and temperatures between 523 and 543K. A high activity and selectivity for ZnO-supported catalysts was found, which also showed a high stability in terms of both activity and selectivity. The maximum value for the activity was 378gMeOH/kgcath at 543K, with a selectivity of 88% towards methanol production. The high performance of these materials in the CO{sub 2} hydrogenation is related to the presence of Ga{sub 2}O{sub 3} promoter and highly dispersed Cu{sup +} species on the surface, determined by XPS and Auger on used catalysts.

  20. Methanol synthesis from CO2 hydrogenation over La-M-Cu-Zn-O (M = Y, Ce, Mg, Zr) catalysts derived from perovskite-type precursors (United States)

    Zhan, Haijuan; Li, Feng; Gao, Peng; Zhao, Ning; Xiao, Fukui; Wei, Wei; Zhong, Liangshu; Sun, Yuhan


    A series of La-M-Cu-Zn-O (M = Y, Ce, Mg, Zr) based perovskite-type catalysts are prepared by sol-gel method and characterized by XRD, BET, TPR, N2O-adsorption, XPS and TPD techniques. The results indicate that all the catalysts exhibit La2CuO4 perovskite structure. The addition of Ce, Mg and Zr lead to smaller particles, lower reduction temperature, higher Cu dispersion, larger amount of hydrogen desorption at low temperature and more amount of basic sites. However, Y has less affects on the physicochemical properties. The catalysts derived from perovskite-type precursors show high selectivity for methanol, which is correlated with the Cuα+ species that exists in the reduced catalysts. More exposed Cu surface area is favorable for high CO2 conversion.

  1. Styrene epoxidation with hydrogen peroxide over calcium oxide catalysts prepared from various precursors

    Institute of Scientific and Technical Information of China (English)

    Qingming Gu; Dan Han; Lei Shi; Qi Sun


    A series of CaO samples were prepared by calcination of commercially available and synthesis of calcium salt precursors such as calcium acetate,carbonate,hydroxide and oxalate etc.CaO samples were found to be effective for the epoxidation of styrene using hydrogen peroxide as an oxidant in the presence of acetonitrile.To determine the influence of the physicochemical properties and surface basicity on the catalytic activity,the prepared CaO samples were characterized using thermogravimetry (TG),X-ray diffraction (XRD),scanning electron microscopy (SEM),N2-adsorption and temperature-programmed desorption of CO2 (CO2-TPD).The results indicate that the amounts of very strong basic sites and high basicity strength on CaO sample are key factors for its excellent catalytic performance.In contrast,the surface area,porosity and the surface structure of CaO sample have a relatively minor effect on the catalytic activity.CaO sample,obtained by the decomposition of Ca(OH)2,prepared by precipitating calcium nitrate with sodium hydroxide in ethylene glycol solution,exhibits the highest amount of very strong basic sites and stronger strength of basic sites,and therefore it catalyses the epoxidation of styrene with the highest rate among the tested CaO samples.Under the selected reaction conditions,the selectivity of 97.5% to styrene oxide at a conversion in excess of 99% could be obtained.

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

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


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

  3. Influence of Ce-precursor and fuel on structure and catalytic activity of combustion synthesized Ni/CeO{sub 2} catalysts for biogas oxidative steam reforming

    Energy Technology Data Exchange (ETDEWEB)

    Vita, Antonio, E-mail:; Italiano, Cristina; Fabiano, Concetto; Laganà, Massimo; Pino, Lidia


    A series of nanosized Ni/CeO{sub 2} catalysts were prepared by Solution Combustion Synthesis (SCS) varying the fuel (oxalyldihydrazide, urea, carbohydrazide and glycerol), the cerium precursor (cerium nitrate and cerium ammonium nitrate) and the nickel loading (ranging between 3.1 and 15.6 wt%). The obtained powders were characterized by X-ray Diffraction (XRD), N{sub 2}-physisorption, CO-chemisorption, Temperature Programmed Reduction (H{sub 2}-TPR) and Scanning Electron Microscopy (SEM). The catalytic activity towards the Oxy Steam Reforming (OSR) of biogas was assessed. The selected operating variables have a strong influence on the nature of combustion and, in turn, on the morphological and structural properties of the synthesized catalysts. Particularly, the use of urea allows to improve nickel dispersion, surface area, particle size and reducibility of the catalysts, affecting positively the biogas OSR performances. - Highlights: • Synthesis of Ni/CeO{sub 2} nanopowders by quick and easy solution combustion synthesis. • The fuel and precursor drive the structural and morphological properties of the catalysts. • The use of urea as fuel allows to improve nickel dispersion, surface area and particle size. • Ni/CeO{sub 2} (7.8 wt% of Ni loading) powders synthesized by urea route exhibits high performances for the biogas OSR process.

  4. Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical (United States)

    Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.


    The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

  5. 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: [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: [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)


    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.

  6. 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


    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.

  7. 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.


    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.

  8. 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


    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.

  9. Continuous-Flow O-Alkylation of Biobased Derivatives with Dialkyl Carbonates in the Presence of Magnesium-Aluminium Hydrotalcites as Catalyst Precursors. (United States)

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


    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.

  10. Helix—Sense—Selective Polymerization of N,N—Diphenyl (Meth) acrylamide by Anionic Catalysts

    Institute of Scientific and Technical Information of China (English)

    HongXUE; YongAnXU; 等


    In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diphenyl methacrylamide (DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.

  11. A Pd/C-CeO2 Anode Catalyst for High-Performance Platinum-Free Anion Exchange Membrane Fuel Cells. (United States)

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


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

  12. Iridium(I) complexes with anionic N-heterocyclic carbene ligands as catalysts for the hydrogenation of alkenes in nonpolar media. (United States)

    Kolychev, Eugene L; Kronig, Sabrina; Brandhorst, Kai; Freytag, Matthias; Jones, Peter G; Tamm, Matthias


    A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium-COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent stability and activity in hydrogenation of alkenes at low catalyst loadings (down to 10 ppm).

  13. Synthesis of carbon nanotubes by catalytic pyrolysis method with Feitknecht compound as precursor of NiZnAl catalyst

    Institute of Scientific and Technical Information of China (English)

    Yan Xiaoqi; Liu Quanrun; Zhang Songlin; Zhang Kun; Chen Jiuling; Li Yongdan


    Carbon nanotubes are synthesized by catalytic pyrolysis method with a kind of new type catalyst--nickel-zinc-alumina catalyst prepared from Feitknecht compound. Tubular carbon nanotubes, bamboo-shaped carbon naotubes, herringbone carbon nanotubues and branched carbon nanotubes are all found formed at moderate temperature. It is important for the formation of quasi-liquid state of the metal nanoparticles at the tip of carbon naotubes during the growth of carbon nanotubes to lead to different kinds of carbon nanotubes. It is likely that the addition of zinc make the activity of nickel catalyst after calcinations and reduction changed strangely.

  14. Anions in Cometary Comae (United States)

    Charnley, Steven B.


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

  15. The effect of precursors salts on surface state of Pd/Al2O3 and Pd/CeO2/Al2O3 catalysts

    Directory of Open Access Journals (Sweden)

    André L. Guimarães


    Full Text Available The influence of the precursors on the promoting effect of ceria on Pd/Al2O3 catalyst, when ceria is coated over alumina was studied. The reaction of propane oxidation proceeded under different feed conditions and the surface active sites were characterized by X-ray photoelectron spectroscopy (XPS and in situ diffuse reflectance spectroscopy (DRS. XPS and DRS results show that PdO/Pd0 interface are the active sites independent of the precursor, while the catalysts containing CeO2 showed formation of palladium species in the highest oxidation state, probably PdO2 (338 eV after the oxidation of propane. Besides, the O/Al and O/Ce ratios evidenced the increase of oxygen storage in the presence of CeO2. In addition, the precursor acetylacetonate favors the oxygen storage in the lattice.Estudo da influência dos precursores sobre os catalisadores de Pd/Al2O3 promovidos com céria ancorado sobre a alumina. A oxidação do propano foi feita sob diferentes condições de alimentação sendo caracterizados os sítios superficiais por Espectroscopia Fotoeletrônica de raios X (XPS e por Refletância Difusa em ''situ''. Resultados de XPS e DRS mostraram a formação de interfaces de PdO/Pd0 como sendo os sítios ativos, independentes do precursor utilizado na preparação, enquanto que os catalisadores contendo CeO2 mostraram a formação de espécies de paládio com estado de oxidação mais altos, provavelmente PdO2 (338 eV após a oxidação do propano. Além disso, as razões O/Al e O/Ce evidenciaram um aumento de oxigênio armazenado na presença de CeO2. O precursor acetilacetonato favoreceu o armazenamento de oxigênio na rede.

  16. 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


    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.

  17. Evaluation of Hydrocalumite-Like Compounds as Catalyst Precursors in the Photodegradation of 2,4-Dichlorophenoxyacetic Acid

    Directory of Open Access Journals (Sweden)

    Manuel Sánchez-Cantú


    Full Text Available Three hydrocalumite-like compounds in a Ca/Al ratio of 2 containing nitrate and acetate anions in the interlaminar region were prepared by a simple, economic, and environmentally friendly method. The solids were characterized by X-ray powder diffraction (XRD, thermogravimetric (TG analysis, nitrogen adsorption-desorption at −196°C, scanning electron microscopy (SEM, infrared spectroscopy (FTIR, and UV-Vis Diffuse Reflectance Spectroscopy (DRS. The catalytic activity of the calcined solids at 700°C was tested in the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D where 57% degradation of 2,4-D (40 ppm and a mineralization percentage of 60% were accomplished within 150 minutes. The photocatalytic properties were attributed to mayenite hydration, since the oxide ions in the cages are capable of reacting with water to form hydroxide anions capable of breaking down the 2,4-D molecules.

  18. Evaluation of Hydrocalumite-Like Compounds as Catalyst Precursors in the Photodegradation of 2,4-Dichlorophenoxyacetic Acid


    Manuel Sánchez-Cantú; Clara Barcelos-Santiago; Claudia M. Gomez; Esthela Ramos-Ramírez; Ma. de Lourdes Ruiz Peralta; Nancy Tepale; González-Coronel, Valeria J.; A. Mantilla; Francisco Tzompantzi


    Three hydrocalumite-like compounds in a Ca/Al ratio of 2 containing nitrate and acetate anions in the interlaminar region were prepared by a simple, economic, and environmentally friendly method. The solids were characterized by X-ray powder diffraction (XRD), thermogravimetric (TG) analysis, nitrogen adsorption-desorption at −196°C, scanning electron microscopy (SEM), infrared spectroscopy (FTIR), and UV-Vis Diffuse Reflectance Spectroscopy (DRS). The catalytic activity of the calcined solid...

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

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


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

  20. The Role of the Coprecipitation Sequence of Salt Precursors on the Genesis of Cu-ZnO-Al2O3 Catalysts: Synthesis, Characterization and Activity for Low Temperature Shift Reaction

    Directory of Open Access Journals (Sweden)

    R.T. Figueiredo


    Full Text Available Cu-ZnO-Al2O3 catalysts for the low-temperature water-gas shift reaction were prepared using methods of direct and reverse coprecipitation. The catalysts obtained were characterized by DRX, TPR, XPS, N2O chemisorption, Hg-Porosimetry and BET surface area. It was observed that the precipitation sequence of the precursors led to significant differences in values of copper dispersion and consequently in the activity of the catalyst for the water-gas shift reaction.

  1. Synthesis of Ni/Mg/Al Layered Double Hydroxides and Their Use as Catalyst Precursors in the Preparation of Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    ZHAO Yun; JIAO Qing-ze; LIANG Ji; LI Chun-hua


    Ni/Mg/Al layered double hydroxides(LDHs) with different n(Ni):n(Mg):n(Al) ratio values were prepared via a coprecipitation reaction. Then Ni/Mg/Al mixed oxides were obtained by calcination of these LDHs precursors. Carbon nanotubes were produced in the catalytic decomposition of propane over the Ni/Mg/Al mixed oxide catalysts. The quality of as-made nanotubes was investigated by SEM and TEM. The nanotubes were multiwall with a high length-diameter ratio and appeared to be flexible. The catalytic activities of these mixed oxides increased with increasing the Ni content. The Ni/Mg/Al mixed oxide with the highest Ni content [n(Ni)/n(Mg)/n(Al)=1/1/1] showed the highest activity and the carbon nanotubes grown on its surface had the best quality.

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

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


    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.

  3. Session 4: Combine reforming of methane over LaCo{sub 1-x}Ni{sub x}O{sub 3} perovskites as catalysts precursors

    Energy Technology Data Exchange (ETDEWEB)

    Goldwasser, M.R.; Lugo, M.L.; Rivas, M.E.; Pietri, E.; Perez-Zurita, M.J.; Cubeiro, M.L. [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, Fac. Ciencias, UCV, Apartado 47102, Los Chaguaramos, Caracas (Venezuela); Griboval-Constant, A.; Leclercq, G. [Universite des Sciences ET Technologies de Lille, Lab. de Catalyse Heterogene et Homogene, 59 - Villeneuve D' Ascq (France)


    The effect of the partial and total substitution of the nickel by cobalt in a LaNiO{sub 3} perovskite as catalyst precursors in the combine reforming of methane with CO{sub 2} and O{sub 2} for the production of syngas was studied. The solids were synthesized by the sol gel method and characterized by IR, BET surface area, XRD, TPR, EDX and in situ XRD under the condition of fresh, reduced and used samples. The results showed that through this synthesis it is possible to obtain highly crystalline, homogeneous and pure solids, with well-defined structures. It was observed that by reduction of the perovskites, the metals (Co, Ni) are in a highly disperse state on a matrix compose of the La{sub 2}O{sub 3}. The stabilization of nickel by the presence of Co was evidenced, decreasing deactivation by avoiding the sintering of metals by coke formation on the surface of the catalysts. (authors)

  4. Exploring Pd adsorption, diffusion, permeation, and nucleation on bilayer SiO2/Ru as a function of hydroxylation and precursor environment: From UHV to catalyst preparation (United States)

    Pomp, Sascha; Kaden, William E.; Sterrer, Martin; Freund, Hans-Joachim


    The hydroxylation-dependent permeability of bilayer SiO2 supported on Ru(0001) was investigated by XPS and TDS studies in a temperature range of 100 K to 600 K. For this, the thermal behavior of Pd evaporated at 100 K, which results in surface and sub-surface (Ru-supported) binding arrangements, was examined relative to the extent of pre-hydroxylation. Samples containing only defect-mediated hydroxyls showed no effect on Pd diffusion through the film at low temperature. If, instead, the concentration of strongly bound hydroxyl groups and associated weakly bound water molecules was enriched by an electron-assisted hydroxylation procedure, the probability for Pd diffusion through the film is decreased via a pore-blocking mechanism. Above room temperature, all samples showed similar behavior, reflective of particle nucleation above the film and eventual agglomeration with any metal atoms initially binding beneath the film. When depositing Pd onto the same SiO2/Ru model support via adsorption of [Pd(NH3)4]Cl2 from alkaline (pH 12) precursor solution, we observe notably different adsorption and nucleation mechanisms. The resultant Pd adsorption complexes follow established decomposition pathways to produce model catalyst systems compatible with those created exclusively within UHV despite lacking the ability to penetrate the film due to the increased size of the initial Pd precursor groups.

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

    KAUST Repository

    Renard, Laetitia


    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.

  6. Surface features and catalytic performance of platinum/alumina catalysts in slurry-phase hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez-Ortiz, M.A.; Gonzalez-Marcos, M.P.; Arnaiz-Aguilar, S.; Gonzalez-Marcos, J.A.; Gonzalez-Velasco, J.R. (Univ. del Pais Vasco/Euskal Hirrika Unibertsitatea, Bilbao (Spain). Dept. de Ingenierlla Quimica)


    Several platinum catalysts supported on three commercial [gamma]-aluminas were prepared by impregnation and anionic exchange using aqueous solutions of H[sub 2]PtCl[sub 6]. A number of methods were used to characterize the precursors as well as the final catalysts, including TGA, TPR, and hydrogen chemisorption at 298 K. TPR measurements showed two reduction peaks for the catalysts: the first one corresponding to reduction of the metal precursor to platinum and the second one associated to formation of a surface complex, Pt-Al[sub 2]O[sub 3[minus]x], With partial reduction of the support. The activity of the different catalysts was tested in the slurry-phase hydrogenation of benzene. The results obtained in the activity measurements have been correlated to the characteristics of the catalysts.

  7. Highly stereospecific polymerization of isoprene with homogeneous binary Ziegler-Natta catalysts based on NCN-pincer neodymium precursor

    Institute of Scientific and Technical Information of China (English)


    The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system.This system exhibited high activity and high cis-1,4 selectivity for the polymerization of isoprene (Tp=20 °C,98.2%;Tp=-20 °C,> 99%).Such catalytic performances remained under a broad range of polymerization temperatures and monomer-to-neodymium ratios (from 500 to 8000),reaching high number-average molecular weight (Mn=1582 kg/mol) and relatively narrow molecular weight distribution (PDI=1.68),which was,however,influenced by the amount and bulkiness of aluminum alkyls.Dynamic investigation of the polymerization was performed,which showed the number-average molecular weight of the resultant polyisoprene had an almost linear correlation with the conversion,suggesting,in some degree,the polymerization with this catalytic system was controllable.

  8. Ionic Liquids as Carbene Catalyst Precursors in the One-Pot Four-Component Assembly of Oxo Triphenylhexanoates (OTHOs

    Directory of Open Access Journals (Sweden)

    Anton Axelsson


    Full Text Available Ionic liquids (ILs are a convenient and inexpensive source of N-heterocyclic carbenes (NHCs. In this study, dialkyl imidazolium-based ILs are used as carbene precursors in a four-component synthesis of oxo triphenylhexanoates (OTHOs, where it was found that IL outperformed commonly used NHC precatalysts in terms of reaction efficiency. The reaction is highly stereoselective, delivering the anti-diastereomer (20:1 dr, and the OTHOs can be obtained in high-to-excellent yields. By virtue of the four-component reaction-setup, facile construction of the OTHO scaffold with a diverse set of functional groups (21 examples can be achieved. In the context of sustainability, the IL can be recovered and reused several times without affecting selectivity or yield. Moreover, most compounds can be isolated by precipitation and filtration, mitigating the use of solvent-demanding chromatography.

  9. 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: [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)


    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.

  10. 阴离子膜燃料电池碳基氧还原催化剂研究进展%Research progress of carbon-based catalysts for oxygen reduction in anion exchange membrane fuel cells

    Institute of Scientific and Technical Information of China (English)

    孙天航; 王晓晔; 黄乃宝; 梁成浩


    对阴离子膜燃料电池中碳基氧还原催化剂的研究进展进行详细评述,分析杂原子掺杂碳基催化剂在阴离子膜燃料电池上应用的可行性.在此基础上,提出杂原子掺杂的多孔纳米碳材料是阴离子膜燃料电池阴极催化剂今后的重要发展方向.%The research progresses of carbon-based catalysts for oxygen reduction in anion exchange membrane fuel cell (AMFC) were reviewed in detail.The application feasibility of heteroatom doped carbon-based catalysts in AMFC was also analyzed.On this basis,heteroatom doped porous nano-carbon materials should be the potential materials of cathodic catalysts for anion exchange membrane fuel cells.

  11. Treatment of a non-azo dye aqueous solution by CWAO in continuous reactor using a Ni catalyst derived from hydrotalcite-like precursor. (United States)

    Vallet, Ana; Besson, Michèle; Ovejero, Gabriel; García, Juan


    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°C. An increase in the reaction temperature (120-180°C), and a decrease in dye concentration (1000-3000 ppm) or liquid flow rate (0.1-0.7 mL min(-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(-1) and 180°C under 5 MPa air.

  12. Anion-π catalysis. (United States)

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


    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

  13. 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


    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.

  14. 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


    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.

  15. Synthesis,Characterization and Application of Benzyl-substituted Cyclopentadienyl lanthanide Complexes as Catalyst Precursors for the Syndiotactic Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    QIAN,Yan-Long(钱延龙); BALA,Muhammad D.; XIE,Xiao-Min(谢小敏); HUANG,Ji-Ling(黄吉玲)


    Benzyl-substituted cyclopentadienyl lanthanide complexes were synthesized and characterized by elemental analysis, MS and IR spectroscopy. The analytical data point out the formation of monomeric, unsolvated complexes.In conjunction with Al(Et)3 as co-catalyst, the title complexes are efficient catalysts for the syndiotactic polymerization of methyl methacrylate. For the complex (C6H5CH2C5H4)2YCI, under the optimum polymerization conditions (60 ℃, n(MMA):n(catalyst):n(co-catalyst)= 1000:1:10), a predominantly syndiotactic (rr=66%) polymer of high molecular weight (Mη = 105000) was obtained.

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

    Directory of Open Access Journals (Sweden)

    Eero eSalminen


    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.

  17. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal (United States)

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


    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.

  18. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng


    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.

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


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


    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 ...

  20. 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)


    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.)

  1. 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


    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...

  2. Synthesis of Arylzinc Thiolates Containing Perfluoroalkyl Chains : Model Catalyst Precursors for the Enantioselective Zinc-Mediated 1,2-Addition of Dialkylzincs to Aldehydes in Fluorous Biphase Systems

    NARCIS (Netherlands)

    Koten, G. van; Kleijn, H.; Rijnberg, E.; Jastrzebski, J.T.B.H.


    The synthesis of perfluoroalkyl-functionalized arene trimethylsilyl ethers and their conversion to ethylzinc thiolates is described. These compounds have been successfully applied as catalysts in the enantioselective addition of diethylzinc to benzaldehyde. This is the first example of a two-phase o

  3. Hydrothermally synthesised Fe{sub 2}O{sub 3} nanoparticles as catalyst precursors for the CVD production of graphitic nanofibres

    Energy Technology Data Exchange (ETDEWEB)

    Edwards, H K [School of Mechanical, Materials and Manufacturing Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Evans, E [School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); McCaldin, S [School of Mechanical, Materials and Manufacturing Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Blood, P [School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Gregory, D H [School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Poliakoff, M [School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Lester, E [School of Chemical Engineering and Mining Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Walker, G S [School of Mechanical, Materials and Manufacturing Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom); Brown, P D [School of Mechanical, Materials and Manufacturing Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD (United Kingdom)


    Graphitic nanofibres (GNFs) have been grown by chemical vapour deposition at 500 deg. C and 700 deg. C, using 6 nm and 20 nm particles of Fe{sub 2}O{sub 3} produced by supercritical water hydrothermal synthesis (scWHS). The morphologies of catalyst and GNFs have been examined using the combined techniques of conventional transmission electron microscopy, high resolution electron microscopy, selected area electron diffraction and powder X-ray diffraction. GNF production varied from well ordered nanofibres with an average diameter of 100 nm, to very large, disordered fibres with diameters ranging from 500 nm to {approx}2 {mu}m. Larger fibres were found to have a compound structure composed of discreet domains of graphite and multiwall nanotubes. 20 nm particles produced by scWHS were associated with significant increases in the yield of GNFs as compared with traditional catalyst precipitation routes.


    Institute of Scientific and Technical Information of China (English)

    Kotohiro Nomura


    Precise,efficient copolymerizations of ethylene with cyclic olefins[norbomene(NBE),cyclopentene (CPE) using nonbridged half-titanocenes of type,Cp'TiCI2(L)(Cp'=cyclopentadienyl group,L=aryloxo,ketimide)-MAO catalyst systems have been summarized.CpTiCI2(N=C'Bu2) exhibited both remarkable camlytic activity and efficient NBE incorporation for ethylene/NBE copolymerization:the NBE incorporation by Cp'TiCI2(X)(X=N=C'Bu2,O-2,6-'Pr2C6H3;Cp'=Cp,C5Me5,indenyl) was related to the calculated coordination energy after ethylene insertion.('BuC5H4)TiCI2(N=C'Bu) exhibited significant catalytic activities with efficient CPE incorporations in ethylene/CPE copolymerization in the presence of MAO.The polymerization proceeded with exclusive 1,2-CPE incorporation.affording high molecular weight (altemating)copolymers with uniform distributions.Therefore,the cyclopentadienyl fragment(Cp')plays an essential role in terms of both the activity and the efficient cyclic olefin incorporation.


    Directory of Open Access Journals (Sweden)

    Seyed Mehdi Sajjadi


    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.

  6. A new class of organocatalysts: sulfenate anions. (United States)

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


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

  7. Vibrational spectroscopy of the double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor (United States)

    Thompson, Simon T.; Lamb, H. Henry; Delley, Bernard; Franzen, Stefan


    Tetraamminepalladium(II) perrhenate, a double complex salt, has significant utility in PdRe catalyst preparation; however, the vibrational spectra of this readily prepared compound have not been described in the literature. Herein, we present the infrared (IR) and Raman spectra of tetraamminepalladium(II) perrhenate and several related compounds. The experimental spectra are complemented by an analysis of normal vibrational modes that compares the experimentally obtained spectra with spectra calculated using DFT (DMol3). The spectra are dominated by features due to the ammine groups and the Resbnd O stretch in Td ReO4-; lattice vibrations due to the D4h Pd(NH3)42+ are also observed in the Raman spectrum. Generally, we observe good agreement between ab initio calculations and experimental spectra. The calculated IR spectrum closely matches experimental results for peak positions and their relative intensities. The methods for calculating resonance Raman intensities are implemented using the time correlator formalism using two methods to obtain the excited state displacements and electron-vibration coupling constants, which are the needed inputs in addition to the normal mode wave numbers. Calculated excited state energy surfaces of Raman-active modes correctly predict relative intensities of the peaks and Franck-Condon activity; however, the position of Raman bands are predicted at lower frequencies than observed. Factor group splitting of Raman peaks observed in spectra of pure compounds is not predicted by DFT.

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

    Energy Technology Data Exchange (ETDEWEB)

    Valderrama, Gustavo [Laboratorio de Catalisis, Petroleo y Petroquimica, Unidad de Estudios Basicos, Universidad de Oriente - Nucleo Bolivar, La Sabanita - Calle San Simon, Estado Bolivar 8001 (Venezuela); Kiennemann, Alain [Laboratoire des Materiaux et Procedes pour la Catalyse, UMR 7515, ECPM, Universite Louis Pasteur, 25 rue Becquerel, 67087 Strasbourg Cedex 2 (France); Goldwasser, Mireya R. [Centro de Catalisis, Petroleo y Petroquimica, Facultad de Ciencias - Universidad Central de Venezuela. Paseo los Ilustres, Los Chaguaramos, Caracas 1040 (Venezuela)


    La{sub 1-x}Sr{sub x}Ni{sub 0.4}Co{sub 0.6}O{sub 3} and La{sub 0.8}Sr{sub 0.2}Ni{sub 1-y}Co{sub y}O{sub 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{sub 2} to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH{sub 4}/CO{sub 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{sub 0.9}Sr{sub 0.1}CoO{sub 3} and/or La{sub 0.9}Sr{sub 0.1}NiO{sub 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{sup 0}, Co{sup 0} with particle sizes in the range of nanometers over the SrO and La{sub 2}O{sub 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. (author)

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

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


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

  11. 金属-有机骨架化合物为前驱体制备CuO/CeO2催化剂及在富氢条件下催化CO的氧化%Preparation of CuO/CeO2 Catalysts from Metal-organic Frameworks Precursor for Preferential CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    徐力; 陈超; 王瑞; 罗家还; 刘云凌; 张宁


    采用金属-有机骨架化合物(MOFs) Ce(1,3,5-BTC)(H2O)6为前驱体浸渍Cu2+离子后焙烧得到CuO/CeO2催化剂(B系列),并应用于富氢气氛中CO优先氧化反应(CO-PROX).通过与CuO/CeO2催化剂(A-600)对比发现,不同的MOFs前驱体对催化剂铜活性物种的分散程度有很大影响.X射线衍射分析(XRD)、透射电子显微镜(TEM)和氛气程序升温还原(H2-TPR)等表征均证明B系列催化剂表面铜有聚集现象,由此增加了催化剂的抗H2O和CO2性能.%Employing metal-organic frameworks (MOFs)as precursors,a series of CuO/CeO2 catalysts was prepared and applied for CO-PROX (preferential oxidation of CO) in H2-rich stream.Compared with previously reported A-600 catalyst [A-600 catalyst was obtained by thermal treatment of the Cu3 (BTC)2 precursors with Ce3+ ions,the calcination temperature was selected to be 600 ℃ for removing the organic species],we can conclude that different precursors lead different catalytic activity.The X-ray diffraction,temperature-programmed reduction in H2 (H2-TPR),transmission electron microscope and X-ray photoelectron spectroscopy analysis characterization indicated the as-synthetic catalysts presented more bulk CuO species on the surface than that of the A-600 catalyst,which resulted in the negative catalytic activity for preferential CO oxidation.But this also prevented the deactivation of catalysts in H2 O and CO2 steam,indicating that the catalysts were promising in the CO-PROX process for proton exchange membrane fuel cell(PEMFC) application.

