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Sample records for active catalyst species

  1. Effect of the dispersants on Pd species and catalytic activity of supported palladium catalyst

    NASA Astrophysics Data System (ADS)

    Hu, Yue; Yang, Xiaojun; Cao, Shuo; Zhou, Jie; Wu, Yuanxin; Han, Jinyu; Yan, Zhiguo; Zheng, Mingming

    2017-04-01

    A series of supported palladium catalysts has been prepared through the precipitation method and the reduction method, using polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) as dispersants. The effects of the dispersants on the properties of catalysts were evaluated and the catalytic performance of the new materials was investigated for the oxidative carbonylation of phenol to diphenyl carbonate (DPC). The catalysts as prepared were also characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM), Brunner-Emmet-Teller (BET) measurements and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the addition of the dispersants had no effect on the crystal phase of the catalysts. However, the dispersion of Pd particles was improved when the dispersants were used. Moreover, the particle sizes of Pd nanoparticles modified by PVA were smaller than those modified by PVP. The catalysts prepared using the dispersants gave better yields of DPC than the catalysts prepared without the dispersants. The highest yield of DPC was 17.9% with the PVA-Red catalyst. The characterization results for the used catalysts showed that the Pd species in the PVA-Red catalyst remained mostly divalent and the lattice oxygen species were consumed during the reaction, which could lead to the higher catalytic activity of the PVA-Red catalyst. The experimental results confirm that PVA effectively inhibited the sintering and reduction of active Pd species in the oxidative carbonylation of phenol.

  2. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    PubMed Central

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J.; Kiely, Christopher J.

    2016-01-01

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviours after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. Correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst. PMID:27671143

  3. Catalyst activator

    DOEpatents

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

    2001-01-01

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

  4. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    SciTech Connect

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; Mineo, Yuki; Haruta, Masatake; Hutchings, Graham J.; Kiely, Christopher J.

    2016-09-27

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviors after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to reveal the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. As a result, correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst.

  5. Population and hierarchy of active species in gold iron oxide catalysts for carbon monoxide oxidation

    DOE PAGES

    He, Qian; Freakley, Simon J.; Edwards, Jennifer K.; ...

    2016-09-27

    The identity of active species in supported gold catalysts for low temperature carbon monoxide oxidation remains an unsettled debate. With large amounts of experimental evidence supporting theories of either gold nanoparticles or sub-nm gold species being active, it was recently proposed that a size-dependent activity hierarchy should exist. Here we study the diverging catalytic behaviors after heat treatment of Au/FeOx materials prepared via co-precipitation and deposition precipitation methods. After ruling out any support effects, the gold particle size distributions in different catalysts are quantitatively studied using aberration corrected scanning transmission electron microscopy (STEM). A counting protocol is developed to revealmore » the true particle size distribution from HAADF-STEM images, which reliably includes all the gold species present. As a result, correlation of the populations of the various gold species present with catalysis results demonstrate that a size-dependent activity hierarchy must exist in the Au/FeOx catalyst.« less

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

    PubMed Central

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

    2016-01-01

    The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

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

    PubMed

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

    2016-08-19

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  9. Copper-Catalyzed Transformations Using Cu-H, Cu-B, and Cu-Si as Active Catalyst Species.

    PubMed

    Tsuji, Yasushi; Fujihara, Tetsuaki

    2016-10-01

    This review summarizes transformations using copper hydride (Cu-H), boryl copper (Cu-B) or silyl copper (Cu-Si) as active catalyst species. Semihydrogenation, hydroboration, and hydrocarboxylation have been developed using Cu-H as active catalyst species. Preferential reduction of sterically hindered ketones is accompanied by Cu-H species bearing a bowl-shaped phosphine as a crucial ligand. Employing Cu-B species, hydroboration of alkynes and allenes, synthesis of 2-boryl-1,3-butadiene, and borylative allyl-allyl coupling are established. Silacarboxylation of alkynes, regiodivergent silacarboxylation of allenes, and silylative allylation of ketones involve Cu-Si species. The key to these selective transformations is regioselective addition of Cu-H, Cu-B, or Cu-Si species to carbon-carbon multiple bonds of alkynes and allenes to afford the corresponding alkenylcopper or allylcopper intermediates.