  12. Oxidation catalyst (United States)

    Ceyer, Sylvia T.; Lahr, David L.


    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.

  13. Preparation of polyamide 6/silica nanocomposites from silica surface initiated ring-opening anionic polymerization

    Directory of Open Access Journals (Sweden)


    Full Text Available Polyamide 6/silica nanocomposites were synthesized by in situ ring-opening anionic polymerization of ε-caprolactam in the presence of sodium caprolactamate as a catalyst and caprolactam-functionalized silica as an initiator. The initiator precursor, isocyanate-functionalized silica, was prepared by directly reacting commercial silica with excess toluene 2,4-diisocyanate. This polymerization was found to occur in a highly efficient manner at relatively low reaction temperature (170°C and short reaction times (6 h. FTIR spectroscopy was utilized to follow the introduction and consumption of isocyanate groups on the silica surface. Thermogravimetric analysis indicated that the polyamide 6 was successfully grown from the silica surface. Transmission electron microscopy was utilized to image polymer-functionalized silica, showing fine dispersion of silica particles and their size ranging from 20 to 40 nm.

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


    Galip Akay


    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...

  15. Topologically unique heterometallic Cu(II)/Li coordination polymers self-assembled from N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid biobuffer: versatile catalyst precursors for mild hydrocarboxylation of alkanes to carboxylic acids. (United States)

    Kirillova, Marina V; Kirillov, Alexander M; Martins, André N C; Graiff, Claudia; Tiripicchio, Antonio; Pombeiro, Armando J L


    The facile aqueous medium reactions of copper(II) nitrate with BES biobuffer [(HOCH(2)CH(2))(2)N(CH(2)CH(2)SO(3)H), hereinafter referred as H(3)bes] in the presence of various benzenecarboxylic acids [benzoic (Hba), 3-hydroxybenzoic (Hhba), and 3,5-dihydroxybenzoic (Hdhba) acid] and lithium hydroxide gave rise to the self-assembly generation of three new heterometallic Cu(II)/Li materials, [Li(H(2)O)(4)][Cu(4)(μ(2)-Hbes)(4)(μ(2)-ba)]·H(2)O (1) and [Cu(4)(μ(3)-Hbes)(4)(L){Li(H(2)O)(2)}](n)·3nH(2)O {L = μ(2)-hba (2) and μ(2)-dhba (3)}. They were isolated as air-stable crystalline solids and fully characterized by infrared (IR) and UV-vis spectroscopy and electrospray ionization (ESI)-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses. The latter revealed that 1-3 have comparable packing patterns and unit cell parameters, being composed of similar [Cu(4)(μ-Hbes)(4)(μ-carboxylate)](-) cores and [Li(H(2)O)(4)](+) cations (in 1) or [μ-Li(H(2)O)(2)](+) groups (in 2 and 3), which are arranged into discrete 0D aggregates in 1 or infinite 3D noninterpenetrating metal-organic networks in 2 and 3. The topological analysis of the coordination polymers 2 and 3 disclosed the trinodal 3,3,4-connected underlying nets with an unprecedented topology defined by the point symbol of (4.6.8)(4)(4(2).6)(2)(6(2).16(2).18(2)), further simplification of which resulted in the binodal 4,4-connected nets with the pts (PtS) topology. Apart from representing very rare examples of coordination compounds derived from H(3)bes, 1-3 feature solubility in water and were applied as efficient and versatile catalyst precursors for the mild (60 °C) single-pot hydrocarboxylation, by CO and H(2)O, of various gaseous, linear, and cyclic C(n) (n = 2-9) alkanes into the corresponding C(n+1) carboxylic acids, in H(2)O/MeCN medium under homogeneous conditions and in the presence of potassium peroxodisulfate. Total yields (based on alkane) of carboxylic acids up to 78% were

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

    Directory of Open Access Journals (Sweden)

    Peter Hesemann


    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.

  17. 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:


    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.

  18. Anion exchange membrane (United States)

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


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

  19. Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts (United States)

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


    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.

  20. Cationic ruthenium alkylidene catalysts bearing phosphine ligands. (United States)

    Endo, Koji; Grubbs, Robert H


    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  1. Methane Tri-reforming over nickel catalysts


    García Vargas, José Manuel


    The present work is part of a research program carried out in the Department of Chemical Engineering at the University of Castilla-La Mancha, focused in the preparation, characterization and evaluation of catalysts that can be applied in industrially relevant reactions. In this way, the PhD work reported here was aimed to study and improve nickel catalysts applied to the tri-reforming process, evaluating the role of support, precursor and promoter and optimizing the catalyst preparation. Furt...

  2. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    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.

  3. 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


    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.

  4. Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol. (United States)

    Zhang, Jie; Zhang, Changbin; He, Hong


    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.

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

    DEFF Research Database (Denmark)


    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.......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...

  6. Methanol Steam Reforming Catalysts for Fuel Cell Driven Electric Vehicles

    Institute of Scientific and Technical Information of China (English)

    Yongfeng Li; Xinfa Dong; Weiming Lin


    Cu/ZnAlO catalysts derived from hydroxycarbonate precursors containing hydrotalcite-likelayered double hydroxides (LDHs) were studied. The influence on the performance of the catalysts wasalso studied when the Al in the Cu/ZnAlO catalyst was partly or completely replaced by Zr or Ce.

  7. 二苯并噻吩在分散型钼催化剂和原位产生的氢存在下的加氢脱硫Ⅲ.催化剂前身物、硫化氢、一氧化碳和水对反应的影响%HDS OF DBT USING in situ GENERATED HYDROGEN IN THE PRESENCE OF DISPERSED Mo CATALYSTS Ⅲ. Effects of Catalyst Precursors, H2S, CO and H2O

    Institute of Scientific and Technical Information of China (English)

    刘晨光; Flora T.T.Ng


    研究了水水/甲苯乳化液中二苯并噻吩(硫芴)在分散型钼酸、磷钼酸和四硫钼酸铵催化剂存在下的加氢脱硫反应.反应在高压釜中于340℃及三种不同的气氛即H2,H2/H2O和CO/H2O(CO和H2O经水煤气转换反应(WGSR)产生原位氢)的存在下进行.用GC和GC-MS鉴定、分析了气体和液体产物的组成.结果表明:对硫芴的加氢脱硫反应,在分散型四硫钼酸铵催化剂存在下,原位产生的氢的效果仅比加入的氢气稍好,而在分散型钼酸和磷钼酸催化剂存在下,原位产生的氢远比加入的氢气有效.实验结果还表明:硫化氢能显著提高分散型钼酸和磷钼酸催化剂的加氢脱硫活性,但在分散型四硫钼酸铵催化剂存在下,硫化氢能促进加氢反应而抑制氢解反应.一氧化碳和水均选择性地抑制氢解反应.%The hydrodesulfurization (HDS) of dibenzothiophene (DBT) was investigated using dispersed catalyst precursors molybdic acid (MA), phosphomolybdic acid (PMA), and ammonium tetrathiomolybdate (ATTM). The results indicated that with ATTM catalyst, in situ hydrogen was slightly more active than the externally supplied molecular H2 for HDS of DBT, but is not so active as with MA and PMA catalysts. The experimental results also indicated that H2S has a significant promotional effect on the catalytic activity of MA or PMA catalyst. While the H2 S promoted the hydrogenation pathway, inhibited the hydrogenolysis pathway with ATTM catalyst.Both CO and H2O selectively inhibited the hydrogenolysis route.


    Energy Technology Data Exchange (ETDEWEB)

    Dr. Yaw D. Yeboah


    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


    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov


    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


    Energy Technology Data Exchange (ETDEWEB)

    Branko N. Popov


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

  11. Sterically shielded diboron-containing metallocene olefin polymerization catalysts (United States)

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


    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.

  12. [(≢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


    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.

  13. Nanoparticular metal oxide/anatase catalysts

    DEFF Research Database (Denmark)


    The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

  14. Effect of palladium precursor on the performance of nanorods CeO2-supported palladium catalyst for toluene catalytic combustion%钯前驱体对纳米棒 CeO2载钯催化剂催化甲苯燃烧性能的影响

    Institute of Scientific and Technical Information of China (English)

    谷广锋; 王红培; 韩玉香; 万海勤; 郑寿荣; 许昭怡


    针对挥发性有机物污染日益严重问题,本文采用水热法制备了纳米棒二氧化铈,并以其为载体,通过浸渍法制备了不同前驱体的 Pd/CeO2催化剂。采用透射电子显微镜、X 射线衍射、X 射线光电子能谱和氢气程序升温还原等手段对催化剂进行了表征,并在微型固定床反应器上评价了催化剂催化甲苯的燃烧性能。结果表明:在采用不同前驱体制备的 Pd/CeO2催化剂中, Pd 均以 Pd2+的形式存在于纳米棒状 CeO2表面;在以硝酸钯和氯化钯为前驱体的 Pd/CeO2催化剂中,前者具有更低的氢气还原温度,同时在甲苯催化燃烧反应中显示出更低的 t50和 t90,分别为219和236℃。结果表明,以硝酸钯为前驱体的催化剂具有更高的催化活性。%For the problem of volatile organic compounds pollution increasing seriously,palladium catalysts with various precur-sors supported on CeO2 nanorods were prepared by impregnation method.These catalysts were characterized using transmission electron microscopy (TEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS)and H2 temperature pro-grammed reduction.The catalytic performance of these catalysts for toluene combustion was evaluated in a fixed-bed microreac-tor.The results show that palladium highly dispersed on the CeO2 nanorods surface as Pd2+ states in all the Pd/CeO2 catalysts with various precursors.Pd-N/CeO2 (palladium nitrate as precursor)shows a lower reduction temperature than that of Pd-C/CeO2 (palladium chloride as precursor),and show a lower t50 and t90 at 219 and 236 ℃,respectively,in toluene catalytic combus-tion,indicating that Pd-N/CeO2 possesses higher catalytic activity than that over Pd-C/CeO2 .

  15. Ureaphosphanes as hybrid, anionic or supramolecular bidentate ligands for asymmetric hydrogenation reactions

    NARCIS (Netherlands)

    Meeuwissen, J.; Detz, R.; Sandee, A. J.; de Bruin, B.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.


    We report the coordination behavior of ureaphosphane ligand 1-[2-(diphenylphosphanyl)ethyl]-3-phenylurea (L1) towards different rhodium precursor complexes. Depending on the nature of the anion and the ligand/metal ratio, L1 acts either as a hybrid P,O-coordinating chelate, as an anionic P,N-coordin

  16. Homogeneous catalysts

    CERN Document Server

    Chadwick, John C; Freixa, Zoraida; van Leeuwen, Piet W N M


    This first book to illuminate this important aspect of chemical synthesis improves the lifetime of catalysts, thus reducing material and saving energy, costs and waste.The international panel of expert authors describes the studies that have been conducted concerning the way homogeneous catalysts decompose, and the differences between homogeneous and heterogeneous catalysts. The result is a ready reference for organic, catalytic, polymer and complex chemists, as well as those working in industry and with/on organometallics.

  17. Preparation and characterizations of Ce-Cu-O monolithic catalysts for ethyl acetate catalytic combustion

    Institute of Scientific and Technical Information of China (English)

    马瑞红; 苏孝文; 金凌云; 鲁继青; 罗孟飞


    Ce-Cu-O monolithic catalysts were prepared by using Ce0.9Cu0.1O1.9 solid solution or nitrate as precursors,and their catalytic performance for the combustion of ethyl acetate were studied.The catalysts calcined at a low temperature showed high catalytic activities.When calcined at high temperatures,the catalyst with Ce0.9Cu0.1O1.9 solid solution as precursor remained a high activity,while the catalyst with metal nitrates as precursors exhibited a suppressed reactivity.Therefore,the catalyst prepared with th...

  18. 溶剂极性对微波辐射老化制备前驱体及CuO/ZnO/Al2O3催化剂结构的影响%Influence of Solvent Polarity on Microstructure of Precursors and CuO/ZnO/Al2O3 Catalysts Aged under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    崔晓曦; 范辉; 郑华艳; 李忠


    在制备CuO/ZnO/Al2O3催化剂的老化过程中,采用微波辐射老化技术,着重研究了溶剂极性对前躯体物相组成,烧后CuO/ZnO/Al2O3催化剂结构及其在浆态床合成甲醇工艺中催化性能的影响.通过XRD、DTG、H2-TPR,FTIR、HR-TEM和XPS对前驱体及催化剂表征表明,沉淀母液在微波辐射条件下进行老化,溶剂的极性对前躯体物相组成及催化剂结构影响显著.随着溶剂极性的增大,Zn2+/Cu2+取代Cu2(CO3)(OH)2/Zn5(CO3)2(OH)6中Cu2+/Zn2+的取代反应增强,使得前躯体中(Cu,Zn)5(CO3)2(OH)6和(Cu,Zn)2(CO3)(OH)2物相的含量增多,结晶度提高,导致烧后CuO/ZnO/Al2O3催化剂中CuO-ZnO协同作用增强,且CuO晶粒减小,表面Cu含量增加,催化剂活性和稳定性提高.水溶剂的极性最大,制备的催化剂活性和稳定性最好,甲醇的时空收率(STY)和平均失活率分别为32O mg· g-1·h-1和0.11%·d-1.%In the preparation of a CuO/ZnO/Al2O3 catalyst for slurry methanol synthesis, microwave irradiation was introduced into the aging process. The effect of solvent polarity was studied on phase composition of the precursor, microstructure of the calcined CuO/ZnO/Al2O3 catalyst and catalytic performance for slurry methanol synthesis. The characterization by XRD, FTIR, DTG, HR-TEM, H2-TPR and XPS showed that the solvent polarity had a significant effect on the composition of the precursor aged under microwave irradiation. The results indicated that solvent polarity benefited to the substitution of Cu27Zn2+ in Cu2(CO3)(OH)2/Zn5(CO3)2(OH)6 by Zn27Cu2+. With the increasing of the solvent polarity, the content and crystallization degree of (Cu, Zn)2(CO3)(OH)2 and (Cu, Zn)5(CO3)2(OH)6 became higher in the precursor, the interaction of CuO/ZnO/Al2O3 between CuO and ZnO became stronger, CuO crystal particles dispersed better and surface CuO content became higher. The performance of CuO/ZnO/Al2O3 catalyst using water as solvent is the best, the methanol sapce-time yield (STY


    Directory of Open Access Journals (Sweden)



    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.

  20. Design of hybrid titania nanocrystallites as supports for gold catalysts. (United States)

    Mendez, Violaine; Caps, Valérie; Daniele, Stéphane


    Citrate-functionalized titania nanocrystallites are successfully synthesized from a heteroleptic titanium alkoxide precursor in a low temperature, hydrolytic process and used as gold catalyst supports for CO oxidation and aerobic stilbene epoxidation.

  1. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

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


    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...... by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

  2. Potentiometric anion selective sensors

    NARCIS (Netherlands)

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


    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 aqu

  3. Catalyst mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Masel, Richard I.; Rosen, Brian A.


    Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

  4. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity (United States)

    Balof, Shawna Lynn


    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

  5. Photo-oxidation catalysts (United States)

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


    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.

  6. Catalyst containing oxygen transport membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lane, Jonathan A.; Wilson, Jamie R.; Christie, Gervase Maxwell; Petigny, Nathalie; Sarantopoulos, Christos


    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 microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. 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.

  7. Catalyst containing oxygen transport membrane (United States)

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


    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.

  8. Supported cobalt catalysts - preparation, characterization and reaction studies


    Backman, Leif


    The aim of this work was to understand on the effect of thermal treatments, precursor and support on the interaction between the support and cobalt species, and further how the interaction affects the reducibility and dispersion of the catalyst. Silica and alumina supported cobalt catalysts were prepared, characterised and tested for catalytic activity. The catalysts were prepared by gas phase deposition techniques from cobalt acetylacetonate and cobalt carbonyl and by incipient wetness impre...

  9. 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


    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

  10. Highly dispersed metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  11. Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Palladium Catalyst

    Institute of Scientific and Technical Information of China (English)

    Wei ZHAO; Wei Guo CHENG; Zeng Xi LI; Lei WANG; Xiang Ping ZHANG; Suo Jiang ZHANG


    Supported palladium catalysts, which were used in the oxidative esterification of methacrolein to methyl methacrylate, have been prepared with different carriers and Pd precursors.Experimental results revealed that Pd catalysts with γ-Al2O3 support and Na2PdCl4 precursor showed good performance. Pd catalyst modified with Pb and Mg indicated that Pd-Mg bimetallic catalyst exhibited considerably higher activity and Pd-Pb exhibited both higher activity and selectivity. 92.27% methacrolein conversion and 90.57% methyl methacrylate selectivity were obtained on Pd-Pb-Mg catalyst.

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

    DEFF Research Database (Denmark)


    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...

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

    DEFF Research Database (Denmark)


    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...

  14. The effect of Pd precursor on Pd/Ce0.67Zr0.33O2 catalysts for automotive emission control%钯前驱体对汽车尾气处理Pd/Ce0.67Zr0.33O2催化剂催化性能的影响

    Institute of Scientific and Technical Information of China (English)

    林嗣煜; 杨林颜; 阳雪; 周仁贤


    分别以Pd(NO3)2, Pd(NH3)4(NO3)2和H2PdCl4为钯前驱体制备了Pd/Ce0.67Zr0.33O2(CZ)催化剂.以硝酸钯为钯前驱体制得的Pd/CZ(NO)催化剂具有较高的储氧量,存在较多的小的钯簇,其钯与载体间相互作用较强,因此在三种新鲜催化剂中对HC和CO的消除表现出了最好的催化活性.以硝酸四氨钯为钯前驱体制得的Pd/CZ(NH)催化剂具有较高的钯分散度,存在较多的大的钯簇,同时存在金属态和氧化态的钯,从而对NO和NO2的消除表现出了较好的催化活性.以氯钯酸为钯前驱体制得的Pd/CZ(Cl)催化剂由于钯分散度较小,钯与载体间作用较弱,存在的CeOCl抑制了氧空穴的生成,因此对各种反应物的催化活性都较低.但Pd/CZ(Cl)催化剂表现出了较好的热稳定性,这是由于老化处理消除了残余的氯物种并且促进了钯与载体间的作用.%A Pd/CZ(NO) catalyst prepared with Pd(NO3)2 as the metal precursor exhibited the best catalytic performance for HC and CO elimination because of a higher oxygen storage capacity, abundant small Pdn clusters and a strong Pd‐support interaction that facilitated electron transfer from PdOx particles to the CZ support. A Pd/CZ(NH) catalyst prepared with Pd(NH3)4(NO3)2 as the metal pre‐cursor exhibited good performance for NO and NO2 elimination due to a higher Pd dispersion, abundant bigger Pdn clusters and oxidized/metallic Pd coexistence. A Pd/CZ(Cl) catalyst prepared with H2PdCl4 as the metal precursor exhibited low catalytic activity due to a low Pd dispersion, weak Pd‐support interaction, and the trace amount of CeOCl which inhibited oxygen vacancy crea‐tion. However, it showed good thermal stability, and benefited when an aging treatment removed the residual chlorine species and also promoted the interaction between PdOx and the support.

  15. Production of hydrogen from methanol over binary Cu/ZnO catalysts Part I. Catalyst preparation and characterisation

    NARCIS (Netherlands)

    Melián-Cabrera, Ignacio; Boutonnet, Magali; Agrell, Johan; Fierro, José L.G.


    Mixed copper–zinc oxide catalysts (Cu/ZnO) were prepared by two different techniques, i.e. from hydroxycarbonate precursors formed in aqueous solution and from oxalate precursors formed in water-in-oil microemulsion. Their physicochemical properties were characterised by nitrogen adsorption–desorpti

  16. Development of a Direct Ethanol Fuel Cell System with Anion Exchange Membranes (United States)


    Fuel Cell System with Anion Exchange Membranes Report Title Based on the Phase I research results, we identified that carbon supported Pd-based catalysts...Report 22-0ct-2012- 21-Jan-2013 4. 1ITLE AND SUBTITLE 5a CONTRACT NUMBER Development of a Direct Ethanol Fuel Cell System with Anion Exchange...14. ABSTRACT Based on the Phase I research results, we identified that carbon supported Pd-based catalysts, such as Pd/C and PdRu!C, had better

  17. Heterogeneous Catalysts

    NARCIS (Netherlands)

    Dakka, J.; Sheldon, R.A.; Sanderson, W.A.


    Abstract of GB 2309655 (A) Heterogeneous catalysts comprising one or more metal compounds selected from the group consisting of tin, molybdenum, tungsten, zirconium and selenium compounds deposited on the surface of a silicalite are provided. Preferably Sn(IV) and/or Mo(VI) are employed. The cat

  18. 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


    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.

  19. Resonant spectra of quadrupolar anions

    CERN Document Server

    Fossez, K; Nazarewicz, W; Michel, N; Garrett, W R; Płoszajczak, M


    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as extreme halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-molecule problem using a non-adiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational ban...

  20. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


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

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

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Kegnæs, Søren


    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 challen...

  2. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis (United States)

    Endo, Koji; Grubbs, Robert H.


    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. PMID:21563826

  3. Developments of Catalysts for Hydrogen Production from Dimethyl Ether

    Institute of Scientific and Technical Information of China (English)

    Kaoru; Takeishi


    1 Results Dimethyl ether (DME) is expected as a clean fuel of the 21st century.I have developed new catalysts for hydrogen production by steam reforming of DME.Cu-Zn/Al2O3 catalysts prepared by the sol-gel method produce large quantities of H2 and CO2 by DME steam reforming under lower reaction temperature[1].However,the sol-gel catalysts will be more expensive than general catalysts prepared by impregnation methods and coprecipitation methods,because the precursor,alkoxides are very expensive.For pract...

  4. Earthquakes: hydrogeochemical precursors (United States)

    Ingebritsen, Steven E.; Manga, Michael


    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.

  5. Anionic surface binders

    Directory of Open Access Journals (Sweden)

    Aljaž-Rožič Mateja


    Full Text Available The MELAMIN Chemical Factory in Kočevje manufactures synthetic resins and binders for the paper industry. Binders based on AKD (alkyl ketene dimer are produced which are used for binding paper and cardboard in the range of neutral and partially basic pH. Cationic and, lately, anionic binders are mostly used for the bulk binding of paper and board. The possibility of using AKD binders on paper or board surfaces is presented. In this case partially cationic AKD binders may be applied. When optical whiteners are used, the application of AKD binders is recommended. In the case of paper it is possible to substitute acrylate binders by AKD binders. The best results are obtained when the paper is first partly treated in bulk and subsequently surface treated.

  6. Modeling Carbon Chain Anions in L1527

    CERN Document Server

    Harada, Nanase


    The low-mass protostellar region L1527 is unusual because it contains observable abundances of unsaturated carbon-chain molecules including CnH radicals, H2Cn carbenes, cyanopolyynes, and the negative ions C4H- and C6H-, all of which are more associated with cold cores than with protostellar regions. Sakai et al. suggested that these molecules are formed in L1527 from the chemical precursor methane, which evaporates from the grains during the heat-up of the region. With the gas-phase osu.03.2008 network extended to include negative ions of the families Cn-, and CnH-, as well as the newly detected C3N-, we modeled the chemistry that occurs following methane evaporation at T~ 25-30 K. We are able to reproduce most of the observed molecular abundances in L1527 at a time of ~5000 yr. At later times, the overall abundance of anions become greater than that of electrons, which has an impact on many organic species and ions. The anion-to-neutral ratio in our calculation is in good agreement with observation for C6H-...

  7. Resonant spectra of quadrupolar anions (United States)

    Fossez, K.; Mao, Xingze; Nazarewicz, W.; Michel, N.; Garrett, W. R.; Płoszajczak, M.


    In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-rotor problem using a nonadiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. The rotor is treated as a linear triad of point charges with zero monopole and dipole moments and nonzero quadrupole moment. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational bands could be identified above the detachment threshold. We study the evolution of a bound state of an anion as it dives into the continuum at a critical quadrupole moment and we show that the associated critical exponent is α =2 . Everything considered, quadrupolar anions represent a perfect laboratory for the studies of marginally bound open quantum systems.

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

    Rannulu, Nalaka S.; Cole, Richard B.


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

  9. Ceramic catalyst materials

    Energy Technology Data Exchange (ETDEWEB)

    Sault, A.G.; Gardner, T.J. [Sandia National Laboratories, Albuquerque, NM (United States); Hanprasopwattanna, A.; Reardon, J.; Datye, A.K. [Univ. of New Mexico, Albuquerque, NM (United States)


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


    Institute of Scientific and Technical Information of China (English)

    XUMancai; OUZhize; 等


    Possibilities for enhancement of catalytic reaction rate by combining phase transfer catalysis and hydrogen bonding of the catalyst with the substrate and reagent were studied.A phase transfer catalyst library with sixty polystyrene-supported quaternary ammonium salt catalysts was synthesized.The reduction of acetophenone by NaBH4 was used as the probing reaction to select out the ost active catalyst in the library by using iterative method.which was the gel-type triethanolamine aminsating strongly asic anion exchange resin with the crosslinking degeree of 2% A hydrogen bonding assisted catalytic mechanism was proposed to explain the high catalytic activity of the catalyst.

  11. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis. (United States)

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


    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.

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

    Directory of Open Access Journals (Sweden)

    E.I. Muresan


    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.

  13. Catalyst Architecture

    DEFF Research Database (Denmark)

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


    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...... meaningful for everyone. The exhibited works are designed by SANAA, Diller Scofidio + Renfro, James Corner Field Operation, JBMC Arquitetura e Urbanismo, Atelier Bow-Wow, Ateliers Jean Nouvel, COBE, Transform, BIG, Topotek1, Superflex, and by visual artist Jane Maria Petersen....

  14. Identification of Desirable Precursor Properties for Solution Precursor Plasma Spray (United States)

    Muoto, Chigozie K.; Jordan, Eric H.; Gell, Maurice; Aindow, Mark


    In solution precursor plasma spray chemical precursor solutions are injected into a standard plasma torch and the final material is formed and deposited in a single step. This process has several attractive features, including the ability to rapidly explore new compositions and to form amorphous and metastable phases from molecularly mixed precursors. Challenges include: (a) moderate deposition rates due to the need to evaporate the precursor solvent, (b) dealing on a case by case basis with precursor characteristics that influence the spray process (viscosity, endothermic and exothermic reactions, the sequence of physical states through which the precursor passes before attaining the final state, etc.). Desirable precursor properties were identified by comparing an effective precursor for yttria-stabilized zirconia with four less effective candidate precursors for MgO:Y2O3. The critical parameters identified were a lack of major endothermic events during precursor decomposition and highly dense resultant particles.

  15. Can Ni phosphides become viable hydroprocessing catalysts?

    Energy Technology Data Exchange (ETDEWEB)

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


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

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

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


    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.

  17. Dipyrrolyl Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts (United States)

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


    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

  18. Effect of precursor nature on the performance of palladium-cobalt electrocatalysts for direct methanol fuel cells (United States)

    Serov, Alexey; Nedoseykina, Tatyana; Shvachko, Oleg; Kwak, Chan

    The performance of platinum-free palladium-cobalt catalysts in oxygen reduction was investigated for a direct methanol fuel cell. The dependence of catalytic activity on precursor nature was determined for two classes of precursors; namely, palladium chloride and palladium nitrate. The nitrate precursor exhibits much higher catalytic performance than the chloride precursor. X-ray absorption fine structure (XAFS) spectra indicate that the structure of palladium catalyst prepared from nitrate is much closer to Pd 3Co structure that can explain high catalytic activity. The MEA prepared from the nitrate catalyst achieved the peak power density of 125 mW cm -2, which is much higher than 19 mW cm -2 measured on the cell prepared from the chloride catalyst.

  19. 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


    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.

  20. Pentaarylfullerenes as noncoordinating cyclopentadienyl anions

    NARCIS (Netherlands)

    Bouwkamp, Marco W.; Meetsma, Auke


    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.

  1. 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


    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....

  2. Photocatalytic Anion Oxidation and Applications in Organic Synthesis. (United States)

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


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

  3. Electrochemical catalyst recovery method (United States)

    Silva, Laura J.; Bray, Lane A.


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

  4. Anion exchange polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. Bound anionic states of adenine

    Energy Technology Data Exchange (ETDEWEB)

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


    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

  6. Dendronized Anionic Gold Nanoparticles: Synthesis, Characterization, and Antiviral Activity. (United States)

    Peña-González, Cornelia E; García-Broncano, Pilar; Ottaviani, M Francesca; Cangiotti, Michela; Fattori, Alberto; Hierro-Oliva, Margarita; González-Martín, M Luisa; Pérez-Serrano, Jorge; Gómez, Rafael; Muñoz-Fernández, M Ángeles; Sánchez-Nieves, Javier; de la Mata, F Javier


    Anionic carbosilane dendrons decorated with sulfonate functions and one thiol moiety at the focal point have been used to synthesize water-soluble gold nanoparticles (AuNPs) through the direct reaction of dendrons, gold precursor, and reducing agent in water, and also through a place-exchange reaction. These nanoparticles have been characterized by NMR spectroscopy, TEM, thermogravimetric analysis, X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, elemental analysis, and zeta-potential measurements. The interacting ability of the anionic sulfonate functions was investigated by EPR spectroscopy with copper(II) as a probe. Different structures and conformations of the AuNPs modulate the availability of sulfonate and thiol groups for complexation by copper(II). Toxicity assays of AuNPs showed that those produced through direct reaction were less toxic than those obtained by ligand exchange. Inhibition of HIV-1 infection was higher in the case of dendronized AuNPs than in dendrons.

  7. Effects of common inorganic anions on the rates of photocatalytic degradation of sodium dodecylbenzenesulfonate over illuminated titanium dioxide

    Institute of Scientific and Technical Information of China (English)


    Experiments were carried out to study the effects of several anions on the photocatalytic degradation rates of sodium dodecylbenzene sulphonate (DBS) with TiO2 as catalyst. The anions were added as Na2 SO4, NaNO3, NaCl, NaHCO3, NaH2 PO4 and Na3 PO4, and two levels of anion content, i.e. 12 mmol/L and 36 mmol/L in terms of Na+ , were studied. The results revealed that: Cl , SO24- , NO-3 and HCO3-retarded the rates of DBS degradation to different degrees; PO43 - increased the DBS degradation rate at low concentration and decreased the rate at high concentration; H2PO-4 accelerated the rate of DBS degradation. The mechanism of the effects of anions on DBS degradation was concluded as the following three aspects: anions compete for the radicals; anions are absorbed on the surface of catalyst and block the active site catalyst.

  8. Boron nitride: A high potential support for combustion catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Postole, G. [Institut de Recherches sur la Catalyse, CNRS, 69626 Villeurbanne Cedex (France); ' I.G.Murgulescu' Institute of Physical Chemistry of the Romanian Academy Spl. Independentei 202, 060041 Bucharest (Romania); Caldararu, M. [' I.G.Murgulescu' Institute of Physical Chemistry of the Romanian Academy Spl. Independentei 202, 060041 Bucharest (Romania); Ionescu, N.I. [' I.G.Murgulescu' Institute of Physical Chemistry of the Romanian Academy Spl. Independentei 202, 060041 Bucharest (Romania); Bonnetot, B. [Laboratoire des Multimateriaux et Interfaces, UMR CNRS 5615, bat Berthollet, UCB Lyon I, 69622 Villeurbanne Cedex (France); Auroux, A. [Institut de Recherches sur la Catalyse, CNRS, 69626 Villeurbanne Cedex (France)]. E-mail:; Guimon, C. [LCPM, 2 Av. President Angot, 64053 Pau Cedex 9 (France)


    High surface area BN powders have been prepared from different precursors to be used as supports for noble metal catalysts. The more suitable boron nitride powders were obtained using polytrichoroborazine, pTCB, as precursor, leading to a surface area higher than 150 m{sup 2}/g. The BN powders were characterized by XRD, XPS, TG, SEM and adsorption microcalorimetry measurements (aniline and ammonia). The preliminary results showed a remarkable stability of the BN supports, even in the presence of moisture. Palladium impregnation of the BN powders was performed using a classical method and the obtained catalysts exhibited a high dispersion with Pd particles of about 4 nm.

  9. {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.


    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)

  10. Amide-based Fluorescent Macrocyclic Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    ZENG, Zhen-Ya(曾振亚); XU, Kuo-Xi(徐括喜); HE, Yong-Bing(何永炳); LIU, Shun-Ying(刘顺英); WU, Jin-Long(吴进龙); WEI, Lan-Hua(隗兰华); MENG, Ling-Zhi(孟令芝)


    Two fluorescent anion receptors (1 and 2) based on amide macrocycle were synthesized and corresponding fluorescence quenching induced by anion complexation was observed in different degree. Receptors form 1: 1 complexes with anions by hydrogen bonding interactions. Receptor 1 bound anions in the order of F->Cl->H2PO4->CH3COO->>Br-, I- and receptor 2 showed high selectivity to F- over other anions.

  11. Towards the Rational Design of Nanoparticle Catalysts (United States)

    Dash, Priyabrat

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

  12. Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

    Institute of Scientific and Technical Information of China (English)


    Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H2 and characterized by X-ray diffraction (XRD),BET,temperature-programmed desorption of ammonia (NH3-TPD) and X-ray photoelectron spectroscopy (XPS).The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined.The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene,pyridine,dibenzothiophene,carbazole and diesel oil as the feed-stock.The TiO2,γ-Al2O3 supports and the Ni,Co promoters could remarkably increase and stabilize active W species on the catalyst surface.A suitable amount of Ni (3%-5%),Co (5%-7%) and V (1%-3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al2O3 catalyst.The WP/γ-Al2O3 catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO2 catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities.The Ni,Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al2O3 catalyst.The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al2O3 catalyst.In general,a support or promoter in the WP/γ-Al2O3 catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.

  13. 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


    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.

  14. Graphite oxide-intercalated anionic clay and its decomposition to graphene-inorganic material nanocomposites. (United States)

    Nethravathi, C; Rajamathi, Jacqueline T; Ravishankar, N; Shivakumara, C; Rajamathi, Michael


    A graphite oxide-intercalated anionic clay (nickel zinc hydroxysalt) has been prepared using the aqueous colloidal dispersions of negatively charged graphite oxide sheets and aminobenzoate-intercalated anionic clay layers as precursors. When the two colloidal dispersions are reacted, the interlayer aminobenzoate ions are displaced from the anionic clay and the negatively charged graphite oxide sheets are intercalated between the positively charged layers of the anionic clay. The thermal decomposition of the intercalated solid at different temperatures yields graphene-metal oxide/metal nanocomposites. Electron microscopic analysis of the composites indicates that the nanoparticles are intercalated between the layers of graphite in many regions of these solids although the graphite layers are largely exfoliated and not stacked well together.

  15. 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.; D'Souza, L.; Meyer, R.J.; Weckhuysen, B.M.; Regalbuto, J.R.


    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 mea

  16. N-doped graphitic layer encased cobalt nanoparticles as efficient oxygen reduction catalysts in alkaline media (United States)

    Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Nsabimana, Anaclet; Guo, Liping


    Nitrogen doped graphitic layer encased cobalt (N-C@Co) nanoparticles, as novel non-precious-metal catalysts for the oxygen reduction reaction (ORR), were fabricated by a facile method using cyanamide and cobalt nitrate as precursors. The N-C@Co catalysts exhibited comparable catalytic performance, better stability and improved methanol tolerance towards the ORR than those of the commercial Pt/C catalyst.Nitrogen doped graphitic layer encased cobalt (N-C@Co) nanoparticles, as novel non-precious-metal catalysts for the oxygen reduction reaction (ORR), were fabricated by a facile method using cyanamide and cobalt nitrate as precursors. The N-C@Co catalysts exhibited comparable catalytic performance, better stability and improved methanol tolerance towards the ORR than those of the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07571d

  17. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst (United States)

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


    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

  18. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst. (United States)

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


    1(st) 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 RuCl(2)(p-cymene)(PCy(3)) 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.

  19. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

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


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

  20. Anions in Nucleic Acid Crystallography. (United States)

    D'Ascenzo, Luigi; Auffinger, Pascal


    Nucleic acid crystallization buffers contain a large variety of chemicals fitting specific needs. Among them, anions are often solely considered for pH-regulating purposes and as cationic co-salts while their ability to directly bind to nucleic acid structures is rarely taken into account. Here we review current knowledge related to the use of anions in crystallization buffers along with data on their biological prevalence. Chloride ions are frequently identified in crystal structures but display low cytosolic concentrations. Hence, they are thought to be distant from nucleic acid structures in the cell. Sulfate ions are also frequently identified in crystal structures but their localization in the cell remains elusive. Nevertheless, the characterization of the binding properties of these ions is essential for better interpreting the solvent structure in crystals and consequently, avoiding mislabeling of electron densities. Furthermore, understanding the binding properties of these anions should help to get clues related to their potential effects in crowded cellular environments.

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

    NARCIS (Netherlands)

    den Breejen, Johan P.; Frey, Anne M.; Yang, Jia; Holmen, Anders; van Schooneveld, Matti M.; de Groot, Frank M. F.; Stephan, Odile; Bitter, Johannes H.; de Jong, Krijn P.


    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 cat

  2. 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


    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...

  3. A Concise Access to C2-Symmetric Chiral 4-Pyrrolidinopyridine Catalysts with Dual Functional Side Chains. (United States)

    Mishiro, Kenji; Takeuchi, Hironori; Furuta, Takumi; Kawabata, Takeo


    A practical method was developed for the preparation of a diastereomeric library of C2-symmetric chiral 4-pyrrolidinopyridine catalysts with dual amide side chains. Use of a racemic precursor is the key to the concise production of catalysts with diverse stereochemisty.

  4. 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


    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.

  5. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst. (United States)

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


    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.

  6. Foundation Flash Catalyst

    CERN Document Server

    Goralski, Greg


    This book offers an introduction to Flash Catalyst for designers with intermediate to advanced skills. It discusses where Catalyst sits within the production process and how it communicates with other programs. It covers all of the features of the Flash Catalyst workspace, teaching you how to create designs from scratch, how to build application designs and add functionality, and how to master the Catalyst/Flex workflow. * Introduces Flash Catalyst * Focuses on production process * Covers the interrelation between Flash Catalyst and Photoshop/Illustrator/Flex/Flash What you'll learn Starting f

  7. Collaboration between primitive cell membranes and soluble catalysts. (United States)

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


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

  8. Alternative Models of Iron and Cobalt Catalysts for Ethylene Oligomerization and Polymerization

    Institute of Scientific and Technical Information of China (English)

    Katrin; Wedeking; Sherrif; Adewuyi; Maliha; Asma; Igor; Vystorop; Saliu; Amolegbe; Elena; Novikova


    1 Results Great progresses have been made in the field of transition metal-based complexes as catalytic precursors for olefin oligomerization and polymerization,in which the core subjects will remain as "know and how" to develop novel catalysts both in academic and industrial consideration.The key advantage of iron and cobalt catalyst for ethylene polymerization is to produce vinyl-type polyethylenes.Therefore following the pioneering works of bis(imino) pyridyl iron and cobalt catalyst by Brookhart[1] ...

  9. Anion release and uptake kinetics: structural changes of layered 2-dimensional ZnNiHN upon uptake of acetate and chlorinated acetate anions. (United States)

    Machingauta, Cleopas; Hossenlopp, Jeanne M


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

  10. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Michael Rajamathi; Grace S Thomas; P Vishnu Kamath


    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 properties together with surface basicity making them materials of importance for many modern applications. In this article, we discuss many different ways of making anionic clays and compare and contrast the rich diversity of this class of materials with the better-known cationic clays.

  11. Porous polymers bearing functional quaternary ammonium salts as efficient solid catalysts for the fixation of CO2 into cyclic carbonates (United States)

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


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

  12. Anion binding in biological systems (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.


    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.

  13. 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: [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)


    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.

  14. 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


    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

  15. Pd Close Coupled Catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhong Hua SHI; Mao Chu GONG; Yao Qiang CHEN


    A catalyst comprised novel high surface area alumina support was prepared to control emission of automobiles. The results showed that prepared catalyst could satisfy the requirements of a high performance close coupled catalyst for its good catalytic activity at low temperature and good stability at high temperature.

  16. Synthesis and Photocatalytic Activity of TiO2/V2O5 Composite Catalyst Doped with Rare Earth Ions

    Institute of Scientific and Technical Information of China (English)


    TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange (MO) in aqueous solution. It is shown that the prepared catalyst is composed of anatase and rutile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce4+ present the best activity to MO.

  17. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

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


    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  18. Precursors of extreme increments

    CERN Document Server

    Hallerberg, S; Holstein, D; Kantz, H; Hallerberg, Sarah; Altmann, Eduardo G.; Holstein, Detlef; Kantz, Holger


    We investigate precursors and predictability of extreme events in time series, which consist in large increments within successive time steps. In order to understand the predictability of this class of extreme events, we study analytically the prediction of extreme increments in AR(1)-processes. The resulting strategies are then applied to predict sudden increases in wind speed recordings. In both cases we evaluate the success of predictions via creating receiver operator characteristics (ROC-plots). Surprisingly, we obtain better ROC-plots for completely uncorrelated Gaussian random numbers than for AR(1)-correlated data. Furthermore, we observe an increase of predictability with increasing event size. Both effects can be understood by using the likelihood ratio as a summary index for smooth ROC-curves.

  19. Gallium based low-interaction anions (United States)

    King, Wayne A.; Kubas, Gregory J.


    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.

  20. Catalysts based on PdO_ZrO2 in the hydrodechlorination reaction of chlorobenzene (United States)

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


    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.

  1. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad


    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.

  2. Efficient Amide Based Halogenide Anion Receptors

    Institute of Scientific and Technical Information of China (English)

    Hong Xing WU; Feng Hua LI; Hai LIN; Shou Rong ZHU; Hua Kuan LIN


    In this paper, we present the synthesis and anion recognition properties of the amide based phenanthroline derivatives 1, 2 and 3. In all cases 1:1 receptor: anion complexes were observed. The receptors were found to be selective for fluoride and chloride respectively over other putative anionic guest species.

  3. Binding Hydrated Anions with Hydrophobic Pockets. (United States)

    Sokkalingam, Punidha; Shraberg, Joshua; Rick, Steven W; Gibb, Bruce C


    Using a combination of isothermal titration calorimetry and quantum and molecular dynamics calculations, we demonstrate that relatively soft anions have an affinity for hydrophobic concavity. The results are consistent with the anions remaining partially hydrated upon binding, and suggest a novel strategy for anion recognition.

  4. PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design (United States)

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


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

  5. Precursor flares in OJ 287


    Pihajoki, P.; Valtonen, M.; Zola, S.; Liakos, A.; Drozdz, M.; Winiarski, M.; Ogloza, W.; Koziel-Wierzbowska, D.; Provencal, J.; Nilsson, K.; Berdyugin, A.; Lindfors, E.; Reinthal, R.; Sillanpää, A.; Takalo, L.


    We have studied three most recent precursor flares in the light curve of the blazar OJ 287 while invoking the presence of a precessing binary black hole in the system to explain the nature of these flares. Precursor flare timings from the historical light curves are compared with theoretical predictions from our model that incorporate effects of an accretion disk and post-Newtonian description for the binary black hole orbit. We find that the precursor flares coincide with the secondary black...

  6. Generation of nonlinear vortex precursors

    CERN Document Server

    Chen, Yue-Yue; Liu, Chengpu


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

  7. Perlite as a potential support for nickel catalyst in the process of sunflower oil hydrogenation (United States)

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


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

  8. Polymerization of anionic wormlike micelles. (United States)

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


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

  9. Laser Cooling of Molecular Anions

    CERN Document Server

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


    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.

  10. Hosting anions. The energetic perspective. (United States)

    Schmidtchen, Franz P


    Hosting anions addresses the widely spread molecular recognition event of negatively charged species by dedicated organic compounds in condensed phases at equilibrium. The experimentally accessible energetic features comprise the entire system including the solvent, any buffers, background electrolytes or other components introduced for e.g. analysis. The deconvolution of all these interaction types and their dependence on subtle structural variation is required to arrive at a structure-energy correlation that may serve as a guide in receptor construction. The focus on direct host-guest interactions (lock-and-key complementarity) that have dominated the binding concepts of artificial receptors in the past must be widened in order to account for entropic contributions which constitute very significant fractions of the total free energy of interaction. Including entropy necessarily addresses the ambiguity and fuzziness of the host-guest structural ensemble and requires the appreciation of the fact that most liquid phases possess distinct structures of their own. Apparently, it is the perturbation of the intrinsic solvent structure occurring upon association that rules ion binding in polar media where ions are soluble and abundant. Rather than specifying peculiar structural elements useful in anion binding this critical review attempts an illumination of the concepts and individual energetic contributions resulting in the final observation of specific anion recognition (95 references).

  11. Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces. (United States)

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


    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.

  12. Dimethylether production on zeolite catalysts activated by Cl-, F-and/or ultrasonication

    Institute of Scientific and Technical Information of China (English)

    Sameh M K Aboul-Fotouh; Noha A K Aboul-Gheit; Mona A Naghmash


    The chlorinated and fluorinated zeolite catalysts were prepared by the impregnation of zeolites ( H-ZSM-5, H-MOR or H-Y) using two halogen precursors ( ammonium chloride and ammonium fluoride ) in this study. The influence of ultrasonic irradiation was evaluated for optimizing both halogen precursors for production of dimethylether ( DME) via methanol dehydration in a fixed bed reactor. The catalysts were characterized by SEM, XRD, BET and NH3-TPD. The reaction conditions were temperatures from 100 to 300℃ and a WHSV =15. 9 h-1 . All halogenated catalysts show higher catalytic activities at all reaction temperatures studied. However, the halogenated zeolite catalysts prepared under ultrasonic irradiation show higher performance for DME formation. The chlorinated zeolite catalysts show higher activity and selectivity for DME production than the respective fluorinated versions.

  13. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan


    . 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.


    Energy Technology Data Exchange (ETDEWEB)

    Pihajoki, P.; Berdyugin, A.; Lindfors, E.; Reinthal, R.; Sillanpaeae, A.; Takalo, L. [Tuorla Observatory, Department of Physics and Astronomy, University of Turku, FI-21500 Piikkioe (Finland); Valtonen, M.; Nilsson, K. [Finnish Centre for Astronomy with ESO, University of Turku, FI-21500 Piikkioe (Finland); Zola, S.; Koziel-Wierzbowska, D. [Astronomical Observatory, Jagiellonian University, ul. Orla 171, PL-30-244 Krakow (Poland); Liakos, A. [Department of Astrophysics, Astronomy and Mechanics, University of Athens, GR 157 84 Zografos, Athens, Hellas (Greece); Drozdz, M.; Winiarski, M.; Ogloza, W. [Mount Suhora Observatory, Pedagogical University, ul. Podchorazych 2, PL-30-084 Krakow (Poland); Provencal, J. [Department of Physics and Astronomy, University of Delaware, Newark, DE 19716 (United States); Santangelo, M. M. M. [O.A.C. Osservatorio Astronomico di Capannori, Via di Valle, I-55060 Vorno, Capannori (Italy); Salo, H. [Department of Physical Sciences, University of Oulu, P.O. Box 3000, FI-90014 University of Oulu (Finland); Chandra, S.; Ganesh, S.; Baliyan, K. S., E-mail: [Astronomy and Astrophysics Division, Physical Research Laboratory, Ahmedabad 380009 (India); and others


    We have studied three most recent precursor flares in the light curve of the blazar OJ 287 while invoking the presence of a precessing binary black hole in the system to explain the nature of these flares. Precursor flare timings from the historical light curves are compared with theoretical predictions from our model that incorporate effects of an accretion disk and post-Newtonian description for the binary black hole orbit. We find that the precursor flares coincide with the secondary black hole descending toward the accretion disk of the primary black hole from the observed side, with a mean z-component of approximately z{sub c} = 4000 AU. We use this model of precursor flares to predict that precursor flare of similar nature should happen around 2020.96 before the next major outburst in 2022.

  15. Catalyst Alloys Processing (United States)

    Tan, Xincai


    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.

  16. Resin Catalyst Hybrids

    Institute of Scientific and Technical Information of China (English)

    S. Asaoka


    @@ 1Introduction: What are resin catalyst hybrids? There are typically two types of resin catalyst. One is acidic resin which representative is polystyrene sulfonic acid. The other is basic resin which is availed as metal complex support. The objective items of this study on resin catalyst are consisting of pellet hybrid, equilibrium hybrid and function hybrid of acid and base,as shown in Fig. 1[1-5].

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  18. Promotional effect of phosphorus doping on the activity of the Fe-N/C catalyst for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Hu, Yang; Zhu, Jianbin; Lv, Qing


    phosphate ester as a dopant in the synthesis, which introduces no change in catalyst morphologies and structures. The linked structure of phosphate ester cations with the nitrogen precursor, i.e., polyaniline chain, is favored for the evenly P doping of the catalyst, showing to a superior ORR activity...

  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


    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. New Trends in Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta


    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

  1. High catalytic activity and pollutants resistivity using Fe-AAPyr cathode catalyst for microbial fuel cell application


    Carlo Santoro; Alexey Serov; Claudia W. Narvaez Villarrubia; Sarah Stariha; Sofia Babanova; Kateryna Artyushkova; Schuler, Andrew J.; Plamen Atanassov


    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in ...

  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


    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. Cumene hydroperoxide hydrogenation over Pd/C catalysts. (United States)

    Zhu, Qing-cai; Shen, Ben-xian; Ling, Hao; Gu, Rong


    Pd/C catalysts were prepared by wet impregnation using K(2)PdCl(4) as precursor and their performance in hydrogenation of cumene hydroperoxide (CHP) was investigated. The catalytic activity was examined on the formaldehyde-reduced and on the hydrogen-reduced Pd/C catalysts. Results from XRD, TEM and CO chemisorption showed that reduction methods have a significant impact on the palladium particles size of resulting catalysts. Formaldehyde-reduced Pd/C catalyst has larger palladium particles than hydrogen-reduced Pd/C catalyst. Consequently, higher activity but lower selectivity to alpha-cumyl alcohol (CA) was obtained on formaldehyde-reduced Pd/C catalyst. Moreover, hydrogenation of CHP over hydrogen-reduced Pd/C catalyst can give similar CA selectivity to Na(2)SO(3) reduction process, an industrial process for CA production. High rate of CHP conversion and CA selectivity can be obtained at an elevated temperature and H(2) pressure. Kinetics studies revealed that CHP hydrogenation is zero-order for CHP concentration and the activation energy was calculated to be 13.6 kJ/mol.

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


    Lina Gan; Feng Guo; Jian Yu; Guangwen Xu


    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...

  5. Tunable electronic interactions between anions and perylenediimide. (United States)

    Goodson, Flynt S; Panda, Dillip K; Ray, Shuvasree; Mitra, Atanu; Guha, Samit; Saha, Sourav


    Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.

  6. Adsorption affinity of anions on metal oxyhydroxides (United States)

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


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

  7. Alloy catalyst material

    DEFF Research Database (Denmark)


    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...

  8. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)


    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...

  9. Reducible oxide based catalysts (United States)

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


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

  10. Magnetic catalyst bodies

    NARCIS (Netherlands)

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


    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 particles.

  11. Brillouin precursors in Debye media

    CERN Document Server

    Macke, Bruno


    We theoretically study the formation of Brillouin precursors in Debye media. We point out that the precursors are only visible at propagation distances such that the impulse response of the medium is essentially determined by the frequency-dependence of its absorption and is practically Gaussian. By simple convolution, we then obtain explicit analytical expressions of the transmitted waves generated by reference incident waves, distinguishing precursor and main signal by physical arguments. These expressions are in good agreement with the signals obtained in numerical or real experiments performed on water and explain some features of these signals that remained mysterious or unnoticed. In addition, we show quite generally that the shape of the Brillouin precursor appearing alone at large enough propagation distance and the law giving its amplitude as a function of this distance do not depend on the precise form of the incident wave but only on its integral properties. The incidence of a static conductivity o...

  12. A nickel iron diselenide-derived efficient oxygen-evolution catalyst (United States)

    Xu, Xiang; Song, Fang; Hu, Xile


    Efficient oxygen-evolution reaction catalysts are required for the cost-effective generation of solar fuels. Metal selenides have been reported as promising oxygen-evolution catalysts; however, their active forms are yet to be elucidated. Here we show that a representative selenide catalyst, nickel selenide, is entirely converted into nickel hydroxide under oxygen-evolution conditions. This result indicates that metal selenides are unstable during oxygen evolution, and the in situ generated metal oxides are responsible for their activity. This knowledge inspired us to synthesize nanostructured nickel iron diselenide, a hitherto unknown metal selenide, and to use it as a templating precursor to a highly active nickel iron oxide catalyst. This selenide-derived oxide catalyses oxygen evolution with an overpotential of only 195 mV for 10 mA cm-2. Our work underscores the importance of identifying the active species of oxygen-evolution catalysts, and demonstrates how such knowledge can be applied to develop better catalysts.

  13. Low metal loading catalysts used for the selective hydrogenation of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Badano, Juan; Lederhos, Cecilia; Quiroga, Monica; L' Argentiere, Pablo [Consejo Nacional de Investigaciones Cientificas y Tecnicas, Santa Fe (Argentina). Universidad Nacional del Litoral. Inst. de Investigaciones en Catalisis y Petroquimica; Coloma-Pascual, Fernando [Universidad de Alicante (Spain). Facultad de Ciencias. Servicios Tecnicos de Investigacion


    A series of Group VIII metal catalysts was obtained for the semi-hydrogenation of styrene. Catalysts were characterized by Hydrogen Chemisorption, TPR and XPS. Palladium, rhodium and platinum low metal loading prepared catalysts presented high activity and selectivity (ca. 98%) during the semi-hydrogenation of styrene, being palladium the most active catalyst. The ruthenium catalyst also presented high selectivity (ca. 98%), but the lowest activity. For the palladium catalyst, the influence of the precursor salt and of the reduction temperature on the activity and selectivity were studied. The following activity series was obtained: PdN-423 > PdCl-673 > PdCl-373> PtCl-673 > RhCl-673 >> RuCl-673. As determined by XPS, differences in activity could be attributed, at least in part, to electronic effects (author)

  14. Precursor effects on the morphology and crystallinity of manganese oxides and their catalytic application for methylene blue degradation (United States)

    Awaluddin, Amir; Agustina, Mutia; Aulia, Rizki Rilda; Muhdarina


    The cryptomelane-type manganese oxide catalysts have been prepared by sol-gel method based on the redox reaction between potassium permanganate and glucose or oxalic acid. These catalysts belong to a class of porous manganese oxides known as octahedral molecular sieves (OMS). The SEM results indicated that the marked difference between the morphology of the cyptomelanes produced from glucose and oxalic acid. The glucose precursor produces cotton-shaped morphology, whereas the oxalic acid precursor leads to the formation of the disk-like appearances. The XRD results indicated that the glucose precursor produces more crystalline cryptomelane than that of oxalic acid. The effect of catalyst dosage on methyelene blue degradation was evaluated. Dye-decomposing activity was proportional to the amount of catalyst used, increasing of the catalyst amount leads to higher degradation of methyelene blue at short period of reaction. With different crystalline structures and morphology appearances of the cyptomelanes, however, the total degradation of methylene blue is relatively the same at 120 minute of reaction time with catalyst amount of 100 mg.