  10. Alcohols synthesis from carbon oxides and hydrogen on palladium and rhodium catalysts. Study of active species

    SciTech Connect

    Kiememann, A.; Hindermann, J.P.; Breault, R.; Idries, H.

    1986-03-01

    The synthesis of primary chemical products and/or gasoline additives of high octane number from synthesis gas obtained by coal gasification has received much attention these past years. Actually, even if methanol has been the most important oxygenated product, intensive research is being carried out for the direct synthesis of higher alcohols: ethanol for organic synthesis, or an alcohol mixture, from C/sub 1/ to C/sub 5/, as an additive to gasoline. For the methanol synthesis, copper-based catalysts, have long been considered as the only effective catalysts. Meanwhile Poutsma et al., showed the possible obtaining of methanol with palladium; this last metal has always been considered inactive for directing production of methane from CO-H/sub 2/. It is also true that the selectivity and activity vary greatly with the support. Even if other factors like the particle size was evoked to explain the change in the selectivity, the support effect seems to be primordial. It can play different roles on: the acidity and basicity, the structure of the active sites, the stabilization of intermediates and the formation of an intimate contact between metallic particles and sodium or lithium ions, a strong metal support interaction (SMSI); in particular with rhodium catalysts.

  11. The influence of Mn species on the SO2 removal of Mn-based activated carbon catalysts

    NASA Astrophysics Data System (ADS)

    Qu, Yi-Fan; Guo, Jia-Xiu; Chu, Ying-Hao; Sun, Ming-Chao; Yin, Hua-Qiang

    2013-10-01

    Using Mn(NO3)2 as precursor, a series of Mn-based activated carbon catalysts were prepared by ultrasound-assisted excessive impregnation method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The influences of Mn species and nitric acid pretreatment on the removal role of SO2 were investigated. MnO and Mn3O4 coexist in catalysts calcined at 650 and 800 °C and exhibit best SO2 removal ability, whereas Mn2O3 formed in the catalyst calcined at 500 °C and shows poor activity. After treatment by nitric acid, the Cdbnd O of activated carbon support increases and the crystal size of MnO decreases, resulting in the enhancement of the catalytic activity. During reaction process, manganese oxides are gradually transferred into MnO2. And this change directly results in a decrease of activity. But the SO2 removal rate has been maintained in the range of 30-40%, indicating that MnO2 still has a certain SO2 removal ability.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Libo; Zhou, Gang

    2016-04-01

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

  13. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    SciTech Connect

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  14. Influence of surface oxygenated groups on the formation of active Cu species and the catalytic activity of Cu/AC catalyst for the synthesis of dimethyl carbonate

    NASA Astrophysics Data System (ADS)

    Zhang, Guoqiang; Li, Zhong; Zheng, Huayan; Hao, Zhiqiang; Wang, Xia; Wang, Jiajun