  15. Ursodeoxycholic acid and superoxide anion

    Institute of Scientific and Technical Information of China (English)

    Predrag Ljubuncic; Omar Abu-Salach; Arieh Bomzon


    AIM: To investigate the ability of ursodeoxycholic acid (UDCA) to scavenge superoxide anion (O2-).METHODS: We assessed the ability of UDCA to scavenge (O2-) generated by xanthine-xanthine oxidase (X-XO) in a cell-free system and its effect on the rate of O2--induced ascorbic acid (AA) oxidation in hepatic post-mitochondrial supernatants.RESULTS: UDCA at a concentration as high as 1 mmol/Ldid not impair the ability of the X-XO system to generate O2-, but could scavenge O2- at concentrations of 0.5 and 1 mmol/L, and decrease the rate of AA oxidation at a concentration of 100 μmol/L.CONCLUSION: UDCA can scavenge O2-, an action that may be beneficial to patients with primary biliary cirrhosis.

  16. 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 L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid


    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.

  17. 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)


    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.

  18. Effect of anions on preparation of ultrafine α-Al2O3 powder

    Institute of Scientific and Technical Information of China (English)


    Ultrafine alumina power was obtained by calcining the precursor at 1 200 ℃C for 2 h, which was prepared by homogeneous precipitation method using aluminium salts and urea as raw materials. The effects of anions on the morphology, particle size, surface area and configuration of the precursors were studied. The results show that the reactions of urea with aluminium nitrate and aluminium chloride result in agglomerates gels with bad filtering performance, the morphology is fibrillar. Aluminium sulphate-urea reactions result in the direct formation of amorphous powders with good filtering performance, of which morphology are regular spherical particles with larger granularity and smaller surface area. The reaction of mutual compound of aluminium sulphate and aluminium nitrate with molar ratio of 40:60 with urea can produce precursor with good filtering performance, spherical morphology,and uniform granularity distribution in the particle size range of 2-3 μm.

  19. Vibrational Spectroscopy of Microhydrated Conjugate Base Anions

    NARCIS (Netherlands)

    Asmis, K. R.; Neumark, D. M.


    Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aeros

  20. Catalyst in Basic Oleochemicals

    Directory of Open Access Journals (Sweden)

    Eva Suyenty


    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: || or local:

  1. Kinetics of germanium nanowire growth by the vapor-solid-solid mechanism with a Ni-based catalyst

    Directory of Open Access Journals (Sweden)

    Shruti V. Thombare


    Full Text Available The kinetics of vapor-solid-solid (VSS Ge nanowire growth using a Ni-based catalyst were investigated to probe the rate-limiting step for this complex nanoscale crystal growth process. The effects of key parameters such as temperature and precursor partial pressure on the nanowire growth rate were studied in order to gain detailed insights into the growth kinetics. Two different regimes were observed for VSS growth of Ge nanowires as function of temperature. At higher temperatures (345 °C–375 °C, kinetics data suggest that mass transport of germane precursor to the catalyst surface is rate limiting. At lower temperatures (<345 °C, either surface reaction of the GeH4 precursor on the catalyst or incorporation of Ge into the nanowire across the wire/catalyst interface is rate limiting.

  2. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood


    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.


    DEFF Research Database (Denmark)


    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... 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...

  4. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand. (United States)

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


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

  5. Anion stripping as a general method to create cationic porous framework with mobile anions. (United States)

    Mao, Chengyu; Kudla, Ryan A; Zuo, Fan; Zhao, Xiang; Mueller, Leonard J; Bu, Xianhui; Feng, Pingyun


    Metal-organic frameworks (MOFs) with cationic frameworks and mobile anions have many applications from sensing, anion exchange and separation, to fast ion conductivity. Despite recent progress, the vast majority of MOFs have neutral frameworks. A common mechanism for the formation of neutral frameworks is the attachment of anionic species such as F(-) or OH(-) to the framework metal sites, neutralizing an otherwise cationic scaffolding. Here, we report a general method capable of converting such neutral frameworks directly into cationic ones with concurrent generation of mobile anions. Our method is based on the differential affinity between distinct metal ions with framework anionic species. Specifically, Al(3+) is used to strip F(-) anions away from framework Cr(3+) sites, leading to cationic frameworks with mobile Cl(-) anions. The subsequent anion exchange with OH(-) further leads to a porous network with mobile OH(-) anions. New materials prepared by anion stripping can undergo ion exchange with anionic organic dyes and also exhibit much improved ionic conductivity compared to the original unmodified MOFs.


    Energy Technology Data Exchange (ETDEWEB)

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


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

  7. Catalyst for microelectromechanical systems microreactors (United States)

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


    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.

  8. Epoxidation catalyst and process (United States)

    Linic, Suljo; Christopher, Phillip


    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.

  9. Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, July--September 1993

    Energy Technology Data Exchange (ETDEWEB)

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


    Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts can be superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. The primary objective of this research is to explore novel bimetallic dispersed catalysts from heterometallic molecular precursors, that can be used in low concentrations but exhibit high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. This quarterly report describes the preparation of two precursors. The first is a heterometallic complex consisting of two transition metals, Mo and Ni, and sulfur in a single molecule synthesized. The second is a thiocubane type cluster consisting of iron and sulfur.

  10. A chameleon catalyst for nonheme iron-promoted olefin oxidation. (United States)

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence


    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  11. New Catalysts for ROMP

    Institute of Scientific and Technical Information of China (English)

    H. Berke; C. Frech; A. Lhamazares; O. Blacque; H.W. Schmalle; C. Adlhart; P. Chen


    @@ 1Introduction Ring Opening Metathesis Polymerization (ROMP) is based on the olefin metathesis reaction, which requires transition metal catalysts. Mainly molybdenum, tungsten and ruthenium based catalysts have up to now been used. The "in-between" metal rhenium was only rarely applied in olefin metathesis reactions, and not at all in ROMP processes.We have found that cationic phosphine substituted dinitrosyl rhenium complexes[1]1a and 1b effectively catalyze ROMP of norbonene, dicyclopentadiene and of cyclooctene. See Fig. 1.

  12. Effect of Impregnation Sequence on Propane Dehydrogenation Performance of PtSnNa/ZSM-5 Catalyst

    Institute of Scientific and Technical Information of China (English)

    Liu Hui; Zhou Yuming; Zhang Yiwei; Sheng Xiaoli; Zhang Zewu; Zhou Shijiang


    The effects of the sequence for impregnation of metal precursors on the performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation to propene were studied in this paper. Some methods such as XRD, TPDA,BET, H2-TPR, XPS, ICP, TEM and hydrogen chemisorption were used to characterize the catalysts. The structure of ZSM-5 zeolite was not destroyed by the introduction of metal components. Meanwhile the different impregnation sequence of metal precursors could affect the behavior of Sn4+ species entering the ZSM-5 channel, and the interaction between platinum and tin species, as well as the degree for reduction of Pt and Sn components. As a result, the prepared catalysts exhibited different reac-tion activity and selectivity. Compared with the co-impregnation treated catalyst, the catalysts prepared by the sequential impregnation method showed better catalytic activity in propane dehydrogenation, especially the one prepared through im-pregnation with tin precursor at ifrst. Finally, a model for the effect of impregnation sequence on the distribution of Pt and Sn species in PtSnNa/ZSM-5 catalyst was proposed.

  13. Anion conductance selectivity mechanism of the CFTR chloride channel. (United States)

    Linsdell, Paul


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

  14. Ni-Cu Hydrotalcite-Derived Mixed Oxides as Highly Selective and Stable Catalysts for the Synthesis of β-Branched Bioalcohols by the Guerbet Reaction. (United States)

    Hernández, Willinton Y; De Vlieger, Kevin; Van Der Voort, Pascal; Verberckmoes, An


    A series of Ni-Cu hydrotalcite-derived mixed oxides have been synthesized and evaluated as heterogeneous catalysts for the dimerization of linear aliphatic alcohols to afford β-branched Guerbet alcohols. The use of the hydrotalcite-structured catalyst precursor highly favors the catalyst stability. This Cu/Ni catalyst has an enhanced reducibility of Ni(2+) species under reaction conditions, favoring the hydrogen transfer and hydrogenation capacity of the catalyst system. Catalytic results are reported for C8 , mixed C8 /C10 , and C18 alcohol feeds, with full conversions and Guerbet product purities of 72.5-96 %.

  15. Anion photoelectron imaging spectroscopy of glyoxal (United States)

    Xue, Tian; Dixon, Andrew R.; Sanov, Andrei


    We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

  16. Trending analysis of precursor events

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Norio [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment


    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)

  17. PAGOSA Sample Problem. Elastic Precursor

    Energy Technology Data Exchange (ETDEWEB)

    Weseloh, Wayne N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Clancy, Sean Patrick [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    A PAGOSA simulation of a flyer plate impact which produces an elastic precursor wave is examined. The simulation is compared to an analytic theory for the Mie-Grüneisen equation of state and an elastic-perfectly-plastic strength model.

  18. Session 4: HDS, HDN and HYD assisted by ultrasound using formic acid as hydrogen precursor

    Energy Technology Data Exchange (ETDEWEB)

    Scott Carlos, E.; Bolivar, C.; Grobas, J. [Universidad Central de Venezuela, Centro de Catalisis Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Caracas (Venezuela)


    The study of chemical effects of ultrasound is a rapidly growing research area, and its use in heavy crude oil upgrading has been explored. In this work, hydrogenation of cyclohexene and biphenyl, hydrodesulfurization of benzothiophene and hydro-denitrogenation of quinoline, in the presence of a hydrogen precursor, a Pd/C catalyst and ultrasound irradiation was studied. It was found, that the use of formic acid as hydrogen precursor in presence of ultrasonic irradiation was an effective system to promote hydrogenation of cyclohexene (98%) and biphenyl (21%), desulfurization of benzothiophene (18%) and hydrogenation of quinoline (19%), at very mild conditions, i.e. ambient temperature and pressure. (authors)

  19. The selective hydrogenation of crotonaldehyde over bimetallic catalysts

    Energy Technology Data Exchange (ETDEWEB)

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


    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.


    Energy Technology Data Exchange (ETDEWEB)

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


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

  1. Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

    DEFF Research Database (Denmark)

    Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann


    was successfully prepared on a gram scale by using a hydrothermal-based route, purification of biphasic M1-M2 (M2 phase - ICSD 55098) oxide systems, and an innovative approach utilizing a superheated water vapor treatment of calcined precursors. The influence of the preparation technique on the particle morphology...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

  2. Influence of preparation method on performance of a metal supported perovskite catalyst for combustion of methane

    Institute of Scientific and Technical Information of China (English)

    翟彦青; 熊杰明; 李翠清; 徐新; 罗国华


    A different method was employed for the preparation of a metal supported perovskite catalyst for the catalytic combustion of methane.The prepared metallic catalysts were characterized by means of X-ray diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and also by ultrasonic and thermal shock tests and catalytic activity.It was found that the process factors during the preparation,e.g.the preparation of the catalyst precursor and the coating slurry,the calcination te...

  3. 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, V.; Rosace, G.


    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 mix

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

    DEFF Research Database (Denmark)

    Glogowska, Edyta; Dyrda, Agnieszka; Cueff, Anne


    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...

  5. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    intrinsic factors and solvent effects is the enhanced reactivity of α-nucleophiles – nucleophiles with a lone-pair adjacent to the attacking site – referred to as the α-effect. This thesis concerns the reactivity of microsolvated anions and in particular how the presence of a single solvent molecule affects...... the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  6. Renal elimination of organic anions in cholestasis

    Institute of Scientific and Technical Information of China (English)

    Adriana Mónica Tortes


    The disposition of most drugs is highly dependent on specialized transporters.OAT1 and OAT3 are two organic anion transporters expressed in the basolateral membrane of renal proximal tubule cells,identified as contributors to xenobiotic and endogenous organic anion secretion.It is well known that cholestasis may cause renal damage.Impairment of kidney function produces modifications in the renal elimination of drugs.Recent studies have demonstrated that the renal abundance of OAT1 and OAT3 plays an important role in the renal elimination of organic anions in the presence of extrahepatic cholestasis.Time elapsed after obstructive cholestasis has an important impact on the regulation of both types of organic anion transporters.The renal expression of OAT1 and OAT3 should be taken into account in order to improve pharmacotherapeutic efficacy and to prevent drug toxicity during the onset of this hepatic disease.

  7. 以类水滑石为前驱体的Cu/Zn/Al/(Zr)/(Y)催化剂制备及其催化CO2加氢合成甲醇的性能%Preparation of Cu/Zn/Al/(Zr)/(Y) Catalysts from Hydrotalcite-Like Precursors and Their Catalytic Performance for the Hydrogenation of CO2 to Methanol

    Institute of Scientific and Technical Information of China (English)

    高鹏; 李枫; 赵宁; 王慧; 魏伟; 孙予罕


    Cu/Zn/Al/(Zr)/(Y) hydrotalcite-like compounds with Cu:Zn:Al:Zr:Y atomic ratios of 2:1:1:0:0, 2:1:0.8:0.2:0, 2:1:0.8:0:0.2, and 2:1:0.8:0.1:0.1 were prepared using the coprecipitation method. The mixed oxides were then obtained by the calcination of the precursors at 500 °C in air, and subsequently evaluated in terms of their catalytic performance for the synthesis of methanol from the hydrogenation of CO2. The as-prepared samples were characterized by X-ray diffraction (XRD), thermogravimetric (TG) analysis, N2 adsorption, reactive N2O adsorption, H2 temperature-programmed reduction (H2-TPR), and H2/CO2 temperature-programmed desorption (H2/CO2 TPD) techniques. The results of these analyses showed that the BET specific surface area increased significantly with the introduction of Zr and Y, which was related to the amount of H2O and CO2 evolved from the precursors during calcination. The Cu specific surface area and Cu dispersion properties increased in the order of Cu/Zn/Alcatalysts for the hydrogenation of CO2 revealed that the CO2 conversion was dependent on the Cu specific surface area, and the CH3OH selectivity increased linearly as the proportion of strongly basic sites increased. The introduction of Zr and Y therefore favored the production of methanol and the maximum CH3OH yield was obtained over the Cu/Zn/Al/Zr/Y catalyst.%采用共沉淀法合成了Cu:Zn:Al:Zr:Y原子比分别为2:1:1:0:0、2:1:0.8:0.2:0、2:1:0.8:0:0.2和2:1:0.8:0.1:0.1的Cu/Zn/Al/(Zr)/(Y)类水滑石化合物.将前驱体材料在空气中500°C焙烧后得到复合金属氧化物,并将其用于CO2加氢合成甲醇反应.采用X射线衍射(XRD)、热重(TG)分析、N2吸附、氧化亚氮(N2O)反应吸附

  8. Fluorescence-lifetime-based sensors for anions (United States)

    Teichmann, Maria; Draxler, Sonja; Kieslinger, Dietmar; Lippitsch, Max E.


    Sensing of anions has been investigated using the fluorescence decaytime as the information carrier. The sensing mechanism is based on the coextraction of an anion and a proton, and the presence of a fluorophore with a rather long fluorescence decaytime inside the membrane to act as a pH indicator. The relevant theory is discussed shortly. As an example a sensor for nitrate is shown, and the influence of ionic additives on the working function has been investigated.

  9. MgO-SBA-15 Supported Pd-Pb Catalysts for Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate☆

    Institute of Scientific and Technical Information of China (English)

    Li Jiang; Yanyan Diao; Junxing Han; Ruiyi Yan; Xiangping Zhang; Suojiang Zhang


    Novel MgO–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein (MAL) with methanol to methyl methacrylate (MMA). The MgO–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The MgO–SBA-15 sup-ports and Pd–Pb/MgO–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of MgO improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3Pb particles on magnesia-modified Pd–Pb/MgO–SBA-15 catalysts was smal er than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/MgO–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/MgO–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by MgO, which led to the different Pd3Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.

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

    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Castillon, F.F.; Bodganchikova, N. [Centro de Investigacion Cientifica y de Educacion Superior, Ensenada (Mexico); Fuentes, S.; Avalos, M. [Univ. Nacional Autonoma de Mexico, Ensenada (Mexico). Inst. de Fisica


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

  12. Heterocyclic Anions of Astrobiological Interest (United States)

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


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

  13. Heterocyclic anions of astrobiological interest

    Energy Technology Data Exchange (ETDEWEB)

    Cole, Callie A.; Demarais, Nicholas J.; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309 (United States); Yang, Zhibo [Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK 73019 (United States); Snow, Theodore P., E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Department of Astrophysical and Planetary Sciences, 391 UCB, University of Colorado, Boulder, CO 80309 (United States)


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

  14. The direct formate fuel cell with an alkaline anion exchange membrane (United States)

    Bartrom, Amy M.; Haan, John L.


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

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

    DEFF Research Database (Denmark)

    Pedersen, Martin Holst Friborg; Baun, Michael


    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 hy...... hydrogenation chemistry with the use of a heterogeneous palladium catalyst and carrier-free tritium gas on a tritium manifold system....

  16. Supported organoiridium catalysts for alkane dehydrogenation (United States)

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


    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.

  17. Precursor polymer compositions comprising polybenzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.


    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.

  18. The Innate Lymphoid Cell Precursor. (United States)

    Ishizuka, Isabel E; Constantinides, Michael G; Gudjonson, Herman; Bendelac, Albert


    The discovery of tissue-resident innate lymphoid cell populations effecting different forms of type 1, 2, and 3 immunity; tissue repair; and immune regulation has transformed our understanding of mucosal immunity and allergy. The emerging complexity of these populations along with compounding issues of redundancy and plasticity raise intriguing questions about their precise lineage relationship. Here we review advances in mapping the emergence of these lineages from early lymphoid precursors. We discuss the identification of a common innate lymphoid cell precursor characterized by transient expression of the transcription factor PLZF, and the lineage relationships of innate lymphoid cells with conventional natural killer cells and lymphoid tissue inducer cells. We also review the rapidly growing understanding of the network of transcription factors that direct the development of these lineages.

  19. Neutral pyrimidine C-H donor as anion receptor

    Institute of Scientific and Technical Information of China (English)

    袁迎雪; 吴娜娜; 韩逸飞; 宋相志; 王洪波


    Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and 1H NMR titration experiments. DFT calculations provided some information for anion recognition. It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl−.

  20. Soluble Precursor Route to Polyanilines (United States)


    condensation were not successful, but further work produced polymer under the following conditions: Synthesis Diketone I (2.40 g, 10.0 mmol) in 10 mL...goal of producing a processible form of the conducting polymer polyaniline (PANI), the Phase I program concentrated on development of the synthesis of...extension of the original research to a Phase II effort. Diketone - Diamine Polycondensation Towards a Soluble PAni Precursor To achieve the

  1. 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;


    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...

  2. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions. (United States)

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


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

  3. 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:; Lupu, Nicoleta [National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050 Iasi (Romania)


    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.

  4. Z-Selective ethenolysis with a ruthenium metathesis catalyst: experiment and theory. (United States)

    Miyazaki, Hiroshi; Herbert, Myles B; Liu, Peng; Dong, Xiaofei; Xu, Xiufang; Keitz, Benjamin K; Ung, Thay; Mkrtumyan, Garik; Houk, K N; Grubbs, Robert H


    The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.

  5. Synthesis of 5'-O-DMT-2'-O-TBS Mononucleosides Using an Organic Catalyst. (United States)

    Lee, Sunggi; Blaisdell, Thomas P; Kasaplar, Pinar; Sun, Xixi; Tan, Kian L


    This unit describes a highly effective method to produce 5'-O-DMT-2'-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2'- and 3'-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps, starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2'-O-TBS protected mono-nucleosides, U, A(Bz), G(Ib), and C(Ac), were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol in the preparation of monomers useful for automated synthesis of RNA.

  6. Effect of the functional groups of carbon on the surface and catalytic properties of Ru/C catalysts for hydrogenolysis of glycerol (United States)

    Gallegos-Suarez, E.; Pérez-Cadenas, M.; Guerrero-Ruiz, A.; Rodriguez-Ramos, I.; Arcoya, A.


    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 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.

  7. Fuel cell catalyst degradation

    DEFF Research Database (Denmark)

    Arenz, Matthias; Zana, Alessandro


    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...

  8. Aerogel derived catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, J. G., LLNL


    Aerogels area class of colloidal materials which have high surface areas and abundant mesoporous structure. SiO{sub 2} aerogels show unique physical, optical and structural properties. When catalytic metals are incorporated in the aerogel framework, the potential exists for new and very effective catalysts for industrial processes. Three applications of these metal-containing SiO{sub 2} aerogels as catalysts are briefly reviewed in this paper--NO{sub x} reduction, volatile organic compound destruction, and partial oxidation of methane.

  9. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  10. Mesoporous molecular sieve catalysts

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane

    be used as solid acid catalysts but can also be used as a size-selective matrix. It was shown that it is possible to encapsulate 1-2 nm sized gold nanoparticles by silicalite-1 or ZSM-5 zeolite crystals thereby forming a sintering-stable and substrate size-selective oxidation catalyst. After carrying out...... calcination experiments, both in situ and ex situ indicated that the gold nanoparticles embedded in the crystals were highly stable towards sintering. The catalytic tests proved that the embedded gold nanoparticles were active in selective aldehyde oxidation and were only accessible through the micropores...

  11. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

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

    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...

  12. Analysis of oxyhalide disinfection by-products and other anions of interest in drinking water by ion chromatography. (United States)

    Hautman, D P; Bolyard, M


    The US Environmental Protection Agency is developing regulations for various drinking water disinfection by-products (DBPs). This effort involves developing analytical methods for the DBPs formed as a result of different disinfection treatments and collecting occurrence data for these species. Ion chromatography is one method being used to analyze drinking water samples for the following inorganic DBPs: chlorite, chlorate and bromate. These anions, however, are difficult to separate from common interfering anions of chloride, carbonate and nitrate. A method is therefore presented by which tetraborate/boric acid is used to separate these anions. Method detection limits of the order of 10 micrograms/l, using conductivity and UV detection were obtained. Stability studies of chlorite showing the effectiveness of ethylenediamine as a preservative and summary data for an occurrence of nitrite, nitrate and the DBP precursor bromide are presented.

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

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


    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.

  14. Theoretical Study on Catalyst Activation of Palladacycles in Heck Reaction

    Institute of Scientific and Technical Information of China (English)

    WANG Chen; FU Yao; LI Zhe; GUO Qing-Xiang


    A computational study with the B3PW91 density functional theory was carried out on the activation process of palladacycles as catalysts in the Heck reaction.Two possible pathways (i.e.anion reductive cleavage of the Pd-C bond,and olefin insertion into the Pd-C bond followed by β-H elimination)were taken into consideration.Computational results indicate that the palladacycles are activated via olefin insertion into the Pd-C bond followed by β-H elimination in the reaction conditions.

  15. Molecular metal catalysts on supports: organometallic chemistry meets surface science. (United States)

    Serna, Pedro; Gates, Bruce C


    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

  16. Studies of anions sorption on natural zeolites. (United States)

    Barczyk, K; Mozgawa, W; Król, M


    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

  17. Chemical imaging of Fischer-Tropsch catalysts under operating conditions (United States)

    Price, Stephen W. T.; Martin, David J.; Parsons, Aaron D.; Sławiński, Wojciech A.; Vamvakeros, Antonios; Keylock, Stephen J.; Beale, Andrew M.; Mosselmans, J. Frederick W.


    Although we often understand empirically what constitutes an active catalyst, there is still much to be understood fundamentally about how catalytic performance is influenced by formulation. Catalysts are often designed to have a microstructure and nanostructure that can influence performance but that is rarely considered when correlating structure with function. Fischer-Tropsch synthesis (FTS) is a well-known and potentially sustainable technology for converting synthetic natural gas (“syngas”: CO + H2) into functional hydrocarbons, such as sulfur- and aromatic-free fuel and high-value wax products. FTS catalysts typically contain Co or Fe nanoparticles, which are often optimized in terms of size/composition for a particular catalytic performance. We use a novel, “multimodal” tomographic approach to studying active Co-based catalysts under operando conditions, revealing how a simple parameter, such as the order of addition of metal precursors and promoters, affects the spatial distribution of the elements as well as their physicochemical properties, that is, crystalline phase and crystallite size during catalyst activation and operation. We show in particular how the order of addition affects the crystallinity of the TiO2 anatase phase, which in turn leads to the formation of highly intergrown cubic close-packed/hexagonal close-packed Co nanoparticles that are very reactive, exhibiting high CO conversion. This work highlights the importance of operando microtomography to understand the evolution of chemical species and their spatial distribution before any concrete understanding of impact on catalytic performance can be realized. PMID:28345057

  18. Carbon Nanotubes Supported Pt-Ru-Ni as Methanol Electro-Oxidation Catalyst for Direct Methanol Fuel Cells

    Institute of Scientific and Technical Information of China (English)

    Fei Ye; Shengzhou Chen; Xinfa Dong; Weiming Lin


    Carbon nanotubes (CNTs) supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction (XRD) and energy dispersive X-ray (EDX) analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy (EIS), linear sweep voltammetries (LSV), and chronoamperometry (CA). The results show that the catalysts exhibit face-centered cubic (fcc) structure.The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.

  19. The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst (United States)

    Du, Xuesen; Yang, Guangpeng; Chen, Yanrong; Ran, Jingyu; Zhang, Li


    Alkali metals are poisonous to the metal oxide catalyst for NO removal. The chemical configuration of alkali containing substance and interacting temperature can affect the poisoning profile. A computational method based on Frontier Molecular Orbital analysis was proposed to determine the reacting behavior of various alkali-containing substances with SCR catalyst. The results reveal that the poisoning reactivities of various substances can be ranked as: E (MOH) > E (M2SO4) > E(MCl) > E(MNO3) > E(MHSO4). The experimental activity tests of the catalysts calcined at stepped temperatures show that NaOH can react with the catalyst below 200 °C. NaCl and NaNO3 start to react with the catalyst at a temperature between 300 and 400 °C. Unlike MOH, MCl and MNO3, which can produce volatile or decomposable species for the anions after reacting with the catalyst, M2SO4 and MHSO4 will leave both cations and anions on the catalyst surface. The sulfate ions left on the catalyst can generate active acid sites for NH3 adsorption. The experimental results also show that Na2SO4 and NaHSO4 will not lower the NO conversion. The after-reaction influences of various alkali metals were studied using theoretical and experimental methods. The theoretical results show that the acidity decreases with doping of alkali metal. Experiments show a consistent result that the NO conversion decreases as undoped >LiCl > NaCl > KCl.

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

    DEFF Research Database (Denmark)


    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....

  1. Isatinphenylsemicarbazones as efficient colorimetric sensors for fluoride and acetate anions - anions induce tautomerism. (United States)

    Jakusová, Klaudia; Donovalová, Jana; Cigáň, Marek; Gáplovský, Martin; Garaj, Vladimír; Gáplovský, Anton


    The anion induced tautomerism of isatin-3-4-phenyl(semicarbazone) derivatives is studied herein. The interaction of F(-), AcO(-), H2PO4(-), Br(-) or HSO4(-) anions with E and Z isomers of isatin-3-4-phenyl(semicarbazone) and N-methylisatin-3-4-phenyl(semicarbazone) as sensors influences the tautomeric equilibrium of these sensors in the liquid phase. This tautomeric equilibrium is affected by (1) the inter- and intra-molecular interactions' modulation of isatinphenylsemicarbazone molecules due to the anion induced change in the solvation shell of receptor molecules and (2) the sensor-anion interaction with the urea hydrogens. The acid-base properties of anions and the difference in sensor structure influence the equilibrium ratio of the individual tautomeric forms. Here, the tautomeric equilibrium changes were indicated by "naked-eye" experiment, UV-VIS spectral and (1)H NMR titration, resulting in confirmation that appropriate selection of experimental conditions leads to a high degree of sensor selectivity for some investigated anions. Sensors' E and Z isomers differ in sensitivity, selectivity and sensing mechanism. Detection of F(-) or CH3COO(-) anions at high weakly basic anions' excess is possible.