    2016-12-01

    Activated carbon (AC) supported Cu catalysts are employed to study the influence of surface oxygenated groups on the formation of active Cu species and the catalytic activity of Cu/AC catalyst for oxidative carbonylation of methanol to dimethyl carbonate (DMC). The AC supports are thermal treated under different temperatures in order to adjust the levels of surface oxygenated groups. The AC supports are characterized by BET, TPD-MS and XRD, and the Cu/AC catalysts are characterized by BET, XRD, TEM, XPS, AAS, CH3OH-TPD and N2O chemisorption. The results show that as the treatment temperature is below 800 °C, the BET surface area of the corresponding AC supports are nearly unchanged and close to that of the original AC (1529.6 m2/g). But as the thermal treatment temperature is elevated from 1000 to 1600 °C, the BET surface area of AC supports gradually decreases from 1407.6 to 972.2 m2/g. After loading of Cu, the BET surface area of copper catalysts is in the range of 834.4 to 1545.3 m2/g, which is slightly less than that of the respective supports. When AC is thermal treated at 400 and 600 °C, the unstable carboxylic acid and anhydrides groups are selectively removed, which has weakened the mobility and agglomeration of Cu species during the calcination process, and thus improve the Cu species dispersion over AC support. But as the treatment temperature is elevated from 600 °C to 1200 °C, the Cu species dispersion begins to decline suggesting further removal of stable surface oxygenated groups is unfavorable for Cu species dispersion. Moreover, higher thermal treatment temperature (above 1200 °C) promotes the graphitization degree of AC and leds to the decrease of Cu loading on AC support. Meanwhile, the removal of surface oxygenated groups by thermal treatment is conducive to the formation of more π-sites, and thus promote the reduction of Cu2+ to Cu+ and Cu0 as active centers. The specific surface area of (Cu+ + Cu0) is improved by thermal treatment of AC

  15. Stereospecific alkane hydroxylation by non-heme iron catalysts: mechanistic evidence for an Fe(V)=O active species.

    PubMed

    Chen, K; Que, L

    2001-07-04

    High-valent iron-oxo species have frequently been invoked in the oxidation of hydrocarbons by both heme and non-heme enzymes. Although a formally Fe(V)=O species, that is, [(Por(*))Fe(IV)=O](+), has been widely accepted as the key oxidant in stereospecific alkane hydroxylation by heme systems, it is not established that such a high-valent state can be accessed by a non-heme ligand environment. Herein we report a systematic study on alkane oxidations with H(2)O(2) catalyzed by a group of non-heme iron complexes, that is, [Fe(II)(TPA)(CH(3)CN)(2)](2+) (1, TPA = tris(2-pyridylmethyl)amine) and its alpha- and beta-substituted analogues. The reactivity patterns of this family of Fe(II)(TPA) catalysts can be modulated by the electronic and steric properties of the ligand environment, which affects the spin states of a common Fe(III)-OOH intermediate. Such an Fe(III)-peroxo species is high-spin when the TPA ligand has two or three alpha-substituents and is proposed to be directly responsible for the selective C-H bond cleavage of the alkane substrate. The thus-generated alkyl radicals, however, have relatively long lifetimes and are susceptible to radical epimerization and trapping by O(2). On the other hand, 1 and the beta-substituted Fe(II)(TPA) complexes catalyze stereospecific alkane hydroxylation by a mechanism involving both a low-spin Fe(III)-OOH intermediate and an Fe(V)=O species derived from O-O bond heterolysis. We propose that the heterolysis pathway is promoted by two factors: (a) the low-spin iron(III) center which weakens the O-O bond and (b) the binding of an adjacent water ligand that can hydrogen bond to the terminal oxygen of the hydroperoxo group and facilitate the departure of the hydroxide. Evidence for the Fe(V)=O species comes from isotope-labeling studies showing incorporation of (18)O from H(2)(18)O into the alcohol products. (18)O-incorporation occurs by H(2)(18)O binding to the low-spin Fe(III)-OOH intermediate, its conversion to a cis-H(18)O

  16. High-Activity Dealloyed Catalysts

    SciTech Connect

    Kongkanand, Anusorn

    2014-09-30

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

  17. Methane activation on supported transition metal catalysts

    NASA Astrophysics Data System (ADS)

    Carstens, Jason Ned

    At present, there is considerable interest in utilizing methane more efficiently as both a fuel source and as a starting material for the production of other, more valuable products. However, methane is a very stable molecule with strong C-H bonds that are difficult to break. This makes methane combustion or the formation of carbon-carbon bonds quite difficult. The present work focuses on the use of supported transition metal catalysts as a means of activating methane (i.e. breaking C-H bonds) at low temperatures to produce valuable products or energy. The conversion of methane into higher hydrocarbons. A low temperature (<750 K), direct process to effectively convert methane into higher hydrocarbons would be quite desirable. Such a process is thermodynamically feasible if the reaction is broken up into two separate steps. The first step is the adsorption of methane onto a transition metal catalyst at temperatures above about 600 K to produce a surface carbon species. The second step is a low temperature (<373 K) hydrogenation to convert the carbon species into higher hydrocarbons. T. Koerts et al. have pursued this approach by dissociatively absorbing methane onto silica supported transition metal catalysts at temperatures ranging between 573 K and 773 K. The result was a surface carbonaceous species and hydrogen. In the second step, the carbonaceous intermediates produced small alkanes upon hydrogenation around 373 K. A maximum yield to higher hydrocarbons of 13% was obtained on a ruthenium catalyst. The present study was conducted to further investigate the nature of the carbonaceous species reported by Koerts. Methane combustion. This investigation was conducted in an effort to better understand the mechanism of methane combustion on Pd catalysts. In the first part of this study, temperature programmed reduction (TPR) was used to investigate the oxidation and reduction dynamics of a 10 wt% Pd/ZrOsb2 catalyst used for methane combustion. TPR experiments indicate

  18. Self-assembled complexes of non-cross-linked amphiphilic polymeric ligands with inorganic species: highly active and reusable solid-phase polymeric catalysts.

    PubMed

    Yamada, Yoichi M A

    2005-07-01

    I present herein the development of highly active and reusable polymeric catalysts produced by self-assembly process of non-cross-linked amphiphilic polymeric ligands with inorganic species. Thus, PWAA 1 prepared from H3PW12O40 and poly[(N-isopropylacrylamide)-co-(acrylamide with ammonium salt)] is suitable for oxidation of alcohols, amines, and sulfides in aqueous hydrogen peroxide. PdAS 2 produced by self-organization of (NH4)2PdCl4 and poly[(N-isopropylacrylamide)10-co-diphenylphosphinostyrene] is an excellent recyclable catalyst for Suzuki-Miyaura reaction in water, water-organic solvent, and organic solvent. It is commercially available from Tokyo Kasei Kogyo (TCI). PdAS-V 3 assembled from (NH4)2PdCl4 and poly[(N-isopropylacrylamide)5-co-diphenylphosphinostyrene] provides recycling system of itself for Mizorogi-Heck reaction. TiSS 4 made from Ti(O-i-Pr)4 and poly(styryl-linked binaphtholate-co-styrene) promotes an enantioselective carbonyl-ene reaction as a recyclable catalyst.

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

    PubMed

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

    2015-12-09

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

  20. Highly Stable and Active Catalyst for Sabatier Reactions

    NASA Technical Reports Server (NTRS)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

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

  1. The electrode as organolithium reagent: catalyst-free covalent attachment of electrochemically active species to an azide-terminated glassy carbon electrode surface.

    PubMed

    Das, Atanu K; Engelhard, Mark H; Liu, Fei; Bullock, R Morris; Roberts, John A S

    2013-12-02

    The reaction of a lithium acetylide-ethylenediamine complex with azide-terminated glassy carbon surfaces affords 1,2,3-triazolyllithium surface groups that are active toward covalent C-C coupling reactions, including salt metathesis with an aliphatic halide and nucleophilic addition at an aldehyde. Surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry of electrode samples shows narrow, symmetric peaks indicating uniform attachment. X-ray photoelectron and reflectance infrared spectroscopic data provide further support for the surface-attached products. Formation of the 1,2,3-triazolyllithium linkage requires neither a catalyst nor a strained alkyne. Coverages obtained by this route are similar to those obtained by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) of ethynylferrocene with surface azides. Preconditioning of the glassy carbon disk electrodes at ambient temperature under nitrogen affords coverages comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen.

  2. The Electrode as Organolithium Reagent: Catalyst-Free Covalent Attachment of Electrochemically Active Species to an Azide-Terminated Glassy Carbon Electrode Surface

    SciTech Connect

    Das, Atanu K.; Engelhard, Mark H.; Liu, Fei; Bullock, R. Morris; Roberts, John A.