  2. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie


    Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold–titania c...... new and environmentally benign routes to caprolactam and cyclohexanone oxime, both of which are precursors for nylon-6....

  3. Impregnation of mesoporous silica for catalyst preparation studied with differential scanning calorimetry

    NARCIS (Netherlands)

    Eggenhuisen, T.M.; van Steenbergen, M.J.; Talsma, H.; de Jongh, P.E.; de Jong, K.P.


    Aqueous impregnation of mesoporous silica as a first step in catalyst preparation was studied to investigate the distribution of the metal-precursor solution over the support. The degree of pore-filling after impregnation was determined using the freezing point depression of confined liquids. A sepa

  4. La/Sr-based perovskites as soot oxidation catalysts for Gasoline Particulate Filters

    NARCIS (Netherlands)

    Hernández, W. Y.; Tsampas, M. N.; Zhao, C.; Boréave, A.; Bosselet, F.; Vernoux, P.


    La0.6Sr0.4BO3 type-perovskites (with B = Fe, Mn or Ti) were synthesized by a complex route from the thermal decomposition of the chelated nitrate precursors, as soot oxidation catalysts under low oxygen partial pressures. The nature of the B-site cation modifies the morphology, the structural symmet

  5. PKP precursors : Implications for global scatterers

    NARCIS (Netherlands)

    Waszek, Lauren; Thomas, Christine; Deuss, Arwen


    Precursors to the core phase PKP are generated by scattering of seismic energy from heterogeneities in the mantle. Here we examine a large global data set of PKP precursors in individual seismograms and array data, to better understand scattering locations. The precursor amplitudes from individual s

  6. Methanol and methyl fuel catalysts. Final technical report, September 1980-August 1983

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.; Simmons, G.W.


    Copper-based catalysts for alcohol synthesis were prepared, tested for catalytic activity and selectivity, and characterized. These catalysts include Cu/ZnO, Cu/Co/ZnO, Cu/Co/Cr/sub 2/O/sub 3/, Cu/Co/Cr/sub 2/O/sub 3//K/sub 2/O, and Cu/ZnO/KOH. The chromia-containing catalysts exhibited a low activity and selectivity, while the Cu/ZnO catalyst was verified to be a very active and selective methanol synthesis catalyst. Cobalt imparted a methanation function to the catalysts, while potassium suppressed the activity and the selectivity. Over the quaternary catalyst, higher pressure and lower GHSV enhanced the selectivity to higher alcohols. Low concentrations of carbon dioxide in H/sub 2//CO synthesis gas over Cu/ZnO catalysts promote methanol synthesis, while at high concentrations it behaves as a retardant of the synthesis. The water gas shift reaction readily proceeds over the Cu/ZnO catalyst. Analogous to the CO/sub 2/ effect, the presence of water in the synthesis gas has a profound effect on the synthesis of methanol. The Cu/ZnO catalyst is a good hydrogenation catalyst. Olefins, aldehydes, and acids are hydrogenated at a faster rate than CO is hydrogenated to methanol, but aromatics are hydrogenated at slower rates. Chemical trapping of the intermediates on these surface sites with amines demonstrates that a kinetically significant intermediate in methanol synthesis is a surface formyl or hydroxycarbene species. These species can be formed from synthesis gas or by alcohols in the reactant stream, and they readily alkylate amines in the reactant gas stream. Over an Fe/Cu/ZnO catalyst, amines inhibit the production of alcohols by trapping the precursor intermediates, while changing the hydrocarbon selectivity from paraffins to predominantly olefins. 68 references, 9 figures, 25 tables.

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

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon


    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.

  8. Templating Routes to Supported Oxide Catalysts by Design

    Energy Technology Data Exchange (ETDEWEB)

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


    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

  9. Nanopore and nanoparticle catalysts. (United States)

    Thomas, J M; Raja, R


    The design, atomic characterization, performance, and relevance to clean technology of two distinct categories of new nanocatalysts are described and interpreted. Exceptional molecular selectivity and high activity are exhibited by these catalysts. The first category consists of extended, crystallographically ordered inorganic solids possessing nanopores (apertures, cages, and channels), the diameters of which fall in the range of about 0.4 to about 1.5 nm, and the second of discrete bimetallic nanoparticles of diameter 1 to 2 nm, distributed more or less uniformly along the inner walls of mesoporous (ca. 3 to 10 nm diameter) silica supports. Using the principles and practices of solid-state and organometallic chemistry and advanced physico-chemical techniques for in situ and ex situ characterization, a variety of powerful new catalysts has been evolved. Apart from those that, inter alia, simulate the behavior of enzymes in their specificity, shape selectivity, regio-selectivity, and ability to function under ambient conditions, many of these new nanocatalysts are also viable as agents for effecting commercially significant processes in a clean, benign, solvent-free, single-step fashion. In particular, a bifunctional, molecular sieve nanopore catalyst is described that converts cyclohexanone in air and ammonia to its oxime and caprolactam, and a bimetallic nanoparticle catalyst that selectively converts cyclic polyenes into desirable intermediates. Nanocatalysts in the first category are especially effective in facilitating highly selective oxidations in air, and those in the second are well suited to effecting rapid and selective hydrogenations of a range of organic compounds.

  10. Hydrogen evolution reaction catalyst (United States)

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


    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.

  11. Heterogeneous chromium catalysts

    NARCIS (Netherlands)


    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based silica-c

  12. Deactivation of Oxidation Catalysts (United States)


    Levenspiel (Reference 10) have proposed an equivalent general expression of the form dS _KST (4) dtk to account for deactivation due to catalyst pore...Voorhies, A., IEC, 1954, vol. 37, p. 318. 10. Szepe, S., and 0. Levenspiel , Proc. 4th Europ. Symp. Chem. React. Eng., Pergamon Press, p. 265. 11. U.S

  13. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  14. Catalysts for Environmental Remediation

    DEFF Research Database (Denmark)

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


    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...

  15. 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


    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.

  16. Characterization of haloacetic acid precursors in source water. (United States)

    Kanokkantapong, Vorapot; Marhaba, Taha F; Pavasant, Prasert; Panyapinyophol, Bunyarit


    Raw water from the Bangkok (Thailand) main municipal water supply canal was examined for its natural organic composition by fractionation with adsorption resins. DAX-8 resin was the first resin employed to fractionate the hydrophobic fractions. Fractionation at neutral pH resulted in the separation of the hydrophobic neutral components; at a high pH level (approx. 10) separation of the hydrophobic base components occurred; and at a low pH level (approx. 2) the hydrophobic acid components were separated. AG-MP-50 cationic resin was then used to separate the hydrophilic base components, and WA-10, a weak anionic resin, was applied finally to fractionate the hydrophilic acid and neutral components. Subsequently, each fraction was tested for its chlorine disinfection by-product (DBP) formation potential. The HAA formation tests demonstrated that the various organic fractions had different reactivity levels for the formation of haloacetic acids (HAAs). For this source water, the hydrophilic neutral fraction dominated over the other five fractions in being the main organic component and the most significant precursor of HAAs formation. On the other hand, in terms of specific HAA formation potential (FP), the hydrophobic and hydrophilic base fractions were the most reactive precursors to the formation of HAAs. In all cases, the quantity of HAAs formed depended linearly upon the amount of organic constituents in the water sample.

  17. Unveiling carbon dimers and their chains as precursor of graphene growth on Ru(0001) (United States)

    Gao, Min; Zhang, Yan-Fang; Huang, Li; Pan, Yi; Wang, Yeliang; Ding, Feng; Lin, Yuan; Du, Shi-Xuan; Gao, Hong-Jun


    Carbon precursor that forms on the catalyst surface by the dissociation of feedstock gas plays an important role in the controllable growth of graphene on metal substrates. However, the configuration about the precursor has so far remained elusive. Here, we report the direct observation of uniformly structured precursor units and their chain formation at the nucleation stage of graphene growing on Ru(0001) substrate by using scanning tunneling microscopy. Combining this experimental information with density function theory calculations, the atomic-resolved structures of carbon precursor are characterized as adsorbed CH2 segments on the substrate. The dissociated carbon feedstock molecules or radicals further react to form nonplanar -[C2H4]- chains adsorbed on hexagonal-close-packed hollow sites of the Ru(0001) substrate before incorporating into the graphene island. These findings reveal that CH2 and nonplanar -[C2H4]- segments act as precursors in graphene growth and are helpful to improve the quality and the domain size of desired graphene by precursor or feedstock control.

  18. 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


    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.)

  19. Molybdenum sulfide/carbide catalysts (United States)

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda


    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

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

    Indian Academy of Sciences (India)

    Divya Jyothi; Parag A Deshpande; B R Venugopal; Srinivasan Chandrasekaran; Giridhar Madras


    Transition metal oxide (TiO2, Fe2O3, 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 associated rate parameters were determined.

  1. Vibrational spectroscopy of microhydrated conjugate base anions. (United States)

    Asmis, Knut R; Neumark, Daniel M


    Conjugate-base anions are ubiquitous in aqueous solution. Understanding the hydration of these anions at the molecular level represents a long-standing goal in chemistry. A molecular-level perspective on ion hydration is also important for understanding the surface speciation and reactivity of aerosols, which are a central component of atmospheric and oceanic chemical cycles. In this Account, as a means of studying conjugate-base anions in water, we describe infrared multiple-photon dissociation spectroscopy on clusters in which the sulfate, nitrate, bicarbonate, and suberate anions are hydrated by a known number of water molecules. This spectral technique, used over the range of 550-1800 cm(-1), serves as a structural probe of these clusters. The experiments follow how the solvent network around the conjugate-base anion evolves, one water molecule at a time. We make structural assignments by comparing the experimental infrared spectra to those obtained from electronic structure calculations. Our results show how changes in anion structure, symmetry, and charge state have a profound effect on the structure of the solvent network. Conversely, they indicate how hydration can markedly affect the structure of the anion core in a microhydrated cluster. Some key results include the following. The first few water molecules bind to the anion terminal oxo groups in a bridging fashion, forming two anion-water hydrogen bonds. Each oxo group can form up to three hydrogen bonds; one structural result, for example, is the highly symmetric, fully coordinated SO(4)(2-)(H(2)O)(6) cluster, which only contains bridging water molecules. Adding more water molecules results in the formation of a solvent network comprising water-water hydrogen bonding in addition to hydrogen bonding to the anion. For the nitrate, bicarbonate, and suberate anions, fewer bridging sites are available, namely, three, two, and one (per carboxylate group), respectively. As a result, an earlier onset of water

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

    Directory of Open Access Journals (Sweden)

    Jidon Adrian Janaun


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    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.

  4. Identification and characterization of anion binding sites in RNA

    Energy Technology Data Exchange (ETDEWEB)

    Kieft, Jeffrey S.; Chase, Elaine; Costantino, David A.; Golden, Barbara L. (Purdue); (Colorado)


    Although RNA molecules are highly negatively charged, anions have been observed bound to RNA in crystal structures. It has been proposed that anion binding sites found within isolated RNAs represent regions of the molecule that could be involved in intermolecular interactions, indicating potential contact points for negatively charged amino acids from proteins or phosphate groups from an RNA. Several types of anion binding sites have been cataloged based on available structures. However, currently there is no method for unambiguously assigning anions to crystallographic electron density, and this has precluded more detailed analysis of RNA-anion interaction motifs and their significance. We therefore soaked selenate into two different types of RNA crystals and used the anomalous signal from these anions to identify binding sites in these RNA molecules unambiguously. Examination of these sites and comparison with other suspected anion binding sites reveals features of anion binding motifs, and shows that selenate may be a useful tool for studying RNA-anion interactions.

  5. Synthesis and characterization of magnesium oxide supported catalysts with a meso-macropore structure. (United States)

    Kim, Sang Woo; Kim, Inho; Moon, Dong Ju


    Nanostructured magnesium oxide catalyst support materials with controlled morphology and size were synthesized from a supercritical carbon dioxide/ethanol solution via chemical reaction of soluble precursors and subsequent thermal decomposition. Leaf-like magnesium hydroxide precursors with high specific surface area were formed by a low-temperature chemical reaction at below 140 degrees C, while magnesium carbonate cubes with a very low surface area less than 3.3 m2/g were formed by temperature-induced phase transition from a loose to a dense structure during carbonation reaction at above 150 degrees C. The specific surface area has significantly increased higher than 90 m2/g due to the creation of highly porous MgO cubes with mesopore structure formed after thermal decomposition of the magnesium carbonate precursors. Ni-magnesium oxide catalysts with bimodal pore structure were finally formed by the consequence of packing heterogeneity of the porous magnesium oxides with different morphologies and sizes.

  6. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar


    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.

  7. Krebs cycle anions in metabolic acidosis. (United States)

    Bowling, Francis G; Morgan, Thomas J


    For many years it has been apparent from estimates of the anion gap and the strong ion gap that anions of unknown identity can be generated in sepsis and shock states. Evidence is emerging that at least some of these are intermediates of the citric acid cycle. The exact source of this disturbance remains unclear, because a great many metabolic blocks and bottlenecks can disturb the anaplerotic and cataplerotic pathways that enter and leave the cycle. These mechanisms require clarification with the use of tools such as gas chromatography-mass spectrometry.

  8. Templating irreversible covalent macrocyclization by using anions. (United States)

    Kataev, Evgeny A; Kolesnikov, Grigory V; Arnold, Rene; Lavrov, Herman V; Khrustalev, Victor N


    Inorganic anions were used as templates in the reaction between a diamine and an activated diacid to form macrocyclic amides. The reaction conditions were found to perform the macrocyclization sufficiently slow to observe a template effect. A number of analytical methods were used to clarify the reaction mechanisms and to show that the structure of the intermediate plays a decisive role in determining the product distribution. For the macrocyclization under kinetic control, it was shown that the amount of a template, the conformational rigidity of building blocks, and the anion affinities of reaction components and intermediates are important parameters that one should take into consideration to achieve high yields.

  9. Preparation, structural characterization and catalytic properties of Co/CeO2 catalysts for the steam reforming of ethanol and hydrogen production (United States)

    Lovón, Adriana S. P.; Lovón-Quintana, Juan J.; Almerindo, Gizelle I.; Valença, Gustavo P.; Bernardi, Maria I. B.; Araújo, Vinícius D.; Rodrigues, Thenner S.; Robles-Dutenhefner, Patrícia A.; Fajardo, Humberto V.


    In this paper, Co/CeO2 catalysts, with different cobalt contents were prepared by the polymeric precursor method and were evaluated for the steam reforming of ethanol. The catalysts were characterized by N2 physisorption (BET method), X-ray diffraction (XRD), UV-visible diffuse reflectance, temperature programmed reduction analysis (TPR) and field emission scanning electron microscopy (FEG-SEM). It was observed that the catalytic behavior could be influenced by the experimental conditions and the nature of the catalyst employed. Physical-chemical characterizations revealed that the cobalt content of the catalyst influences the metal-support interaction which results in distinct catalyst performances. The catalyst with the highest cobalt content showed the best performance among the catalysts tested, exhibiting complete ethanol conversion, hydrogen selectivity close to 66% and good stability at a reaction temperature of 600 °C.

  10. Solvent effects on Pt-Ru/C catalyst for methanol electro-oxidation

    Institute of Scientific and Technical Information of China (English)

    Jinwei Chen; Chunping Jiang; Hui Lu; Lan Feng; Xin Yang; Liangqiong Li; Ruilin Wang


    Alloying degree,particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent(s) used in the preparation process can affect the particle size and alloying degree of the object substance,which lead to a great positive impact on its properties. In this work,three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction (XRD) and Transmission electron microscopy (TEM). The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry (CV) and Chronoamperometry (CA). Pt-Ru/C catalyst prepared in H_2O or binary solvents of H_2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems,Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity,lower onset and peak potentials,compared with the above catalysts. Moreover,the catalyst prepared in ternary solvents of isopropanol,water and tetrahydrofuran had the smallest particle size,and the high alloying degree and the dispersion kept unchanged. Therefore,this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.

  11. 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;


    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...

  12. Thermal Stability of Nanoporous Raney Gold Catalyst

    Directory of Open Access Journals (Sweden)

    Matthew C. Tai


    Full Text Available Nanoporous “Raney gold” sponge was prepared by de-alloying an Au-Al precursor alloy. Catalytic tests using a micro-reactor confirmed that Raney gold can serve as an active heterogeneous catalyst for CO oxidation, reduction of NO to N2, and oxidation of NO to NO2. In general, the specific surface area of a heterogeneous catalyst has an influence on its catalytic efficacy. Unfortunately, gold sponges coarsen readily, leading to sintering of their structure and reduction in surface area. This potentially places constraints on their upper operating temperature in catalytic reactors. Here we analyzed the behavior of Raney gold when the temperature was raised. We examined the kinetics and mechanism of coarsening of the sponge using a combination of in situ optical measurements and Metropolis Monte Carlo modeling with a Lennard-Jones interatomic potential. Modeling showed that the sponges started with an isotropic “foamy” morphology with negative average “mean curvature” but that subsequent thermally activated coarsening will drive the morphology through a bi-continuous fibrous state and on, eventually, to a sponge consisting of sintered blobs of predominantly positive “mean curvature”.

  13. Imidazolium ionic liquid-supported sulfonic acids: Efficient and recyclable catalysts for esterification of benzoic acid

    Institute of Scientific and Technical Information of China (English)

    Yue Qin Cai; Guo Qiang Yu; Chuan Duo Liu; Yuan Yuan Xu; Wei Wang


    Several imidazolium ionic liquid (IL)-supported sulfonic acids with different anions,[C3SO3Hmim]HSO4,[C3SO3Hmim]BF4,[C3SO3Hmim]PF6,and [C3SO3Hmim]CF3SO3,were synthesized and applied as catalysts for esterification reaction of benzoic acid.The experimental results indicate that imidazolium IL-supported sulfonic acid containing anion of HSO4- shows the best catalytic activity.Only when less [C3SO3Hmim]HSO4 (0.3 equiv.) applied,was the product obtained with high yield of 97%.Furthermore,the produced esters could be separated by decantation,and the catalyst could be reused after the removal of water.

  14. Dimerization of Propylene by Nickel (Ⅱ) and Cobalt (Ⅱ) Catalysts Based on Bidentate Nitrogen-phosphino Chelating Ligands

    Institute of Scientific and Technical Information of China (English)

    Si Zhong WU; Shi Wei LU


    The catalytic property of propylene dimerization by several nickel (Ⅱ), cobalt (Ⅱ)complexes containing N-P bidentate ligands was studied in combination with organoaluminumco-catalysts. The effects of the type of aluminum co-catalysts and its relative amount, the natureof precursors in terms of ligand backbone and metal center were investigated. The resultsindicated that precursor I (N,N-dimethyl-2-(diphenylphosphino)aniline nickel (Ⅱ) dichloride)exhibited high activity in propylene dimerization in the presence of the strong Lewis acid Et3Al2Cl3,whereas low productivity by its cobalt analogues was observed under identical reaction conditions.

  15. Fluorination process using catalysts (United States)

    Hochel, R.C.; Saturday, K.A.


    A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

  16. Fluorination process using catalyst (United States)

    Hochel, Robert C.; Saturday, Kathy A.


    A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

  17. Photo catalyst; Ko shokubai

    Energy Technology Data Exchange (ETDEWEB)



    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)

  18. High-Activity Dealloyed Catalysts

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  19. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  20. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

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


    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...... alkali metal chlorides as well as BaCl2, NaBr and (CH3CH2CH2)(4)NBr were used to investigate the effects of both the ionic charge, size and shape. In 1: 1 electrolytes using small ions only three peaks are present: a sharp cathodic peak at ca. - 0.6 V vs, SCE representing both the insertion of cations...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  1. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

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


    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...

  2. Donnan Membrane Technique (DMT) for Anion Measurement

    NARCIS (Netherlands)

    Alonso Vega, M.F.; Weng, L.P.; Temminghoff, E.J.M.; Riemsdijk, van W.H.


    Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl-, 1-2 days for NO3-, 1-4 days for SO42-

  3. Anionic/cationic complexes in hair care. (United States)

    O'Lenick, Tony


    The formulation of cosmetic products is always more complicated than studying the individual components in aqueous solution. This is because there are numerous interactions between the components, which make the formulation truly more than the sum of the parts. This article will look at interactions between anionic and cationic surfactants and offer insights into how to use these interactions advantageously in making formulations.

  4. Wigner photoemission time delay from endohedral anions (United States)

    Kumar, Ashish; Varma, Hari R.; Deshmukh, Pranawa C.; Manson, Steven T.; Dolmatov, Valeriy K.; Kheifets, Anatoli


    Characteristic features of Wigner photoemission time delay from endohedral anions A@C60q along with their dependence on the anion charge q are unraveled. Specifically, significant enhancement of the time delay in the innermost dipole photoionization channels near threshold is found, owing to the presence of the Coulomb confined resonances (CRs). Moreover, it is shown that interchannel coupling of the inner-shell Coulomb CRs with outer-shell photoionization channels results in resonantly enhanced time delay in the release of the outer-shell photoelectron well above, several hundreds eV, the outer-shell thresholds. It is also demonstrated that, and explained why, photoionization cross sections of the innermost subshells as well as outer subshells (near the inner-subshell threshold) depends only very weakly on the anion charge q , but the dependence of the corresponding time delays on q can be significant. Furthermore, Coulomb CRs are found to emerge in the innermost quadrupole photoionization channels as well, thereby causing considerable time delay in the quadrupole photoemission. These findings are illustrated in calculations of the photoionization of inner and outer subshells of the endohedral anions Ne@C60-1 and Ne@C60-5 that were chosen as case studies.

  5. Stoichiometry of uranyl salophene anion complexes

    NARCIS (Netherlands)

    Antonisse, Martijn M.G.; Snellink-Ruel, Bianca H.M.; Engbersen, Johan F.J.; Reinhoudt, David N.


    In PVC/NPOE ion-selective membranes of potentiometric sensors, the guest-host stoichiometry of the anion complex of H2PO4 - and F- selective uranyl salophene derivatives is 2:1. This stoichiometry is different from the stoichiometry observed in DMSO solution (1H NMR) or solid state (X-ray crystal st

  6. Steam reforming of biomass gasification tar using benzene as a model compound over various Ni supported metal oxide catalysts. (United States)

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


    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.

  7. 通过阴离子型和阳离子型活性链的偶合反应合成甲基丙烯酸甲酯-四氢呋喃嵌段共聚物%Synthesis of Poly (methyl methacrylate)-biock-polytetrahydrofuran by Coupling of Cationic and Anionic Living Chains

    Institute of Scientific and Technical Information of China (English)


    The diblock copolymer poly (methyl methacrylate)-block-polytetrahydrofuran (PMMA-bPTHF) was successfully synthesized by means of the coupling reaction of living cationic PTHF+,SbF-6 and living anionic PMMA-,Li+.Lithium chloride,which is frequently used as a ligand in the polymerization of (meth)acrylates,obstructs the coupling reaction between the anionic and the cationic precursors due to the combination of the chlorine anion with the PTHF cation.Thus,the anionic polymerization should be carried out in the absence of LiCl.

  8. Anionic phospholipids modulate peptide insertion into membranes. (United States)

    Liu, L P; Deber, C M


    While the insertion of a hydrophobic peptide or membrane protein segment into the bilayer can be spontaneous and driven mainly by the hydrophobic effect, anionic lipids, which comprise ca. 20% of biological membranes, provide a source of electrostatic attractions for binding of proteins/peptides into membranes. To unravel the interplay of hydrophobicity and electrostatics in the binding of peptides into membranes, we designed peptides de novo which possess the typical sequence Lys-Lys-Ala-Ala-Ala-X-Ala-Ala-Ala-Ala-Ala-X-Ala-Ala-Trp-Ala-Ala-X-Ala-Al a-Ala-Lys-Lys-Lys-Lys-amide, where X residues correspond to "guest" residues which encompass a range of hydrophobicity (Leu, Ile, Gly, and Ser). Circular dichroism spectra demonstrated that peptides were partially (40-90%) random in aqueous buffer but were promoted to form 100% alpha-helical structures by anionic lipid micelles. In neutral lipid micelles, only the relatively hydrophobic peptides (X = L and I) spontaneously adopted the alpha-helical conformation, but when 25% of negatively charged lipids were mixed in to mimic the content of anionic lipids in biomembranes, the less hydrophobic (X = S and G) peptides then formed alpha-helical conformations. Consistent with these findings, fluorescence quenching by the aqueous-phase quencher iodide indicated that in anionic (dimyristoylphosphatidylglycerol) vesicles, the peptide Trp residue was buried in the lipid vesicle hydrophobic core, while in neutral (dimyristoylphosphatidylcholine) vesicles, only hydrophobic (X = L and I) peptides were shielded from the aqueous solution. Trp emission spectra of peptides in the presence of phospholipids doxyl-labeled at the 5-, 7-, 10-, 12-, and 16-fatty acid positions implied not only a transbilayer orientation for inserted peptides but also that mixed peptide populations (transbilayer + surface-associated) may arise. Overall results suggest that for hydrophobic peptides with segmental threshold hydrophobicity below that which

  9. Low-temperature growth of nitrogen-doped carbon nanofibers by acetonitrile catalytic CVD using Ni-based catalysts

    Directory of Open Access Journals (Sweden)

    Tomohiro Iwasaki


    Full Text Available Abstract To synthesize nitrogen-doped carbon nanofibers (N-CNFs at high growth rates and low temperatures less than 673 K, nickel species (metallic nickel and nickel oxide supported on alumina particles were used as the catalysts for an acetonitrile catalytic chemical vapor deposition (CVD process. The nickel:alumina mass ratio in the catalysts was fixed at 0.05:1. The catalyst precursors were prepared from various nickel salts (nitrate, chloride, sulfate, acetate, and lactate and then calcined at 1073 K for 1 h in oxidative (air, reductive (hydrogen-containing argon, or inert (pure argon atmospheres to activate the nickel-based catalysts. The effects of precursors and calcination atmosphere on the catalyst activity at low temperatures were studied. We found that the catalysts derived from nickel nitrate had relatively small crystallite sizes of nickel species and provided N-CNFs at high growth rates of 57 ± 4 g-CNF/g-Ni/h at 673 K in the CVD process using 10 vol% hydrogen-containing argon as the carrier gas of acetonitrile vapor, which were approximately 4 times larger than that of a conventional CVD process. The obtained results reveal that nitrate ions in the catalyst precursor and hydrogen in the carrier gas can contribute effectively to the activation of catalysts in low-temperature CVD. The fiber diameter and nitrogen content of N-CNFs synthesized at high growth rates were several tens of nanometers and 3.5 ± 0.3 at.%, respectively. Our catalysts and CVD process may lead to cost reductions in the production of N-CNFs.