    2013-12-02

    Glassy carbon electrodes have been activated for modification with azide groups and subsequent coupling with ferrocenyl reagents by a catalyst-free route using lithium acetylide-ethylenediamine complex, and also by the more common Cu(I)-catalyzed alkyne-azide coupling (CuAAC) route, both affording high surface coverages. Electrodes were preconditioned at ambient temperature under nitrogen, and ferrocenyl surface coverages obtained by CuAAC were comparable to those reported with preconditioning at 1000 °C under hydrogen/nitrogen. The reaction of lithium acetylide-ethylenediamine with the azide-terminated electrode affords a 1,2,3-triazolyllithium-terminated surface that is active toward covalent C-C coupling reactions including displacement at an aliphatic halide and nucleophilic addition at an aldehyde. For example, surface ferrocenyl groups were introduced by reaction with (6-iodohexyl)ferrocene; the voltammetry shows narrow, symmetric peaks indicating uniform attachment. Coverages are competitive with those obtained by the CuAAC route. X-ray photoelectron spectroscopic data, presented for each synthetic step, are consistent with the proposed reactions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

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

    SciTech Connect

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

    2015-09-03

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

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

    SciTech Connect

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

    1996-06-01

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

  5. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

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

  6. Relations between coke deposition and activity of HDS catalysts

    SciTech Connect

    Brito, J.; Golding, R.; Severino, F.; Laine, J.

    1982-09-01

    Results of studies of coke deposition due to degradation of 1,3-butadiene at 400/sup 0/C are reported for studies employing supported molybdate catalysts, with and without promoters (Co and Ni) and with or without presulfiding. Initial hydrosulfurization (HDS) behavior of the catalysts was also examined. The results suggest that deposition of coke is one of the reasons for the difference in catalyst activity, and higher initial and steady state activities of presulfided catalysts suggest that H/sub 2/S treatment reduces the deactivation processes such as coke deposition. The cobalt promoted catalysts were found to be more prone to coke formation that the nickel promoted catalysts. (BLM)

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

    PubMed

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

    2012-12-21

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

  8. Process of activation of a palladium catalyst system

    SciTech Connect

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

    2011-08-02

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

  9. Activation of catalysts for synthesizing methanol from synthesis gas

    DOEpatents

    Blum, David B.; Gelbein, Abraham P.

    1985-01-01

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

  10. Activation of molecular catalysts using semiconductor quantum dots

    DOEpatents

    Meyer, Thomas J [Chapel Hill, NC; Sykora, Milan [Los Alamos, NM; Klimov, Victor I [Los Alamos, NM

    2011-10-04

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

  11. Surface structure and thiophene hydrodesulfurization activity of Mo/TiO sub 2 catalysts

    SciTech Connect

    Quincy, R.B.; Houalla, M.; Proctor, A.; Hercules, D.M. )

    1989-07-27

    Thiophene hydrodesulfurization (HDS) activity was measured for a series of Mo/TiO{sub 2} catalysts having Mo loadings of 0.5-13.5 wt% MoO{sub 3}. Raman data and thiophene HDS activity measurements suggest that three molybdenum species are present on oxidic Mo/TiO{sub 2} catalysts. A surface Mo interaction species is formed up to Mo loadings of 2.5 wt% MoO{sub 3} and is the oxidic precursor to the most active species for thiophene HDS (intrinsic thiophene HDS activity of 816 cm{sup 3} of C{sub 4} product/(h g of MoO{sub 3})). For higher Mo loadings, a second surface Mo interaction species is formed, which contributes to the background on the low-frequency side of the broad 950-960-cm{sup {minus}1} Raman peak and is less active for thiophene HDS (intrinsic activity of 250 cm{sup 3} of C{sub 4} product/(h g of MoO{sub 3})). X-ray photoelectron spectroscopic data show that both Mo surface species have similar dispersions. Catalysts with Mo loadings of > 8-9 wt % MoO{sub 3} also contain bulk MoO{sub 3}. The distribution of the three Mo species for the oxidic Mo/TiO{sub 2} catalysts is derived from Raman and HDS measurements.

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

    PubMed Central

    2016-01-01

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

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

    PubMed

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

    2014-02-18

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

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

    DOEpatents

    Lucki, Stanley J.; Brennan, James A.

    1980-01-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    1995-12-31

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

  17. Active Site Structures in Nitrogen-Doped Carbon-Supported Cobalt Catalysts for the Oxygen Reduction Reaction.

    PubMed

    Qian, Yingdan; Liu, Zheng; Zhang, Hui; Wu, Ping; Cai, Chenxin

    2016-12-07

    The catalytic mechanism and the nature of active sites are revealed for the oxygen reduction reaction (ORR) with new non-noble-metal nitrogen-doped carbon-supported transition-metal catalysts (metal-N-C catalyst). Specifically, new nitrogen-doped carbon-supported cobalt catalysts (Co-N-C catalysts) are made by pyrolyzing various ratios of the nitrogen-atom rich heterocycle compound, 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-dca) and cobalt salt (Co(NO3)2). The ORR activity (JK at 0.8 V vs RHE, in 0.1 M KOH solution) of a typical catalyst in this family, Co15-N-C800, is 8.25 mA/mg, which is much higher than the ORR activity values of N-C catalysts (0.41 mA/mg). The active site in the catalyst is found to be the Co-N species, which is most likely in the form of Co2N. Metallic cobalt (Co) particles, Co3C species, and N-C species are not catalytically active sites, nor do these moieties interact with the Co-N active sites during the catalysis of the ORR. Increasing the Co salt content during the synthesis favors the formation of Co-N active sites in the final catalyst. Higher pyrolysis temperatures (e.g., a temperature higher than 800 °C) do not favor the formation of the Co-N active sites, but cause the formed Co-N active sites to decompose, which, therefore, leads to a lower catalytic activity. This reveals that the control of the parameters that affect the final structure is critical to catalyst performance and, therefore, the effective development of high-performance heteroatom-doped non-noble-metal ORR catalysts.

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

    PubMed

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

    2014-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Balof, Shawna Lynn

    2011-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  1. Fine tuning of activity for nanoscale catalysts.

    SciTech Connect

    Strmcnik, D.; van derVliet, D.; Lucas, C.; Karapetrov, G.; Markovic, N.; Stamenkovic, V.; Materials Science Division

    2008-01-01

    similar levels of catalytic enhancement have been established for corresponding nanoscale materials. In addition to electronic properties we have found how catalytic activity could be affected by the arrangement of surface defects on nanoscale surfaces. Ability to control surface and near surface catalyst properties enables fine tuning of catalytic activity and stability of nanoscale surfaces.

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

    PubMed

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

    2014-06-01

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

  3. Development and understanding of cobaloxime activity through electrochemical molecular catalyst screening.

    PubMed

    Wakerley, David W; Reisner, Erwin

    2014-03-28

    Electrochemical molecular catalyst screening (EMoCS) has been developed. This technique allows fast analysis and identification of homogeneous catalytic species through tandem catalyst assembly and electrochemistry. EMoCS has been used to study molecular proton reduction catalysts made from earth abundant materials to improve their viability for water splitting systems. The efficacy of EMoCS is proven through investigation of cobaloxime proton reduction activity with respect to the axial ligand in aqueous solution. Over 20 axial ligands were analysed, allowing rapid identification of the most active catalysts. Structure-activity relationships showed that more electron donating pyridine ligands result in enhanced catalytic currents due to the formation of a more basic Co-H species. The EMoCS results were validated by isolating and assaying the most electroactive cobaloximes identified during screening. The most active catalyst, [Co(III)Cl(dimethyl glyoximato)2(4-methoxypyridine)], showed high electro- and photoactivity in both anaerobic and aerobic conditions in pH neutral aqueous solution.