  10. Low-temperature growth of nitrogen-doped carbon nanofibers by acetonitrile catalytic CVD using Ni-based catalysts (United States)

    Iwasaki, Tomohiro; Makino, Yuri; Fukukawa, Makoto; Nakamura, Hideya; Watano, Satoru


    To synthesize nitrogen-doped carbon nanofibers (N-CNFs) at high growth rates and low temperatures less than 673 K, nickel species (metallic nickel and nickel oxide) supported on alumina particles were used as the catalysts for an acetonitrile catalytic chemical vapor deposition (CVD) process. The nickel:alumina mass ratio in the catalysts was fixed at 0.05:1. The catalyst precursors were prepared from various nickel salts (nitrate, chloride, sulfate, acetate, and lactate) and then calcined at 1073 K for 1 h in oxidative (air), reductive (hydrogen-containing argon), or inert (pure argon) atmospheres to activate the nickel-based catalysts. The effects of precursors and calcination atmosphere on the catalyst activity at low temperatures were studied. We found that the catalysts derived from nickel nitrate had relatively small crystallite sizes of nickel species and provided N-CNFs at high growth rates of 57 ± 4 g-CNF/g-Ni/h at 673 K in the CVD process using 10 vol% hydrogen-containing argon as the carrier gas of acetonitrile vapor, which were approximately 4 times larger than that of a conventional CVD process. The obtained results reveal that nitrate ions in the catalyst precursor and hydrogen in the carrier gas can contribute effectively to the activation of catalysts in low-temperature CVD. The fiber diameter and nitrogen content of N-CNFs synthesized at high growth rates were several tens of nanometers and 3.5 ± 0.3 at.%, respectively. Our catalysts and CVD process may lead to cost reductions in the production of N-CNFs.

  11. Al(HSO_4)_3/silica gel as a novel catalytic system for the ring opening of epoxides with thiocyanate anion under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Ali; Reza; Kiasat; Arash; Mouradzadegun; Somayeh; Elahi; Mehdi; Fallah-Mehrjardi


    For the first time,metal hydrogen sulfates and phosphates/silica gel have been studied as efficient and powerful solid acid catalysts in the ring opening of epoxides with thiocyanate anion.The most significant result was obtained by Al(HSO_4)_3/SiO_2 which afforded the corresponding β-hydroxy thiocyanates under mild reaction conditions and in very short reaction times.The cheapness, availability of the catalyst,ease of procedure and work-up make this method attractive for the organic synthesis.

  12. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst (United States)

    Zelenay, Piotr; Wu, Gang


    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.

  13. Preparation and characterization of Mn/MgAlFe as transfer catalyst for SOx abatement

    Institute of Scientific and Technical Information of China (English)

    Ruiyu Jiang; Honghong Shan; Chunyi Li; Chaohe Yang


    A series of manganese-promoted MgAlFe mixed oxides,used as sulfur transfer catalysts,were prepared by acid-processed gelatin method and characterized by TGA-DTA,XRD,N2 adsorption-desorption and FT-IR techniques.It was found that the sulfur transfer catalysts with 0.5-3.0 wt% manganese showed its good dispersion in the precursor.The novel Mn/MgAlFe catalysts with 0.5-5.0 wt% manganese oxide showed a high oxidative adsorption rate and sulfur adsorption capacity,and 5.0 wt% Mn/MgAlFe sample was superior to the others for SO2 removal.Moreover,the presence of CO had no obvious effect on the adsorption activity of sulfur transfer catalysts for SO2 uptake.

  14. Static and dynamic structural characterization of nanomaterial catalysts (United States)

    Masiel, Daniel Joseph

    Heterogeneous catalysts systems are pervasive in industry, technology and academia. These systems often involve nanostructured transition metal particles that have crucial interfaces with either their supports or solid products. Understanding the nature of these interfaces as well as the structure of the catalysts and support materials themselves is crucial for the advancement of catalysis in general. Recent developments in the field of transmission electron microscopy (TEM) including dynamic transmission electron microscopy (DTEM), electron tomography, and in situ techniques stand poised to provide fresh insight into nanostructured catalyst systems. Several electron microscopy techniques are applied in this study to elucidate the mechanism of silica nanocoil growth and to discern the role of the support material and catalyst size in carbon dioxide and steam reforming of methane. The growth of silica nanocoils by faceted cobalt nanoparticles is a process that was initially believed to take place via a vapor-liquid-solid growth mechanism similar to other nanowire growth techniques. The extensive TEM work described here suggests that the process may instead occur via transport of silicate and silica species over the nanoparticle surface. Electron tomography studies of the interface between the catalyst particles and the wire indicate that they grow from edges between facets. Studies on reduction of the Co 3O4 nanoparticle precursors to the faceted pure cobalt catalysts were carried out using DTEM and in situ heating. Supported catalyst systems for methane reforming were studied using dark field scanning TEM to better understand sintering effects and the increased activity of Ni/Co catalysts supported by carbon nanotubes. Several novel electron microscopy techniques are described including annular dark field DTEM and a metaheuristic algorithm for solving the phase problem of coherent diffractive imaging. By inserting an annular dark field aperture into the back focal

  15. 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)


    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.

  16. Privileged chiral ligands and catalysts

    CERN Document Server

    Zhou, Qi-Lin


    This ultimate ""must have"" and long awaited reference for every chemist working in the field of asymmetric catalysis starts with the core structure of the catalysts, explaining why a certain ligand or catalyst is so successful. It describes in detail the history, the basic structural characteristics, and the applications of these ""privileged catalysts"". A novel concept that gives readers a much deeper insight into the topic.

  17. Oxygen-reducing catalyst layer

    Energy Technology Data Exchange (ETDEWEB)

    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)


    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.

  18. Catalyst systems and uses thereof (United States)

    Ozkan, Umit S.; Holmgreen, Erik M.; Yung, Matthew M.


    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 C.

  19. Ion-assisted precursor dissociation and surface diffusion: Enabling rapid, low-temperature growth of carbon nanofibers (United States)

    Denysenko, I.; Ostrikov, K.


    Growth kinetics of carbon nanofibers in a hydrocarbon plasma is studied. In addition to gas-phase and surface processes common to chemical vapor deposition, the model includes (unique to plasma-exposed catalyst surfaces) ion-induced dissociation of hydrocarbons, interaction of adsorbed species with incoming hydrogen atoms, and dissociation of hydrocarbon ions. It is shown that at low, nanodevice-friendly process temperatures the nanofibers grow via surface diffusion of carbon adatoms produced on the catalyst particle via ion-induced dissociation of a hydrocarbon precursor. These results explain a lower activation energy of nanofiber growth in a plasma and can be used for the synthesis of other nanoassemblies.

  20. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins. (United States)

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S


    Ionic organic contaminants (OCs) are a growing concern for water treatment and the environment and are removed inefficiently by many existing technologies. This study examined removal of anionic OCs by anion exchange resins (AXRs) as a promising alternative. Results indicate that two polystyrene AXRs (IRA910 and IRA96) have higher sorption capacities and selectivity than a polyacrylate resin (A860). For the polystyrene resins, selectivity follows: phenolates ≥ aromatic dicarboxylates > aromatic monocarboxylates > benzenesulfonate > aliphatic carboxylates. This trend can be explained based on hydration energy, the number of exchange groups, and aromaticity and hydrophobicity of the nonpolar moiety (NPM) of the anions. For A860, selectivity only varies within a narrow range (0.13-1.64). Despite the importance of the NPM of the anions, neutral solutes were sorbed much less, indicating synergistic combinations of electrostatic and nonelectrostatic interactions in the overall sorption. By conducting multiple linear regression between Abraham's descriptors and nature log of selectivity, induced dipole-related interactions and electrostatic interactions were found to be the most important interaction forces for sorption of the anions, while solute H-bond basicity has a negative effect. A predictive model was then developed for carboxylates and phenolates based on the poly parameter linear free energy relationships established for a diverse range of 16 anions and 5 neutral solutes, and was validated by accurate prediction of sorption of five test solutes within a wide range of equilibrium concentrations and that of benzoate at different pH.

  1. Anion-π interactions involving [MX(n)](m-) anions: a comprehensive theoretical study. (United States)

    Estarellas, Carolina; Quiñonero, David; Deyà, Pere M; Frontera, Antonio


    In this manuscript we perform a systematic study on the geometric and energetic features of anion-π complexes, wherein the anion is a metal complex of variable shapes and charges. Such a study is lacking in the literature. For the calculations we used the ab initio RI-MP2/def2-TZVPP level of theory. A search in the Cambridge Structural Database (CSD) provides the experimental starting point that inspired the subsequent theoretical study. The influence of [MX(n)](m-) on the anion-π interaction was analyzed in terms of energetic, geometric, and charge transfer properties and Bader's theory of "atom-in-molecules" (AIM). The binding energy depends on the coordination index, geometric features and different orientations adopted by the metallic anion. The binding mode resembling a stacking interaction for linear, trigonal planar and square-planar anions is the most favorable. For tetrahedral and octahedral anions the most favorable orientation is the one with three halogen atoms pointing to the ring.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jonathan L. Sessler


    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  3. Atomic Layer Deposited Catalysts for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Johansson, Anne-Charlotte Elisabeth Birgitta

    layer deposition (ALD), on the other hand, is a highly suitable and still relatively unexplored approach for the synthesis of noble metal catalysts. It is a vapor phase growth method, primarily used to deposit thin lms. ALD is based on self-limiting chemical reactions of alternately injected precursors...... for the realization of such tiny devices. It is a mature technology, suitable for mass production, where versatile structuring is available at the micro and nano regime. Carbon black supported catalysts synthesized by wet chemistry methods are not readily applicable for standard microfabrication techniques. Atomic...... on the sample surface. Its unique growth characteristic enables conformal and uniform lms of controlled thickness and composition. In certain conditions ALD commences by island growth, resulting in discrete nanoparticle formation, which is generally preferred for catalytic applications. Pt-Ru is the best...

  4. Three hydroxy aurone compounds as chemosensors for cyanide anions. (United States)

    Chen, Huihui; Sun, Yunhui; Zhou, Chuanjian; Cao, Duxia; Liu, Zhiqiang; Ma, Lin


    Three new 4-hydroxy aurone compounds 1-3 with dimethylamino (1), bromine (2) and cyano (3) as terminal group have been synthesized. Their photophysical properties as well as recognition properties for cyanide anions in acetonitrile and aqueous solution have also been examined. These compounds exhibit remarkable response to cyanide anions with obvious color and fluorescence change owing to hydrogen bonding reaction between cyanide anions and the O-H moiety of the sensors, which allows naked eye detection of cyanide anions.

  5. Color Responses of a Tripodal Colorimetric Sensor toward Anions

    Institute of Scientific and Technical Information of China (English)

    WEI Lan-Hua; HE Yong-Bing; WU Jin-Long; QIN Hai-Juan; XU Kuo-Xi; MENG Ling-Zhi


    A thiourea-based tripodal colorimetric anion sensor was synthesized. Its binding abilities with AcO- and halide anions in DMSO were studied by UV-Vis spectra. The sensor showed different color responses to these anions. The association constants and different stoichiometries were deduced by nonlinear least-square curve fitting or linear fitting.

  6. Automated identification and quantification of glycerophospholipid molecular species by multiple precursor ion scanning

    DEFF Research Database (Denmark)

    Ejsing, Christer S.; Duchoslav, Eva; Sampaio, Julio


    We report a method for the identification and quantification of glycerophospholipid molecular species that is based on the simultaneous automated acquisition and processing of 41 precursor ion spectra, specific for acyl anions of common fatty acids moieties and several lipid class-specific fragment...... ions. Absolute quantification of identified species was linear within a concentration range of 10 nM-100 microM and was achieved by spiking into total lipid extracts a set of synthetic lipid standards with diheptadecanoyl (17:0/17:0) fatty acid moieties, representing six common classes...

  7. Steam Reforming of Ethylene Glycol over MgAl₂O₄ Supported Rh, Ni, and Co Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Donghai; Lebarbier, Vanessa M.; Xing, Rong; Albrecht, Karl O.; Dagle, Robert A.


    Steam reforming of ethylene glycol (EG) over MgAl₂O₄ supported metal (15 wt.% Ni, 5 wt.% Rh, and 15 wt.% Co) catalysts were investigated using combined experimental and theoretical methods. Compared to highly active Rh and Ni catalysts with 100% conversion, the steam reforming activity of EG over the Co catalyst is comparatively lower with only 42% conversion under the same reaction conditions (500°C, 1 atm, 119,000 h⁻¹, S/C=3.3 mol). However, CH₄ selectivity over the Co catalyst is remarkably lower. For example, by varying the gas hour space velocity (GHSV) such that complete conversion is achieved for all the catalysts, CH₄ selectivity for the Co catalyst is only 8%, which is much lower than the equilibrium CH₄ selectivity of ~ 24% obtained for both the Rh and Ni catalysts. Further studies show that varying H₂O concentration over the Co catalyst has a negligible effect on activity, thus indicating zero-order dependence on H₂O. These experimental results suggest that the supported Co catalyst is a promising EG steam reforming catalyst for high hydrogen production. To gain mechanistic insight for rationalizing the lower CH₃ selectivity observed for the Co catalyst, the initial decomposition reaction steps of ethylene glycol via C-O, O-H, C-H, and C-C bond scissions on the Rh(111), Ni(111) and Co(0001) surfaces were investigated using density functional theory (DFT) calculations. Despite the fact that the bond scission sequence in the EG decomposition on the three metal surfaces varies, which leads to different reaction intermediates, the lower CH₄ selectivity over the Co catalyst, as compared to the Rh and Ni catalysts, is primarily due to the higher barrier for CH₄ formation. The higher S/C ratio enhances the Co catalyst stability, which can be elucidated by the facile water dissociation and an alternative reaction path to remove the CH species as a coking precursor via the HCOH formation. This work was financially supported by the United

  8. Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials (United States)

    Ghampson, Isaac Tyrone

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

  9. Performance Comparison of Two Newly Developed Bimetallic (X-Mo/Al2O3, X=Fe or Co) Catalysts for Reverse Water Gas Shift Reaction

    Institute of Scientific and Technical Information of China (English)

    Abolfazl Gharibi Kharaji; Ahmad Shariati


    The performance of the two newly developed bimetallic catalysts based on the precursor, Mo/Al2O3, was com-pared for reverse water gas shift (RWGS) reaction. The structures of the precursor and the catalysts were studied using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, inductively coupled plasma-atomic emission spec-trometry (ICP-AES), CO chemisorption, temperature programmed reduction of hydrogen (H2-TPR) and scanning electron microscopy (SEM) techniques. The activity of Fe-Mo and Co-Mo catalysts was compared in a ifxed bed reactor at different temperatures. It is shown that the Co-Mo catalyst has higher CO2 conversion at all temperature level. The time-on-stream (TOS) analysis of the activity of catalysts for the RWGS reaction was carried out over a continuous period of 60 h for both catalysts. The Fe-Mo/Al2O3 catalyst exhibits good stability within a period of 60 h, however, the Co-Mo/Al2O3 is gradually deactivated after 50 h of reaction time. Existence of Fe2(MoO4)3 phase in Fe-Mo/Al2O3 catalyst makes this catalyst more stable for RWGS reaction.

  10. Synthesis of Ni-Mo-W sulfide nanorods as catalyst for hydrodesulfurization of dibenzothiophene. (United States)

    Paraguay-Delgado, F; García-Alamilla, R; Lumbreras, J A; Cizniega, E; Alonso-Núñez, G


    Two trimetallic sulfurs, MoWNiS and MoWSNi, were synthesized to be used as a catalyst in hydrodesulfurization reactions. The mixed oxide mesoporous nanostructured MoO3 -WO3 with an Mo:W atomic ratio of 1:1 was used as the precursor. The first catalyst was prepared by impregnating nickel in the oxide precursor and then subsequent sulfiding with an H2S/H2 mix at 400 degrees C for 2 hours. The second catalyst was prepared by sulfiding the precursor and then impregnating the nickel, and finally reducing the material with a H2/N2 at 350 degrees C. In both catalysts the Mo:W:Ni atomic ratio was maintained at 1:1:0.5. The materials obtained were characterized by physical adsorption of nitrogen, X-ray diffraction, scanning electron microscopy, transmission electron microscopy. Furthermore, the materials obtained were evaluated by a dibenzothiophene hydrodesulfuration reaction. The diffraction patterns show that both materials are polycrystalline and mainly of MoS2 and WS2 phases.


    Energy Technology Data Exchange (ETDEWEB)

    Conrad Ingram; Mark Mitchell


    Al-SBA-15 mesoporous catalysts with strong Broensted acid sites and Al stabilized in a totally tetrahedral coordination was synthesized from the addition of hydrothermally aged zeolite Y precursor to SBA-15 synthesis mixture under mildly acidic condition of pH 5.5. The materials possessed surface areas 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 parent SBA-15 synthesized under similar conditions. Up to 2 wt. % Al was present in the most aluminated sample that was investigated, and the Al remained stable in totally tetrahedral coordination, even after calcination at 550 C. The Al-SBA-15 mesoporous catalyst showed significant catalytic activity for cumene dealkylation, and activity increased as the amount of zeolite precursor added to the SBA-15 mixture was increased. The catalyst's activity was not affected by the aging time of the precursor for up to the 24 hr aging time investigated. This method of introducing Al and maintaining it in a total tetrahedral coordination is very effective, in comparison to other direct and post synthesis alumination methods reported. The catalytic performance of the zeolite Y/SBA-15 composite materials will be compared with that of pure SBA-15. The catalysts will then be evaluated for the conversion of heavy petroleum feedstocks.

  12. Synthesis, solid-state NMR characterization, and application for hydrogenation reactions of a novel Wilkinson's-type immobilized catalyst. (United States)

    Abdulhussain, Safaa; Breitzke, Hergen; Ratajczyk, Tomasz; Grünberg, Anna; Srour, Mohamad; Arnaut, Danjela; Weidler, Heiko; Kunz, Ulrike; Kleebe, Hans Joachim; Bommerich, Ute; Bernarding, Johannes; Gutmann, Torsten; Buntkowsky, Gerd


    Silica nanoparticles (SiNPs) were chosen as a solid support material for the immobilization of a new Wilkinson's-type catalyst. In a first step, polymer molecules (poly(triphenylphosphine)ethylene (PTPPE); 4-diphenylphosphine styrene as monomer) were grafted onto the silica nanoparticles by surface-initiated photoinferter-mediated polymerization (SI-PIMP). The catalyst was then created by binding rhodium (Rh) to the polymer side chains, with RhCl3⋅x H2O as a precursor. The triphenylphosphine units and rhodium as Rh(I) provide an environment to form Wilkinson's catalyst-like structures. Employing multinuclear ((31)P, (29)Si, and (13)C) solid-state NMR spectroscopy (SSNMR), the structure of the catalyst bound to the polymer and the intermediates of the grafting reaction have been characterized. Finally, first applications of this catalyst in hydrogenation reactions employing para-enriched hydrogen gas (PHIP experiments) and an assessment of its leaching properties are presented.


    NARCIS (Netherlands)

    Sie, S.T.


    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

  14. 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


    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)

  15. Mechanochemistry, catalysis, and catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Butyagin, P.Yu.


    The physical basis of mechanochemistry and the reasons for the initiation and acceleration of chemical reactions upon the mechanical treatment of solids have been considered. The phenomenon of mechanical catalysis has been described in the example case of the oxidation of CO on oxide surfaces, and the nature of the active sites and the laws governing the mechanically activated chemisorption of gases on cleavage and friction surfaces of solids have been examined. The possibilities of the use of the methods of mechanochemistry in processes used to prepare catalysts have been analyzed in examples of decomposition reactions of inorganic compounds and solid-phase synthesis.

  16. Mössbauer Spectroscopy Investigation and Hydrodesulfurization Properties of Iron–nickel Phosphide Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaudette, Amy F.; Burns, Autumn W.; Hayes, John R.; Smith, Mica C.; Bowker, Richard H.; Seda, Takele; Bussell, Mark E.


    Unsupported and silica-supported FexNi2-xPy catalysts having a range of metal compositions (0 < x 6 2.0) were investigated using Mössbauer spectroscopy, and the results correlated with the surface and hydrodesulfurization (HDS) properties of the supported catalysts. Mössbauer spectroscopy permits determination of the relative site occupancy of Fe atoms in tetrahedral (M(1)) and pyramidal (M(2)) sites in the FexNi2-xPy materials. Fe atoms preferentially occupy M(2) sites for materials with significant Fe contents (x > ~0.60), but the Fe site preference reverses as the Fe content decreases (x < ~0.60). Similar occupation trends are observed for the unsupported and silica-supported FexNi2-xPy materials. Thiophene HDS measurements of the FexNi2-xPy/SiO2 catalysts revealed catalysts with high Fe contents (0.80 6 x 6 2.00) to have low activities, while the activities of Ni-rich catalysts increased dramatically with increased Ni content (0.03 6 x 6 0.60). The highest HDS activity was measured for a catalyst having a nominal precursor composition of Fe0.03Ni1.97P2.00/SiO2; this catalyst was 40% more active than a optimized nickel phosphide catalyst prepared from a precursor having a nominal composition of Ni2.00P1.60/SiO2. The 25 wt.% Fe0.03Ni1.97P2.00/SiO2 catalyst also had a dibenzothiophene HDS activity just over 10% higher than that of the 25 wt.% Ni2.00P1.60/SiO2 catalyst at 548 K. The trend of increasing HDS activity for the FexNi2-xPy/ SiO2 catalysts correlates with preferential Fe occupation of M(1) sites (and, therefore, Ni occupation of M(2) sites). Supported by X-ray photoelectron spectroscopy and oxygen chemisorption measurements, we conclude that the high activity of Ni-rich FexNi2-xPy/SiO2 catalysts can be traced to a high surface density of Ni in M(2) sites that are resistant to site blockage due to S incorporation.

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

    Directory of Open Access Journals (Sweden)

    D. Chaitanya Kumar Rao


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

  18. 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:; Ma, Hong; Cheng, Fei


    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.

  19. Enhanced Activity of Supported Ni Catalysts Promoted by Pt for Rapid Reduction of Aromatic Nitro Compounds

    Directory of Open Access Journals (Sweden)

    Huishan Shang


    Full Text Available To improve the activities of non-noble metal catalysts is highly desirable and valuable to the reduced use of noble metal resources. In this work, the supported nickel (Ni and nickel-platinum (NiPt nanocatalysts were derived from a layered double hydroxide/carbon composite precursor. The catalysts were characterized and the role of Pt was analysed using X-ray diffraction (XRD, high-resolution transmission electron microscopy (HRTEM, energy dispersive X-ray spectroscopy (EDS mapping, and X-ray photoelectron spectroscopy (XPS techniques. The Ni2+ was reduced to metallic Ni0 via a self-reduction way utilizing the carbon as a reducing agent. The average sizes of the Ni particles in the NiPt catalysts were smaller than that in the supported Ni catalyst. The electronic structure of Ni was affected by the incorporation of Pt. The optimal NiPt catalysts exhibited remarkably improved activity toward the reduction of nitrophenol, which has an apparent rate constant (Ka of 18.82 × 10−3 s−1, 6.2 times larger than that of Ni catalyst and also larger than most of the reported values of noble-metal and bimetallic catalysts. The enhanced activity could be ascribed to the modification to the electronic structure of Ni by Pt and the effect of exposed crystal planes.


    Energy Technology Data Exchange (ETDEWEB)

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


    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).

  1. Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

    Institute of Scientific and Technical Information of China (English)

    Sergey Danov; Anton Esipovich; Artem Belousov; Anton Rogozhin


    Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl−anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.

  2. Specific anion effects in Artemia salina. (United States)

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero


    The specific anion effect on the vitality of Artemia salina was investigated by measuring the Lethal Time LT50 of the crustaceans in the presence of different sodium salts solutions at room temperature and at the same ionic strength as natural seawater. Fluoride, thiocyanate and perchlorate are the most toxic agents, while chloride, bromide and sulfate are well tolerated. The rates of oxygen consumption of brine shrimps were recorded in mixed NaCl+NaF or NaCl+NaSCN solutions as a function of time. The results are discussed in terms of the Hofmeister series, and suggest that, besides the biochemical processes that involve F(-), SCN(-) and ClO4(-), the different physico-chemical properties of the strong kosmotropic and chaotropic anions may contribute in determining their strong toxicity for A. salina.

  3. Electron anions and the glass transition temperature

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; Hosono, Hideo


    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32]2+ ∙ (e)2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

  4. In-situ characterization of heterogeneous catalysts

    CERN Document Server

    Rodriguez, Jose A; Chupas, Peter J


    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

  5. Stability and Characteristics of the Halogen Bonding Interaction in an Anion-Anion Complex: A Computational Chemistry Study. (United States)

    Wang, Guimin; Chen, Zhaoqiang; Xu, Zhijian; Wang, Jinan; Yang, Yang; Cai, Tingting; Shi, Jiye; Zhu, Weiliang


    Halogen bonding is the noncovalent interaction between the positively charged σ-hole of organohalogens and nucleophiles. In reality, both the organohalogen and nucleophile could be deprotonated to form anions, which may lead to the vanishing of the σ-hole and possible repulsion between the two anions. However, our database survey in this study revealed that there are halogen bonding-like interactions between two anions. Quantum mechanics calculations with small model complexes composed of halobenzoates and propiolate indicated that the anion-anion halogen bonding is unstable in vacuum but attractive in solvents. Impressively, the QM optimized halogen bonding distance between the two anions is shorter than that in a neutral system, indicating a possibly stronger halogen bonding interaction, which is verified by the calculated binding energies. Furthermore, natural bond orbital and quantum theory of atoms in molecule analyses also suggested stronger anion-anion halogen bonding than that of the neutral one. Energy decomposition by symmetry adapted perturbation theory revealed that the strong binding might be attributed to large induction energy. The calculations on 4 protein-ligand complexes from PDB by the QM/MM method demonstrated that the anion-anion halogen bonding could contribute to the ligands' binding affinity up to ∼3 kcal/mol. Therefore, anion-anion halogen bonding is stable and applicable in reality.

  6. New way for iron introduction in LDH matrix used as catalysts for Friedel–Crafts reactions

    Directory of Open Access Journals (Sweden)

    S. Kerchiche


    Full Text Available The alkylation of toluene, reaction employing benzyl chloride as the alkylating agent over basic hydrotalcite materials: Fe–Mg–Al-LDH prepared by different synthesis methods, including the method of co-precipitation, impregnation and a new method called the method of intercalation by anion exchange in the lamellar space of the host structure LDH. Our prepared solids were characterized by chemical analysis, XRD analysis, BET method and thermogravimetric analysis (TGA and tested in the alkylation of toluene by benzyl chloride reaction. Fe–Mg–Al-LDH clay without or with calcination (at 773 K has been investigated. The catalyst derived from the hydrotalcite by its calcination at 773 K shows high catalytic activity for the alkylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the oxides of iron on the catalyst surface.

  7. Lowest autodetachment state of the water anion (United States)

    Houfek, Karel; Čížek, Martin


    The potential energy surface of the ground state of the water anion H2O- is carefully mapped using multireference CI calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O-+H2 and OH-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The autodetachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O- + H2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slighly off the linear geometry and is separated by a saddle from the autodetachment region. The autodetachment region is directly accessible from the OH-+H asymptote. For the molecular geometries in the autodetachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  8. Politseiuuringud kooskõlastamisele / Liivia Anion

    Index Scriptorium Estoniae

    Anion, Liivia


    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

  9. Preparation of VPO Catalysts and Effect of Zirconium Promoter on the Selective Oxidation of Pentane

    Institute of Scientific and Technical Information of China (English)

    Chen Shengli; Lao Lihua; Shao Hancheng


    This study focuses on the effects of reducing solvents used in the preparation of vanadyl pyrophosphate (VPO), and ZrO2 and (ZrO)2P2O7 promoters on the structure and catalytic performance of VPO catalysts. The VPO catalysts were prepared by the following steps: 1) Formation of vanadium phosphate by the reaction of V2O5 and H3PO4, 2) Synthesis of VPO precursor through the reduction of vanadium phosphate by reducing solvents, and 3) Activation of the precursor. For Zr promoted VPO, Zr was added to the precursor before activation. The P/V atomic ratios of different VPO catalysts, which were prepared by using different reducing solvents, were different. The precursor prepared by using isobutanol or isobutanol-benzyl alcohol contained VO(H2PO4)2 and VOHPO4×0.5H2O. The precursor prepared by using hexanol also contained VO(H2PO4)2 and VOHPO4×0.5H2O crystal phases, but the amount of VOHPO4×0.5H2O was much less than that of VO(H2PO4)2. After activation, all the VPO catalysts, prepared by using different reducing solvents, contained only the (VO)2P2O7 crystal phase. The VPO prepared by using isobutanol-petroleum ether as reducing solvent was the most active, while the VPO prepared by using hexanol had the lowest activity. Nevertheless, their total selectivity to phthalic and maleic anhydrides was almost the same. Both ZrO2 and (ZrO)2P2O7 promoters increased the activity and selectivity of VPO, but ZrO2 promoter increased the activity of VPO more drastically than (ZrO)2P2O7 promoter.