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

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

  5. Artificial hydrogenase: biomimetic approaches controlling active molecular catalysts.

    PubMed

    Onoda, Akira; Hayashi, Takashi

    2015-04-01

    Hydrogenase catalyses reversible transformation of H2 to H(+) using an active site which includes an iron or nickel atom. Synthetic model complexes and molecular catalysts inspired by nature have unveiled the structural and functional basis of the active site with remarkable accuracy and this has led to the discovery of active synthetic catalysts. To further improve the activity of such molecular catalysts, both the first and outer coordination spheres should be well-organized and harmonized for an efficient shuttling of H(+), electrons, and H2. This article reviews recent advances in the design and catalytic properties of artificial enzymes that mimic the hydrogenase active site and the outer coordination sphere in combination with a peptide or protein scaffold.

  6. Support effects on hydrotreating activity of NiMo catalysts

    SciTech Connect

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

    2007-10-15

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

  7. Improved activity and durability of Rh-based three-way catalyst under diverse aging atmospheres by ZrO2 support.

    PubMed

    Cao, Yidan; Ran, Rui; Wu, Xiaodong; Zhao, Baohuai; Weng, Duan

    2017-02-01

    The catalytic activity and durability of Rh/ZrO2 catalyst were investigated compared with Rh/Al2O3 catalyst under diverse aging atmospheres, including lean, rich and lean-rich cyclic aging atmospheres, to simulate the real working conditions of three-way catalyst. Oxidation states and microstructures of rhodium species were investigated to correlate with the catalytic performance of the catalysts. The catalytic performance and durability of the Rh catalyst under diverse aging atmospheres were drastically enhanced by ZrO2 support. ZrO2 support was confirmed to be able to effectively inhibit rhodium sintering even under diverse aging conditions. It can also successfully keep Rh species in an active low-valence state on the surface of the catalyst. The superiority of ZrO2 support compared to Al2O3 was verified by the Rh-based monolith catalyst.

  8. Perspective: On the active site model in computational catalyst screening

    NASA Astrophysics Data System (ADS)

    Reuter, Karsten; Plaisance, Craig P.; Oberhofer, Harald; Andersen, Mie

    2017-01-01

    First-principles screening approaches exploiting energy trends in surface adsorption represent an unparalleled success story in recent computational catalysis research. Here we argue that our still limited understanding of the structure of active sites is one of the major bottlenecks towards an ever extended and reliable use of such computational screening for catalyst discovery. For low-index transition metal surfaces, the prevalently chosen high-symmetry (terrace and step) sites offered by the nominal bulk-truncated crystal lattice might be justified. For more complex surfaces and composite catalyst materials, computational screening studies will need to actively embrace a considerable uncertainty with respect to what truly are the active sites. By systematically exploring the space of possible active site motifs, such studies might eventually contribute towards a targeted design of optimized sites in future catalysts.

  9. Heterogeneous catalytic degradation of phenolic substrates: catalysts activity.

    PubMed

    Liotta, L F; Gruttadauria, M; Di Carlo, G; Perrini, G; Librando, V

    2009-03-15

    This review article explored the catalytic degradation of phenol and some phenols derivates by means of advanced oxidation processes (AOPs). Among them, only the heterogeneous catalyzed processes based on catalytic wet peroxide oxidation, catalytic ozonation and catalytic wet oxidation were reviewed. Also selected recent examples about heterogeneous photocatalytic AOPs will be presented. In details, the present review contains: (i) data concerning catalytic wet peroxide oxidation of phenolic compounds over metal-exchanged zeolites, hydrotalcites, metal-exchanged clays and resins. (ii) Use of cobalt-based catalysts, hydrotalcite-like compounds, active carbons in the catalytic ozonation process. (iii) Activity of transition metal oxides, active carbons and supported noble metals catalysts in the catalytic wet oxidation of phenol and acetic acid. The most relevant results in terms of catalytic activity for each class of catalysts were reported.