  10. The Interrelationships of Mathematical Precursors in Kindergarten (United States)

    Cirino, Paul T.


    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…

  11. Rapid synthesis of macrocycles from diol precursors

    DEFF Research Database (Denmark)

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


    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...

  12. Donnan membrane technique (DMT) for anion measurement. (United States)

    Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H


    Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

  13. Synthesis of 5′-O-DMT-2′-O-TBS mononucleosides using an organic catalyst (United States)

    Lee, Sunggi; Blaisdell, Thomas P.; Kasaplar, Pinar; Sun, Xixi


    This unit describes a highly effective method to produce 5′-O-DMT-2′-O-TBS mononucleosides selectively using a small organic catalyst. This methodology avoids the tedious protection/deprotection strategy necessary to differentiate the 2′- and 3′-hydroxyl groups in a ribonucleoside. The catalyst was synthesized in two steps starting from the condensation of valinol and cyclopentyl aldehyde, followed by anionic addition of N-methylimidazole. Ring closure of the amino alcohol with N,N-dimethylformamide dimethyl acetal in methanol furnishes the catalyst. All four 2′-O-TBS protected mono-nucleosides, U, ABz, GIb, and CAc, were produced in a single step using 10 to 20 mol% of the catalyst at room temperature with excellent yields and selectivity. Further transformation to phosphoramidite demonstrates the utility of this protocol toward the preparation of monomers useful for automated synthesis of RNA. PMID:24961720

  14. Following the crystallisation of Bi2Mo2O9 catalyst by combined XRD/QuEXAFS

    Indian Academy of Sciences (India)

    Andrew M Beale; Gopinathan Sankar


    The formation of -phase Bi2Mo2O9 catalyst from a precursor precipitate has been studied using the in situ combined XRD/QuEXAFS technique and DSC during calcination. Accordingly the precursor was observed to undergo a number of changes in both the molybdenum (VI) coordination and long-range ordering during this heating. Initially the two other forms of bismuth molybdate (-and -phases) were observed to form from the poorly crystalline precursor at about 230°C, however, the -phase eventually crystallised after prolonged heating at 560°C.

  15. Latent catalyst; Senzaisei shokubai

    Energy Technology Data Exchange (ETDEWEB)



    Epoxy resin, an important function material to support such main industries as electric and electronic devices, automobiles, civil engineering, and building construction, is demanded of development of single liquid type resin having excellent quick hardening performance and storage stability. This requirement comes from environmental problems with an intention of saving energies and reducing resin wastes. The Company, using freely its independent phase separation technology that controls molecular structure of catalysts, developed a latent catalyst having excellent storage stability and high-temperature quick hardening performance. Its major features may be summarized as follows: (1) excellent storage stability at room temperature keeping the product stable for 2.5 months or longer (2 days in conventional products); (2) quick hardening performance hardening the resin in seven seconds at 150 degrees C (equivalent to conventional products); and (3) excellent insulation performance of hardened resin at 140 degrees C of 7 times 10 {sup 13} (ohm) (center dot) cm (2 times 10 {sup 12} (ohm) (center dot) cm in conventional products) (translated by NEDO)

  16. Catalyst design for biorefining. (United States)

    Wilson, Karen; Lee, Adam F


    The quest for sustainable resources to meet the demands of a rapidly rising global population while mitigating the risks of rising CO2 emissions and associated climate change, represents a grand challenge for humanity. Biomass offers the most readily implemented and low-cost solution for sustainable transportation fuels, and the only non-petroleum route to organic molecules for the manufacture of bulk, fine and speciality chemicals and polymers. To be considered truly sustainable, biomass must be derived from resources which do not compete with agricultural land use for food production, or compromise the environment (e.g. via deforestation). Potential feedstocks include waste lignocellulosic or oil-based materials derived from plant or aquatic sources, with the so-called biorefinery concept offering the co-production of biofuels, platform chemicals and energy; analogous to today's petroleum refineries which deliver both high-volume/low-value (e.g. fuels and commodity chemicals) and low-volume/high-value (e.g. fine/speciality chemicals) products, thereby maximizing biomass valorization. This article addresses the challenges to catalytic biomass processing and highlights recent successes in the rational design of heterogeneous catalysts facilitated by advances in nanotechnology and the synthesis of templated porous materials, as well as the use of tailored catalyst surfaces to generate bifunctional solid acid/base materials or tune hydrophobicity.

  17. Anion order in perovskites: a group-theoretical analysis. (United States)

    Talanov, M V; Shirokov, V B; Talanov, V M


    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results.

  18. The effect of preparation factors on the structural and catalytic properties of mesoporous nanocrystalline iron-based catalysts for high temperature water gas shift reaction

    Energy Technology Data Exchange (ETDEWEB)

    Meshkani, Fereshteh; Rezaei, Mehran [University of Kashan, Kashan (Iran, Islamic Republic of)


    A systematic study was done on the effect of preparation factors on the structural and catalytic properties of mesoporous nanocrystalline iron-based catalysts in high temperature water gas shift reaction. The catalysts were prepared by coprecipitation method, and the effect of the main preparation factors (pH, refluxing temperature, refluxing time, concentration of the precursors solution) was studied. The catalysts were characterized by powder X-ray diffraction (XRD), N{sub 2} adsorption (BET), Temperature programmed reduction (TPR), transmission and scanning electron microscopies (TEM, SEM) techniques. The results revealed that the preparation factors affected the textural and catalytic properties of the Fe-Cr-Cu catalyst. The results showed that the prepared catalyst with the highest activity showed higher specific surface area compared to commercial catalyst and consequently exhibited higher activity in high temperature water gas shift reaction. The TEM analysis showed a nanostructure for this sample with crystallite size less than 20 nm.

  19. Synthesis of water-soluble cystine C60 derivative with catalyst and its active oxygen radical scavenging ability

    Institute of Scientific and Technical Information of China (English)

    Wen Chao Guan; Xiang Ying Tang; Li Zhen Huang; Hong Xu


    A novel water-soluble cystine C60 derivative was synthesized in the presence of the catalyst, tetrabutylammonium hydroxide (TBAH). The product was characterized by FT-IR, UV, 1H NMR, 13C NMR, MS and elemental analysis. Furthermore, the that cystine C60 derivative showed an excellent efficiency in eliminating superoxygen anion radical and hydroxyl radical. The 50%inhibition concentration (IC50) for superoxygen anion radical and hydroxyl radical were 0.167 and 0.008 mg/mL, respectively.

  20. Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors (United States)

    Johnson, Kelsea R.; Arevalo Rodriguez, Paul; Brewer, Christopher R.; Brannaka, Joseph A.; Shi, Zhiwei; Yang, Jing; Salazar, Bryan; McElwee-White, Lisa; Walker, Amy V.


    Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

  1. Diverse organo-peptide macrocycles via a fast and catalyst-free oxime/intein-mediated dual ligation. (United States)

    Satyanarayana, Maragani; Vitali, Francesca; Frost, John R; Fasan, Rudi


    Macrocyclic Organo-Peptide Hybrids (MOrPHs) can be prepared from genetically encoded polypeptides via a chemoselective and catalyst-free reaction between a trifunctional oxyamino/amino-thiol synthetic precursor and an intein-fusion protein incorporating a bioorthogonal keto group.

  2. Solvent- and catalyst-free huisgen cycloaddition to rufinamide in flow with a greener, less expensive dipolarophile. (United States)

    Borukhova, Svetlana; Noël, Timothy; Metten, Bert; de Vos, Eric; Hessel, Volker


    Give it a flow: A continuous-flow process for the synthesis of a 1,2,3-triazole precursor of Rufinamide has been developed. The protocol involves a solvent- and catalyst-free operation and utilizes reaction temperatures above the melting point of the target product to prevent microreactor clogging, resulting in a decrease of the operating time from hours to minutes.

  3. Ethanol steam reforming on Ni/Al{sub 2}O{sub 3} catalysts: Effect of Mg addition

    Energy Technology Data Exchange (ETDEWEB)

    Vizcaino, A.J.; Carrero, A.; Calles, J.A. [Department of Chemical and Environmental Technology, ESCET, Universidad Rey Juan Carlos, C/Tulipan s/n, 28933 Mostoles, Madrid (Spain); Arena, P.; Baronetti, G.; Laborde, M.A.; Amadeo, N. [Chemical Engineering Department, School of Engineering, Universidad de Buenos Aires, Pabellon de Industrias, Ciudad Universitaria, 1428 Buenos Aires (Argentina)


    Ethanol steam reforming is an interesting alternative for hydrogen production since ethanol can be renewably obtained. Use of lamellar double hydroxides (LDHs) as precursors of nickel catalysts leads to highly dispersed metal particles in an aluminium structure. In this sense, a Ni(II)Al(III) catalyst was synthesized from a LDH precursor and tested in ethanol steam reforming. Although this catalyst presents high stability, acidity of alumina promotes carbon deposition from ethylene through ethanol dehydration. For this reason, in order to neutralize acid sites, a series of catalysts was prepared by Mg addition to LDH precursors varying Mg/Ni ratio. The effect of Mg/Ni ratio in the catalyst on coke formation during ethanol steam reforming was studied, resulting in significant reduction of the amount of deposited carbon for Mg/Ni ratio higher than 0.1. Moreover, Mg addition increases the catalytic activity due to lower ethylene formation, which competes with ethanol for the same Ni active sites. (author)

  4. Stereospecific olefin polymerization catalysts (United States)

    Bercaw, John E.; Herzog, Timothy A.


    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

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

    Directory of Open Access Journals (Sweden)

    Lina Gan


    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.

  6. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions. (United States)

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L


    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions.

  7. Preparation of precursor for stainless steel foam

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xiang-yang; LI Shan-ni; LI Jie; LIU Ye-xiang


    The effects of polyurethane sponge pretreatment and slurry compositions on the slurry loading in precursor were discussed, and the,performances of stainless steel foams prepared from precursors with different slurry loadings and different particle sizes of the stainless steel powder were also investigated. The experimental results show that the pretreatment of sponge with alkaline solution is effective to reduce the jam of cells in precursor and ensure the slurry to uniformly distribute in sponge, and it is also an effective method for increasing the slurry loading in precursor; the mass fraction of additive A and solid content in slurry greatly affect the slurry loading in precursor, when they are kept in 9%-13% and 52%-75%, respectively, the stainless steel foam may hold excellent 3D open-cell network structure and uniform muscles; the particle size of the stainless steel powder and the slurry loading in precursor have great effects on the bending strength, apparent density and open porosity of stainless steel foam; when the stainless steel powder with particle size of 44 tan and slurry loading of 0.5 g/cm3 in precursor are used, a stainless steel foam can be obtained, which has open porosity of 81.2%, bending strength of about 51.76 MPa and apparent density of about 1.0 g/cm3.

  8. Interaction of anions with substituted buckybowls. The anion's nature and solvent effects. (United States)

    Campo-Cacharrón, Alba; Cabaleiro-Lago, Enrique M; González-Veloso, Iván; Rodríguez-Otero, Jesús


    Complexes formed by CN-substituted corannulene and sumanene with monovalent anions have been computationally studied to evaluate the effect of anion's nature and solvent upon the interaction. The results indicate that the most stable complex arrangement corresponds in all cases to the anion located by the center of the concave face of the bowl. All complexes are remarkably stable in the gas phase, with interaction energies ranging from -47 to -24 kcal/mol depending on the anion and the bowl considered. The order of stability for the different anion complexes in the gas phase is CO2H(-) > Cl(-) > Br(-) > NO3(-) ≫ ClO4(-) > BF4(-). Regarding the bowl employed, the intensity of the interaction is largest with the sumanene derivative substituted in the C-H aromatic groups. The weakest interactions are obtained with the sumanene derivative substituted in the CH2 groups, whereas complexes with the corannulene derivative give intermediate values. NO3(-) is oriented parallel to the bowl in the most stable complexes, whereas CO2H(-) prefers being oriented perpendicular to the bowl; ClO4(-) and BF4(-) arrange themselves with three bonds pointing to the bowl. These orientations are preferred on the basis of larger electrostatic and dispersion interactions. The preference of anions for the concave face of the bowl not only is mainly related to larger electrostatic interactions but also is because dispersion and induction are larger than in other arrangements considered. The presence of solvent modeled with a continuum model has a deep impact on the interaction energies already in solvents with low dielectric constant. All complexes remain stable, though energies in water hardly reach -7 kcal/mol. Br(-) complexes are the most stable in solvent, whereas CO2H(-) ones suffer a large penalty in solvent, becoming among the least stable complexes despite being the most stable in the gas phase.

  9. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide. (United States)

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


    Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

  10. Steam reforming of tar derived from lignin over pompom-like potassium-promoted iron-based catalysts formed on calcined scallop shell. (United States)

    Guan, Guoqing; Kaewpanha, Malinee; Hao, Xiaogang; Zhu, Ai-Min; Kasai, Yutaka; Kakuta, Seiji; Kusakabe, Katsuki; Abudula, Abuliti


    In order to understand the improvement effect of potassium (K) on the catalytic activity of iron-loaded calcined scallop shell (CS) for the steam reforming tar derived from biomass, various K precursors were applied for the catalyst preparation. It is found that pompom-like iron-based particles with a mesoporous structure were easily formed on the surface of calcined scallop shell (CS) when K2CO3 was used as K precursor while no such kind of microsphere was formed when other kinds of K precursors such as KOH and KNO3 were applied. The optimum K-loading amount for the preparation of this catalyst was investigated. Based on the experimental results obtained, a mechanism for the formation of these microspheres was proposed. This pompom-like potassium-promoted iron-based catalyst showed a better catalytic activity and reusability for the steam reforming of tar derived from lignin.

  11. Novel oxidation of aromatic aldehydes catalyzed by Preyssler's anion, [NaP{sub 5}W{sub 30}O{sub 110}]{sup 14-}

    Energy Technology Data Exchange (ETDEWEB)

    Bamoharram, F.F.; Roshani, M.; Moghayadi, M. [Islamic Azad University-Mashhad Branch, Mashhad (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail:; Alizadeh, M.H. [Ferdowsi University of Mashhad, Mashhad (Iran, Islamic Republic of). Dept. of Chemistry; Razavi, H. [Georgetown University, Washington, DC (United States). Dept. of Chemistry


    Preyssler's anion, with formula [NaP{sub 5}W{sub 30}O{sub 110}]{sup 14-}, catalyzes the oxidation of aromatic aldehydes to related carboxylic acids by hydrogen peroxide as oxidizing agent, under microwave irradiation, or at 70 deg C. Both homogeneous and heterogeneous Preyssler's catalysts (as H{sub 14}[NaP{sub 5}W{sub 30}O{sub 110}]) were used and had their activity compared with those of some Keggin structures. Our data indicate that Sodium30-tungsto pentaphosphate, the so-called Preyssler's anion, with high hydrolytic (pH=0-12) and thermal stability is the best catalyst with high yield and good selectivity. Under microwave irradiation, this polyanion supported on SiO{sub 2} was found to be an excellent catalyst for aldehydes with low loss factor in 1-2 min (the loss factor is a measure of the ability of the material to dissipate energy). The effects of various parameters, including catalyst type, nature of the substituent in the aldehyde and temperature, on the yield of the carboxylic acids were studied. (author)

  12. Synthesis and structures of metal chalcogenide precursors (United States)

    Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.


    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.

  13. Atomic Layer Deposition from Dissolved Precursors. (United States)

    Wu, Yanlin; Döhler, Dirk; Barr, Maïssa; Oks, Elina; Wolf, Marc; Santinacci, Lionel; Bachmann, Julien


    We establish a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD) known with gaseous precursors toward precursors dissolved in a liquid. An established ALD reaction behaves similarly when performed from solutions. "Solution ALD" (sALD) can coat deep pores in a conformal manner. sALD offers novel opportunities by overcoming the need for volatile and thermally robust precursors. We establish a MgO sALD procedure based on the hydrolysis of a Grignard reagent.


    Energy Technology Data Exchange (ETDEWEB)

    Panagiotis G. Smirniotis; Robert G. Jenkins


    The work performed during this project focused on the identification of materials capable of providing high activity and selectivity for the selective catalytic reduction of nitric oxide with ammonia. The material surface characteristics were correlated with the catalytic behavior of our catalysts to increase our understanding and to help improve the DeNO{sub x} efficiency. The catalysts employed in this study include mixed oxide composite powders (TiO{sub 2}-Cr{sub 2}O{sub 3}, TiO{sub 2}-ZrO{sub 2}, TiO{sub 2}-WO{sub 3}, TiO{sub 2}-SiO{sub 2}, and TiO{sub 2}-Al{sub 2}O{sub 3}) loaded with varying amounts of V{sub 2}O{sub 5}, along with 5 different commercial sources of TiO{sub 2}. V{sub 2}O{sub 5} was added to the commercial sources of TiO{sub 2} to achieve monolayer coverage. Since the valence state of vanadium in the precursor solution during the impregnation step significantly impacted catalytic performance, catalysts were synthesized from both V{sup +4} and V{sup +5} solutions explain this phenomenon. Specifically, the synthesis of catalysts from V{sup 5+} precursor solutions yields lower-performance catalysts compared to the case of V{sup 4+} under identical conditions. Aging the vanadium precursor solution, which is associated with the reduction of V{sup 5+} to V{sup 4+} (VO{sub 2}{sup +} {yields} VO{sup 2+}), prior to impregnation results in catalysts with excellent catalytic behavior under identical activation and operating conditions. This work also added vanadia to TiO{sub 2}-based supports with low crystallinity. These supports, which have traditionally performed poorly, are now able to function as effective SCR catalysts. Increasing the acidity of the support by incorporating oxides such as WO{sub 3} and Al{sub 2}O{sub 3} significantly improves the SCR activity and nitrogen selectivity. It was also found that the supports should be synthesized with the simultaneous precipitation of the corresponding precursors. The mixed oxide catalysts possess

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

    KAUST Repository

    Widger, Peter C. B.


    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.

  16. Sequential C-Si Bond Formations from Diphenylsilane: Application to Silanediol Peptide Isostere Precursors

    DEFF Research Database (Denmark)

    Nielsen, Lone; Skrydstrup, Troels


    and the first new carbon-silicon bond. The next step is the reduction of this hydridosilane with lithium metal providing a silyl lithium reagent, which undergoes a highly diastereoselective addition to an optically active tert-butanesulfinimine, thus generating the second C-Si bond. This method allows......-step assembly of the carbon-silicon backbone of a silane-containing dipeptide fragment. The synthetic scheme is comprised of an alkene hydrosilylation step with the simple precursor, diphenylsilane, using either a radical initiator or RhCl(PPh3)3, Wilkinson's catalyst, for the creation of a hydridosilane...

  17. 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


    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.

  18. Precursor type affecting surface properties and catalytic activity of sulfated zirconia

    Directory of Open Access Journals (Sweden)

    Zarubica Aleksandra R.


    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.

  19. Synthesis of MgO granule and its precursors via common ion effect. (United States)

    Choi, Se-Bum; Lee, Dong-Kyu; Yu, Hyunung


    It is well known that the shape and size of inorganic nanostructures have much influence on their optical, electrical and physical properties. MgO is a promising material with potential applications in a variety of fields such as catalyst support, reinforcing reagent and good component in superconductors. In this study, flower-like Mg(OH)2 and cubic MgCO3 have been successfully prepared via hydrolysis control of magnesium salt and alkaline solution with common ions under hydrothermal condition by the formation of nano-platelets assembly. Subsequent calcination converts both Mg(OH)2 and MgCO3 into the corresponding MgO granules of similar flower-like and cubic morphology and size to each precursor. The physical and chemical properties of MgO and its precursors of Mg(OH)2 and MgCO3 are investigated by SEM, XRD, FT-IR, and TGA analysis.

  20. Comparative TPR and TPD Studies of Cu and Ca Promotion on Fe-Zn- and Fe-Zn-Zr-Based Fischer-Tropsch Catalysts

    Directory of Open Access Journals (Sweden)

    James Olusola O.


    Full Text Available The present study demonstrates the effect of zirconium promotion on Fe-Zn-based catalysts to boost the active sites of Fischer-Tropsch (FT catalysts. The catalysts are also promoted by Cu and Ca and the active sites are examined using Temperature-Programmed Reduction (TPR with H2 and CO and Temperature-Programmed Desorption (TPD with NH3 and CO2. The results are presented as a comparative study between Fe-Zn- and Fe-Zn-Zr-based catalysts. The results show that addition of Zr to Fe-Zn catalysts increases the availability and dispersion of the precursor to the active sites and promotion with Cu and Ca independently and synergistically enhances reduction of Fe-Zn-Zr-based catalysts. The presence of Ca promotes carburisation, while Cu inhibits carburisation. The impact of the Ca and Cu on the surface acidity/basicity is governed by the nature of the interaction between the phases in the catalysts. The extent of reduction reflects the availability and dispersion of the precursor to the active phase, while the extent of carburisation will impact on the selectivity of the catalysts.

  1. Organic superconductors with an incommensurate anion structure

    Directory of Open Access Journals (Sweden)

    Tadashi Kawamoto and Kazuo Takimiya


    Full Text Available 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(AuI20.436 and (MDT-ST(I30.417 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 reciprocal lattice vector of the anion lattice. The selection rule of the reconstructing vectors is associated with the magnitude of the incommensurate potential. The considerably large interlayer transfer integral and three-dimensional superconducting properties are due to the direct donor–donor interactions coming from the characteristic corrugated conducting sheet structure. The materials with high superconducting transition temperature, Tc, have large ratios of the observed cyclotron masses to the bare ones, which indicates that the strength of the many-body effect is the major determinant of Tc. (MDT-TS(AuI20.441 shows a metal–insulator transition at TMI=50 K, where MDT-TS is 5H-2-(1,3-diselenol-2-ylidene-1,3,4,6-tetrathiapentalene, and the insulating phase is an antiferromagnet with a high Néel temperature (TN=50 K and a high spin–flop field (Bsf=6.9 T. There is a possibility that this material is an incommensurate Mott insulator. Hydrostatic pressure suppresses the insulating state and induces superconductivity at Tc=3.2 K above 1.05 GPa, where Tc rises to the maximum, Tcmax=4.9 K at 1.27 GPa. This compound shows a usual temperature–pressure phase diagram, in which the superconducting phase borders on the antiferromagnetic insulating phase, despite the unusual band filling.

  2. Designing Catalysts for Clean Technology, Green Chemistry, and Sustainable Development (United States)

    Meurig Thomas, John; Raja, Robert


    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.

  3. Probes for anionic cell surface detection (United States)

    Smith, Bradley D.


    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.

  4. Electroculture for crop enhancement by air anions (United States)

    Pohl, H. A.; Todd, G. W.


    Electroculture, the practice of applying strong electric fields or other sources of small air ions to growing plants, has potential to markedly increase crop production and to speed crop growth. The considerable evidence for its effectiveness, and the studies of the mechanisms for its actions are discussed. A mild current of air anions (4 pA/cm2) stimulates bean crop growth and also earlier blossoming and increased growth in the annual, Exacum affine (Persian violet), as well as in seedling geraniums. The present results would indicate that the growing period required until the plants reach a saleable stage of maturity can be shortened by about two weeks under greenhouse conditions.

  5. On the electronic structure of fullerene anions

    Energy Technology Data Exchange (ETDEWEB)

    Bergomi, L.; Jolicoeur, T. (CEA Centre d' Etudes de Saclay, 91 - Gif-sur-Yvette (France). Service de Physique Theorique)


    The authors study the electronic states of isolated fullerene anions C[sub 60][sup n-] (1 [<=] n [<=] 6) taking into account the effective interaction between electrons due to exchange of intramolecular phonons. If the vibronic coupling is strong enough such an effect may overwhelm Hund's rule and lead to an ordering of levels that can be interpreted as on-ball pairing, in a manner similar to the pairing in atomic nuclei. The authors suggest that such effects may be sought in solutions of fulleride ions and discuss recent experimental results.

  6. Impeded solid state reactions and transformations in ceramic catalysts supports and catalysts

    Directory of Open Access Journals (Sweden)

    Ernő E. Kiss


    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.

  7. Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds. (United States)

    Franken, Andreas; Carr, Michael J; Clegg, William; Kilner, Colin A; Kennedy, John D


    B(10)H(14) reacts with para-C(6)H(4)(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-COOH)](-) anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-COOH)](-) anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-COOH)](-) anion 3. Similarly, B(10)H(14) with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB(9)H(13)-6-(COOH)](-) anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(COOH)](-) anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB(9)H(9)-1-(COOH)](-) anion 6. Reduction of the [COOH] anions 3 and 6 with diisobutylaluminium hydride gives the [CH(2)OH] hydroxy anions [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) and [closo-1-CB(9)H(9)-1-(CH(2)OH)](-) 8 respectively. The [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) anion 7 can also be made via isomerisation of the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-CH(2)OH)](-) anion 9, in turn obtained from the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-CH(2)OH)](-) anion 10, which is obtained from the reaction of B(10)H(14) with terephthaldicarboxaldehyde, C(6)H(4)-para-(CHO)(2), in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CHO)](-) anion 11 and the aldehydic [closo-1-CB(9)H(9)-1-(CHO)](-) anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB(9)H(9)-1-C(6)H(4)-para-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion 13 and the [closo-1-CB(9)H(9)-1-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion respectively.

  8. Novel experimental setup for time-of-flight mass spectrometry ion detection in collisions of anionic species with neutral gas-phase molecular targets. (United States)

    Oller, J C; Ellis-Gibbings, L; da Silva, F Ferreira; Limão-Vieira, P; García, G

    We report a novel experimental setup for studying collision induced products resulting from the interaction of anionic beams with a neutral gas-phase molecular target. The precursor projectile was admitted into vacuum through a commercial pulsed valve, with the anionic beam produced in a hollow cathode discharge-induced plasma, and guided to the interaction region by a set of deflecting plates where it was made to interact with the target beam. Depending on the collision energy regime, negative and positive species can be formed in the collision region and ions were time-of-flight (TOF) mass-analysed. Here, we present data on O2 precursor projectile, where we show clear evidence of O(-) and O2(-) formation from the hollow cathode source as well as preliminary results on the interaction of these anions with nitromethane, CH3NO2. The negative ions formed in such collisions were analysed using time-of-flight mass spectrometry. The five most dominant product anions were assigned to H(-), O(-), NO(-), CNO(-) and CH3NO2(-).

  9. Progress in molecular precursors for electronic materials

    Energy Technology Data Exchange (ETDEWEB)

    Buhro, W.E. [Washington Univ., St. Louis, MO (United States)


    Molecular-precursor chemistry provides an essential underpinning to all electronic-materials technologies, including photovoltaics and related areas of direct interest to the DOE. Materials synthesis and processing is a rapidly developing field in which advances in molecular precursors are playing a major role. This article surveys selected recent research examples that define the exciting current directions in molecular-precursor science. These directions include growth of increasingly complex structures and stoichiometries, surface-selective growth, kinetic growth of metastable materials, growth of size-controlled quantum dots and quantum-dot arrays, and growth at progressively lower temperatures. Continued progress in molecular-precursor chemistry will afford precise control over the crystal structures, nanostructures, and microstructures of electronic materials.

  10. Rational design of precursors for oxide ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Apblett, A.W.; Georgieva, G. [Tulane Univ., New Orleans, LA (United States)


    The use of molecular species as precursors for inorganic materials has received considerable attention in recent years. As a result, metal-organic precursors are becoming increasingly sophisticated as particular decomposition mechanisms and specific stoichiometry are integrated into their design. The authors have pursued both of these design aspects for the development of low-temperature precursors for mono- and bi-metallic oxide materials. Thus, a great variety of metal complexes with 2- and 3-oximinocarboxylic acids, acyloin oximes, 2,4-diols, and diacetone alcohol have been prepared and their thermal behavior investigated. The results of this investigation and their application to the preparation of a variety of metal, oxide ceramics, will be discussed. Particular attention will be paid to precursors for alumina, titania, zirconia, perovskite-phase ferroelectric materials, and ferrites.

  11. Precursor Parameter Identification for IGBT Prognostics (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...

  12. Gold/Iron Carbonyl Clusters for Tailored Au/FeOx Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Stefania Albonetti


    Full Text Available A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO16] and [NEt4][AuFe4(CO16] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H2 (PROX as model reactions. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions.

  13. Catalytic ozone oxidation of benzene at low temperature over MnOx/Al-SBA-16 catalyst. (United States)

    Park, Jong Hwa; Kim, Ji Man; Jin, Mingshi; Jeon, Jong-Ki; Kim, Seung-Soo; Park, Sung Hoon; Kim, Sang Chai; Park, Young-Kwon


    The low-temperature catalytic ozone oxidation of benzene was investigated. In this study, Al-SBA-16 (Si/Al = 20) that has a three-dimensional cubic Im3m structure and a high specific surface area was used for catalytic ozone oxidation for the first time. Two different Mn precursors, i.e., Mn acetate and Mn nitrate, were used to synthesize Mn-impregnated Al-SBA-16 catalysts. The characteristics of these two catalysts were investigated by instrumental analyses using the Brunauer-Emmett-Teller method, X-ray diffraction, X-ray photoelectron spectroscopy, and temperature-programmed reduction. A higher catalytic activity was exhibited when Mn acetate was used as the Mn precursor, which is attributed to high Mn dispersion and a high degree of reduction of Mn oxides formed by Mn acetate than those formed by Mn nitrate.

  14. Catalytic oxidation of benzene with ozone over nanoporous Mn/MCM-48 catalyst. (United States)

    Park, Jong-Hwa; Jurng, Jongsoo; Bae, Gwi-Nam; Park, Sung Hoon; Jeon, Jong-Ki; Kim, Sang Chai; Kim, Ji Man; Park, Young-Kwon


    The catalytic oxidation of a representative volatile organic compound, benzene, with ozone at a low temperature was investigated. A nanoporous MCM-48 material with a high specific surface area was used as the support for the catalytic oxidation for the first time. Mn, which has high activity at a low temperature, was used as the metal catalyst. To examine the effect of the Mn precursor, MCM-48 was impregnated with two different Mn precursors: Mn acetate and Mn nitrate. The characteristics of the synthesized catalysts were analyzed by Brunauer Emmett Teller surface area, X-ray diffraction, X-ray photoelectron spectroscopy, and temperature-programmed reduction. MCM-48 impregnated with Mn acetate showed higher catalytic activity than MCM-48 impregnated with Mn nitrate. This result was attributed to the better dispersion within nanoporous MCM-48 and higher oxygen mobility of Mn oxides produced by Mn acetate. The catalytic activity was also shown to depend closely on the ozone concentration.

  15. In situ formation of cobalt oxide nanocubanes as efficient oxygen evolution catalysts. (United States)

    Hutchings, Gregory S; Zhang, Yan; Li, Jian; Yonemoto, Bryan T; Zhou, Xinggui; Zhu, Kake; Jiao, Feng


    Oxygen evolution from water poses a significant challenge in solar fuel production because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen evolution reaction (OER). Here, a new strategy was developed to synthesize nonsupported ultrasmall cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.023 per second per cobalt in photocatalytic water oxidation. X-ray absorption results suggested a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen in an octahedral arrangement to form 8 Co4O4 cubanes, which may be responsible for the exceptionally high OER activity.

  16. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lai-Sheng, E-mail: [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States)


    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  17. Zero-point energy effects in anion solvation shells. (United States)

    Habershon, Scott


    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  18. DFT study on the impact of the methylaluminoxane cocatalyst in ethylene oligomerization using a titanium-based catalyst

    KAUST Repository

    Pasha, Farhan Ahmad


    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.

  19. Effect of tellurium promoter on vanadium phosphate catalyst for partial oxidation of n-butane

    Institute of Scientific and Technical Information of China (English)

    Y. H. Taufiq-Yap; S. Nor Asrina; G. J. Hutchings; N. F. Dummer; J. K. Bartley


    Te-promoted (1%) vanadium phosphate catalyst (VPDTe) was prepared via VOPO4·2H2O by calcining its precursor VOHPO4·0·5H2O in a flow of n-b(u)ane/air.VPDTe catalyst has resulted a higher existence of V5+ phase with V5+/V4+ ratio of 0.23.SEM micrographs show that Te addition altered the arrangement of the platelets from "rose-like" clusters to layer with irregular shape.Te addition has also markedly lowered the reduction activation energies of the vanadium phosphate catalyst as revealed by TPR profile.The amount of active oxygen species associated with V4+ phase of the Te promoted catalyst was significantly higher than those of the unpromoted catalyst.These observations suggest that high mobility and availability of reactive oxygen species contributed to the enhancement of n-butane conversion up to 80% at 673 K,while only 47% over unpromoted catalyst (2400 h-1,1.7% n-butane in air).

  20. A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration. (United States)

    Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop


    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.

  1. TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity (United States)

    Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.


    High surface area TiO2 nanotubes (Ti-NT) synthesized by alkali hydrothermal method were used as a support for NiW hydrodesulphurization catalyst. Nickel salt of 12-tungstophosphoric acid - Ni3/2PW12O40 was applied as oxide precursor of the active components. The catalyst was characterized by SBET, XRD, UV-vis DRS, Raman spectroscopy, XPS, TPR and HRTEM. The results obtained were compared with those for the NiW catalysts prepared over high surface area titania and alumina supports. A polytungstate phase evidenced by Raman spectroscopy was observed indicating the destruction of the initial heteropolyanion. The catalytic experiments revealed two times higher thiophene conversion on NiW catalyst supported on Ti-NT than those of catalysts supported on alumina and titania. Increased HDS activity of the NiW catalyst supported on Ti-NT could be related to a higher amount of W oxysulfide entities interacting with Ni sulfide particles as consequence of the electronic effects of the Ti-NT observed with XPS analysis.

  2. Characterization of a surface modified carbon cryogel and a carbon supported Pt catalyst

    Directory of Open Access Journals (Sweden)



    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.

  3. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)


    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.

  4. Isatin phenylhydrazones: anion enhanced photochromic behaviour. (United States)

    Cigáň, M; Jakusová, K; Gáplovský, M; Filo, J; Donovalová, J; Gáplovský, A


    The photochemical properties of two basic easily synthesized isatin N(2)-phenylhydrazones were investigated. Contrary to the corresponding isatin N(2)-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the C=N double bond creates conditions for the formation of a simple on-off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis-Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore-inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism.

  5. The influence of anionic ligands on stereoisomerism of Ru carbenes and their importance to efficiency and selectivity of catalytic olefin metathesis reactions. (United States)

    Torker, Sebastian; Khan, R Kashif M; Hoveyda, Amir H


    Investigations detailed herein provide insight regarding the mechanism of stereochemical inversion of stereogenic-at-Ru carbene complexes through a nonolefin metathesis-based polytopal rearrangement pathway. Computational analyses (DFT) reveal that there are two key factors that generate sufficient energy barriers that are responsible for the possibility of isolation and characterization of high-energy, but kinetically stable, intermediates: (1) donor-donor interactions that involve the anionic ligands and the strongly electron donating carbene groups and (2) dipolar effects arising from the syn relationship between the anionic groups (iodide and phenoxide). We demonstrate that a Brønsted acid lowers barriers to facilitate isomerization, and that the positive influence of a proton source is the result of its ability to diminish the repulsive electronic interactions originating from the anionic ligands. The implications of the present studies regarding a more sophisticated knowledge of the role of anionic units on the efficiency of Ru-catalyzed olefin metathesis reactions are discussed. The electronic basis for the increased facility with which allylic alcohols participate in olefin metathesis processes will be presented as well. Finally, we illustrate how a better understanding of the role of anionic ligands has served as the basis for successful design of Ru-based Z-selective catalysts for alkene metathesis.

  6. 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


    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.

  7. Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst. (United States)

    Jaya, N; Selvan, B Karpanai; Vennison, S John


    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.

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

    KAUST Repository

    Ahmed, Syud M.


    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.

  9. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.


    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and AcO-) to a s......The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  10. A model for underpotential deposition in the presence of anions (United States)

    Giménez, M. C.; Ramirez-Pastor, A. J.; Leiva, E. P. M.


    A simple model to study the effect of on top coadsorption of anions in underpotential deposition is formulated. It considers a lattice-gas model with pair potential interactions between nearest neighbors. As test system, the electrodeposition of silver on gold is studied by means of grand canonical Monte Carlo simulations. The influence of anions on the adsorption isotherms is analyzed. It is found that as the interaction between silver atoms and anions increases, the monolayer adsorbs at more negative chemical potentials. For large interactions between silver atoms and anions, a expanded structure occurs for the silver monolayer.

  11. The innovation catalysts. (United States)

    Martin, Roger L


    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.

  12. Effect of different nickel precursors on capacitive behavior of electrodeposited NiO thin films (United States)

    Kore, R. M.; Ghadge, T. S.; Ambare, R. C.; Lokhande, B. J.


    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.

  13. Selective side-chain oxidation of alkyl aromatic compounds catalyzed by cerium modified silver catalysts

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Schimmoeller, Bjoern; Hansen, Thomas Willum


    an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation......Silver supported on silica effectively catalyzes the aerobic side-chain oxidation of alkyl aromatic compounds under solvent-free conditions. Toluene, p-xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene...... and flame spray pyrolysis. Addition of a Ce precursor to the FSP catalyst resulted in significantly smaller silver particles. Ce-doped FSP catalysts in general exhibited a superior catalytic performance with TONs up to 2000 except for cumene oxidation that appeared to proceed mainly by homogeneous catalysis...

  14. Benefits of mesopores in nanocristalline Pd/SnO2 catalysts for nitrate hydrogenation

    Directory of Open Access Journals (Sweden)

    Kovačević Marijana K.


    Full Text Available Mesoporous nanocristalline SnO2 supports were synthesized by a modified sol-gel method starting from SnCl2·2H2O and citric acid at pH 2.0 and 9.5. Noble metal was introduced via wet impregnation using PdCl2 as active phase precursor. Catalysts activities in water denitration were correlated with their textural, structural and morphological properties using LTNA (BET, XRD and SEM/EDS analysis. Lower pH value during the catalyst synthesis resulted in a final material characterized with more developed porosity and higher surface area. Although both catalysts turned out to be tailored from nanoscale crystallites, higher pore fraction of mesopores resulting from the synthesis in acidic conditions, was found to be responsible for superior catalytic behavior.

  15. Low Temperature Growth of Vertically Aligned Carbon Nanotubes via Floating Catalyst Chemical Vapor Deposition Method

    Institute of Scientific and Technical Information of China (English)

    M.R. Atiyan; D.R. Awang Biak; F. Ahmadun; I.S. Ahamad; F. Mohd Yasin; H. Mohamed Yusoff


    Synthesis of carbon nanotubes (CNTs) below 600℃ using supporting catalyst chemical vapor deposition method was reported by many research groups. However, the floating catalyst chemical vapor deposition received less attention due to imperfect nanotubes produced. In this work, the effects of varying the preheating temperature on the synthesis of CNT were investigated. The reaction temperature was set at 570℃. The preheating set temperature was varied from 150 to 400℃ at 50℃ interval. Three O-ring shape heating mantels were used as heating source for the preheater. In situ monitoring device was used to observe the temperature profile in the reactor. Benzene and ferrocene were used as the carbon source and catalyst precursor, respectively. Vertically aligned CNTs were synthesized when the preheating temperature was set at 400℃. When the preheating temperature was increased up to 400℃, both the length and the alignment of CNTs produced were improved.

  16. 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)


    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.

  17. Cation/Anion Substitution in Cu2ZnSnS4 for Improved Photovoltaic Performance


    Balakrishna Ananthoju; Jeotikanta Mohapatra; Jangid, Manoj K.; Bahadur, D.; Medhekar, N. V.; ASLAM, M.


    Cations and anions are replaced with Fe, Mn, and Se in CZTS in order to control the formations of the secondary phase, the band gap, and the micro structure of Cu2ZnSnS4. We demonstrate a simplified synthesis strategy for a range of quaternary chalcogenide nanoparticles such as Cu2ZnSnS4 (CZTS), Cu2FeSnS4 (CFTS), Cu2MnSnS4 (CMTS), Cu2ZnSnSe4 (CZTSe), and Cu2ZnSn(S0.5Se0.5)4 (CZTSSe) by thermolysis of metal chloride precursors using long chain amine molecules. It is observed that the crystal s...

  18. Synthesis of cubic Ia-3d mesoporous silica in anionic surfactant templating system with the aid of acetate. (United States)

    Deng, Shao-Xin; Xu, Xue-Yan; He, Wen-Chao; Wang, Jin-Gui; Chen, Tie-Hong


    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.

  19. 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: [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)


    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. Anion-Channel Blockers Inhibit S-Type Anion Channels and Abscisic Acid Responses in Guard Cells. (United States)

    Schwartz, A.; Ilan, N.; Schwarz, M.; Scheaffer, J.; Assmann, S. M.; Schroeder, J. I.


    The effects of anion-channel blockers on light-mediated stomatal opening, on the potassium dependence of stomatal opening, on stomatal responses to abscisic acid (ABA), and on current through slow anion channels in the plasma membrane of guard cells were investigated. The anion-channel blockers anthracene-9-carboxylic acid (9-AC) and niflumic acid blocked current through slow anion channels of Vicia faba L. guard cells. Both 9-AC and niflumic acid reversed ABA inhibition of stomatal opening in V. faba L. and Commelina communis L. The anion-channel blocker probenecid also abolished ABA inhibition of stomatal opening in both species. Additional tests of 9-AC effects on stomatal aperture in Commelina revealed that application of this anion-channel blocker allowed wide stomatal opening under low (1 mM) KCI conditions and increased the rate of stomatal opening under both low and high (100 mM) KCI conditions. These results indicate that anion channels can function as a negative regulator of stomatal opening, presumably by allowing anion efflux and depolarization, which prohibits ion up-take in guard cells. Furthermore, 9-AC prevented ABA induction of stomatal closure. A model in which ABA activation of anion channels contributes a rate-limiting mechanism during ABA-induced stomatal closure and inhibition of stomatal opening is discussed.

  1. The efficient synthesis of a molybdenum carbide catalyst via H2-thermal treatment of a Mo(VI)-hexamethylenetetramine complex. (United States)

    Wang, Zhi-Qiang; Zhang, Zhong-Biao; Zhang, Ming-Hui


    An efficient method for preparation of Mo(2)C catalyst is described, where Mo(2)C is obtained by the heat treatment of a single solid precursor containing (NH(4))(6)Mo(7)O(24) and hexamethylenetetramine (HMT) at 923 K in H(2) flow without conventional prolonged carbonization. The catalysts are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area measurement, and transmission electron microscopy (TEM). Furthermore, these catalysts are evaluated in the dibenzothiophene (DBT) hydrodesulfurization (HDS) reaction, and proved to be superior to those prepared by a temperature-programmed reduction (TPRe) method. The better catalytic performance is ascribed to higher dispersion of Mo(2)C on the support and a lower surface polymeric carbon content. This hydrogen thermal treatment (HTT) method provided a new strategy for the preparation of a highly active molybdenum carbide catalyst.

  2. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    KAUST Repository

    Balasamy, Rabindran J.


    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.

  3. Electrochemical performance of annealed cobalt-benzotriazole/CNTs catalysts towards the oxygen reduction reaction. (United States)

    Morozan, Adina; Jégou, Pascale; Jousselme, Bruno; Palacin, Serge


    One of the major limitations yet to the global implementation of polymer electrolyte membrane fuel cells (PEMFCs) is the cathode catalyst. The development of efficient platinum-free catalysts is the key issue to solve the problem of slow kinetics of the oxygen reduction reaction (ORR) and high cost. We report a promising catalyst for ORR prepared through the annealing treatment under inert conditions of the cobalt-benzotriazole (Co-BTA) complex supported on carbon nanotubes (CNTs). The N-rich benzotriazole precursor was chosen based on its ability to complex Co(II) ions and generate under annealing highly reactive radicals able to tune the physicochemical properties of CNTs. X-Ray photoelectron spectroscopy (XPS) was used to follow the surface structure changes and highlight the active electrocatalytic sites towards the ORR. To achieve further evaluation of the catalysts in acidic medium, voltamperometry, rotating disk electrode (RDE), rotating ring-disk electrode (RRDE) and half-cell measurements were performed. The resulting catalysts (Co/N/CNTs) all show catalytic activity towards the ORR, the most active one resulting from annealing at 700 °C. The overall electron transfer number for the catalyzed ORR was determined to be ∼3.7 with no change upon the catalyst loading, suggesting that the ORR was dominated by a 4e(-) transfer process. The results indicate a promising alternative cathode catalyst for ORR in fuel cells, although its performance is still lower (overpotential around 110 mV evaluated by RDE and RRDE) than the reference Pt/C catalyst.

  4. Anion permselective membrane. [For redox fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, S.S.; Hodgdon, R.B.


    Experimental anion permeselective membranes were improved and characterized for use as separators in a chemical redox, power storage cell being developed at the NASA Lewis Research Center. The goal of minimal Fe/sup +3/ ion transfer was achieved for each candidate membrane system. Minimal membrane resistivity was demonstrated by reduction of film thickness using synthetic backing materials but usefulness of thin membranes was limited by the scarcity of compatible fabrics. The most durable and useful backing fabrics were modacrylics. One membrane, a copolymer of 4 vinylpyridine and vinyl benzylchloride was outstanding in overall electrochemical and physical properties. Long term (1000 hrs) membrane chemical and thermal durability in redox environment was shown by three candidate polymers and two membranes. The remainder had good durability at ambient temperature. Manufacturing capability was demonstrated for large scale production of membrane sheets 5.5 ft/sup 2/ in area for two candidate systems.

  5. Structural evolution of small ruthenium cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Waldt, Eugen [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Hehn, Anna-Sophia; Ahlrichs, Reinhart [Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany); Kappes, Manfred M.; Schooss, Detlef, E-mail: [Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany); Institute für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstrasse 12, 76128 Karlsruhe (Germany)


    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  6. Once upon Anion: A Tale of Photodetachment (United States)

    Lineberger, W. Carl


    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!

  7. Advanced polymer chemistry of organometallic anions

    Energy Technology Data Exchange (ETDEWEB)

    Chamberlin, R.M.; Abney, K.D. [Los Alamos National Lab., NM (United States); Balaich, G.J.; Fino, S.A. [Air Force Academy, CO (United States)


    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes.

  8. Adsorption of an anionic dispersant on lignite

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty


    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  9. Anion channelrhodopsins for inhibitory cardiac optogenetics (United States)

    Govorunova, Elena G.; Cunha, Shane R.; Sineshchekov, Oleg A.; Spudich, John L.


    Optical control of the heart muscle is a promising strategy for cardiology because it is more specific than traditional electrical stimulation, and allows a higher temporal resolution than pharmacological interventions. Anion channelrhodopsins (ACRs) from cryptophyte algae expressed in cultured neonatal rat ventricular cardiomyocytes produced inhibitory currents at less than one-thousandth of the light intensity required by previously available optogenetic tools, such as the proton pump archaerhodopsin-3 (Arch). Because of their greater photocurrents, ACRs permitted complete inhibition of cardiomyocyte electrical activity under conditions in which Arch was inefficient. Most importantly, ACR expression allowed precisely controlled shortening of the action potential duration by switching on the light during its repolarization phase, which was not possible with previously used optogenetic tools. Optical shortening of cardiac action potentials may benefit pathophysiology research and the development of optogenetic treatments for cardiac disorders such as the long QT syndrome. PMID:27628215

  10. Promotional Effect on Selective Catalytic Reduction of NOx with NH3 over Overloaded W and Ce on V2O5/TiO2 Catalysts


    Seunghee Youn; Inhak Song; Do Heui Kim


    W and Ce are known to be a good promoters to improve selective catalytic reduction (SCR) activity for V2O5/TiO2 catalysts. This work aimed at finding the optimum ratio and loading of promoters (W and Ce) on V2O5/TiO2 catalyst in order to improve SCR reactivity in low temperature region and to minimize N2O formation in high temperature region. In addition, we changed the order of impregnation between W and Ce precursors on V2O5/TiO2 catalyst during the preparation and observed its effect on SC...

  11. Palladium deposits spontaneously grown on nickel foam for electro-catalyzing methanol oxidation: Effect of precursors (United States)

    Niu, Xiangheng; Zhao, Hongli; Lan, Minbo


    Methanol, a high-energy substance, is widely used for green fuel cells. However, the sluggish electrochemical methanol oxidation reaction (MOR) on state-of-the-art catalysts still requires for exploring high-performance and low-cost materials to further promote the reaction kinetics at low overpotentials. Here we carried out the first electrocatalytic comparison study of two Ni foam-supported Pd nanomaterials (Pd-2-Ni and Pd-4-Ni, respectively), obtained through the spontaneous galvanic replacement of Ni with different palladic precursors ([PdCl4]2- and [PdCl6]2-, respectively), toward MOR. With replacement, Pd deposits with discrepant arrangements and coverages were grown on the porous Ni support. Compared to commercial Pd/C, both Pd-2-Ni and Pd-4-Ni exhibited better mass activity and catalytic durability for MOR in alkaline media. More interestingly, different palladic precursors made a significant effect on the catalytic performance of the Ni foam-supported Pd deposits. In Pd-4-Ni, the 2:1 stoichiometric replacement of Ni with [PdCl6]2- enabled the incompact arrangement of Pd structures, with more exposure of Ni atoms adjoined to Pd atoms on the catalytic interface compared to Pd-2-Ni. As a result, with the favorable Ni-neighbor-Pd regime and the higher utilization efficiency of Pd atoms, the synthesized Pd-4-Ni catalyst provided a mass activity of approximately 1.5 times higher than Pd-2-Ni toward MOR.

  12. Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes (United States)

    Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael


    The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

  13. Molecularly imprinted Ru complex catalysts integrated on oxide surfaces. (United States)

    Muratsugu, Satoshi; Tada, Mizuki


    Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such

  14. Regulation of organic anion transport in the liver

    NARCIS (Netherlands)

    Roelofsen, H; Jansen, PLM


    In several liver diseases the biliary transport is disturbed, resulting in, for example, jaundice and cholestasis. Many of these symptoms can be attributed to altered regulation of hepatic transporters. Organic anion transport, mediated by the canalicular multispecific organic anion transporter (cmo

  15. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud


    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined...



    Sprik, M.


    By means of a fully polarizable model for the chloride ion-water interaction we show that the modelling of anion solvation suffers from a similar inconsistency as the current electron-solvent potentials. Either the bulk hydration enthalpies are correct with the first hydration shell overbound, or the potential is adapted to describe the local environment of the solute at the expense of a major loss of solvation enthalpy. It is argued that boundary effects in the simulation are at least partly...

  17. Extraction of monoclonal antibodies (IgG1) using anionic and anionic/nonionic reverse micelles. (United States)

    George, Daliya A; Stuckey, David C


    Purification schemes for antibody production based on affinity chromatography are trying to keep pace with increases in cell culture expression levels and many current research initiatives are focused on finding alternatives to chromatography for the purification of Monoclonal antibodies (MAbs). In this article, we have investigated an alternative separation technique based on liquid-liquid extraction called the reverse micellar extraction. We extracted MAb (IgG1) using reverse micelles of an anionic surfactant, sodium bis 2-ethyl-hexyl sulfosuccinate (AOT) and a combination of anionic (AOT) and nonionic surfactants (Brij-30, Tween-85, Span-85) using isooctane as the solvent system. The extraction efficiency of IgG1 was studied by varying parameters, such as pH of the aqueous phase, cation concentration, and type and surfactant concentration. Using the AOT/Isooctane reverse micellar system, we could achieve good overall extraction of IgG1 (between 80 and 90%), but only 30% of the bioactivity of IgG1 could be recovered at the end of the extraction by using its binding to affinity chromatography columns as a surrogate measure of activity. As anionic surfactants were suspected as being one of the reasons for the reduced activity, we decided to combine a nonionic surfactant with an anionic surfactant and then study its effect on the extraction efficiency and bioactivity. The best results were obtained using an AOT/Brij-30/Isooctane reverse micellar system, which gave an overall extraction above 90 and 59% overall activity recovery. An AOT/Tween-85/Isooctane reverse micellar system gave an overall extraction of between 75 and 80% and overall activity recovery of around 40-45%. The results showed that the activity recovery of IgG1 can be significantly enhanced using different surfactant combination systems, and if the recovery of IgG1 can be further enhanced, the technique shows considerable promise for the downstream purification of MAbs.

  18. Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator. (United States)

    Seenivasan, Kalaivani; Sommazzi, Anna; Bonino, Francesca; Bordiga, Silvia; Groppo, Elena


    X-ray powder diffraction (XRPD), Infrared, Raman, and UV/Vis spectroscopy have been used to investigate the structural, vibrational, and optical properties of Ti and Mg chloride tetrahydrofuranates as precursors of heterogeneous Ziegler-Natta catalysts for polyethylene production; as well as their interaction compound (pro-catalyst) and the final catalyst obtained after interaction with the AlR(3) activator. Although the structure of the precursors and of the pro-catalyst were well known, that of the catalyst (obtained by reaction of the pro-catalyst with AlR(3)) was not easily obtainable from XRPD data. IR and Raman spectroscopy provided important information on tetrahydrofuran (thf) coordination and on the ν(M-Cl) region; whereas UV/Vis spectroscopy gave the direct proof on both the formal oxidation state and the coordination environment of the active Ti sites. Those presented herein are among the first direct experimental data on the structure of the active Ti sites in Ziegler-Natta catalysts, and can be used to validate the many computational studies that have been increasing exponentially in the last few decades.

  19. Novel precursors for the deposition of rare earth oxides; Neuartige Precursor zur Abscheidung von Selten-Erd-Oxiden

    Energy Technology Data Exchange (ETDEWEB)

    Ahlers, Mareike


    During this work rare earth solvates with nitrate and perchlorate anions have been investigated. All compounds have been structurally characterized and analyzed using thermal gravimetric analysis. The decomposition residues were analyzed using powder diffraction methods. Almost all compounds showed a characteristically intense exothermic decomposition step during the thermal decomposition, most likely caused by an intramolecular redox reaction between the nitrate or perchlorate anion respectively and the organic solvent molecules. The nitrates RE(NO{sub 3}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2} (RE = Sm, Eu) were isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. The known compound group of dimethoxyethane solvates was then expanded with RE(NO{sub 3}){sub 3}(O{sub 2}C{sub 4}H{sub 10}) (RE = La, Sm, Eu). Considering the possible use as precursor material the already described neodymium compound is also discussed. The thermal decomposition of these compounds yields the respective cubic rare earth oxide and shows the typical intense exothermic decomposition reaction. A variety of different precursor system based on nitrate solvates for the deposition of rare earth oxide layers on a silicon surface was developed and investigated in collaboration with the group of Prof. Dr. Al-Shamery (Univ. Oldenburg). Ultra thin films on a H-Si(111) surface were obtained via the deposition of the precursor, which was dissolved in organic solvents. An oxide layer was detected after the heating of the sample. The film thickness was measured as < 10 nm, whereas the thickness of the film was controlled by the concentration of the precursor solution. Sm(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 3} was isolated and characterized for the first time as the intermediate of the dehydration reaction with trimethyl orthoformate. Eu(ClO{sub 4}){sub 3}(CH(OCH{sub 3}){sub 3}){sub 2}(MeOH){sub 2} was obtained without

  20. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis. (United States)

    Song, Hyun-Ouk; Ryu, Jae-Sook


    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.