  10. Sink effect in activated carbon-supported hydrodesulfurization catalysts

    SciTech Connect

    Laine, J.; Labady, M.; Severino, F.; Yunes, S.

    1997-03-01

    A synergistic effect has been proposed in previous papers, attempting to explain the higher activity of activated carbon-supported hydrodesulfurization (HDS) catalysts with respect to conventional alumina-supported catalysts, reported earlier. However, activated carbon characteristics can be strongly affected by the raw material and the method of activation. Thus, previous work using Ni-Mo catalysts supported on two different activated carbons (one prepared by {open_quotes}physical{close_quotes} and the other by {open_quotes}chemical{close_quotes} activation) showed different optimal Ni concentrations for higher HDS activity, such difference being attributed to the predominance of Topsoe`s Type I {open_quotes}NiMoS{close_quotes} phase in one carbon and the predominance of Type II in the other. Due to the lack of proper characterization of the activated carbon supported catalysts of the previous work, this paper presents further data suggesting that microporosity provided by the activated carbon may be the responsible for the above referred synergism. 12 refs., 1 fig., 3 tabs.

  11. Reactivity Descriptors for the Activity of Molecular MN4 Catalysts for the Oxygen Reduction Reaction.

    PubMed

    Zagal, José H; Koper, Marc T M

    2016-11-14

    Similarities are established between well-known reactivity descriptors of metal electrodes for their activity in the oxygen reduction reaction (ORR) and the reactivity of molecular catalysts, in particular macrocyclic MN4 metal complexes confined to electrode surfaces. We show that there is a correlation between the M(III) /M(II) redox potential of MN4 chelates and the M-O2 binding energies. Specifically, the binding energy of O2 (and other O species) follows the M(III) -OH/M(II) redox transition for MnN4 and FeN4 chelates. The ORR volcano plot for MN4 catalysts is similar to that for metal catalysts: catalysts on the weak binding side (mostly CoN4 chelates) yield mainly H2 O2 as the product, with an ORR onset potential independent of the pH value on the NHE scale (and therefore pH-dependent on the RHE scale); catalysts on the stronger binding side yield H2 O as the product with the expected pH-dependence on the NHE scale. The suggested descriptors also apply to heat-treated pyrolyzed MN4 catalysts.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    SciTech Connect

    Xiang-Dong Peng

    2002-05-01

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

  14. Catalytically Active and Spectator Ce(3+) in Ceria-Supported Metal Catalysts.

    PubMed

    Kopelent, René; van Bokhoven, Jeroen A; Szlachetko, Jakub; Edebeli, Jacinta; Paun, Cristina; Nachtegaal, Maarten; Safonova, Olga V

    2015-07-20

    Identification of active species and the rate-determining reaction steps are crucial for optimizing the performance of oxygen-storage materials, which play an important role in catalysts lowering automotive emissions, as electrode materials for fuel cells, and as antioxidants in biomedicine. We demonstrated that active Ce(3+) species in a ceria-supported platinum catalyst during CO oxidation are short-lived and therefore cannot be observed under steady-state conditions. Using time-resolved resonant X-ray emission spectroscopy, we quantitatively correlated the initial rate of Ce(3+) formation under transient conditions to the overall rate of CO oxidation under steady-state conditions and showed that ceria reduction is a kinetically relevant step in CO oxidation, whereas a fraction of Ce(3+) was present as spectators. This approach can be applied to various catalytic processes involving oxygen-storage materials and reducible oxides to distinguish between redox and nonredox catalytic mechanisms.

  15. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    Shao-Horn, Yang

    2015-07-28

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

  16. Highly active thermally stable nanoporous gold catalyst

    SciTech Connect

    Biener, Juergen; Wittstock, Arne; Biener, Monika M.; Bagge-Hansen, Michael; Baeumer, Marcus; Wichmann, Andre; Neuman, Bjoern

    2016-12-20

    In one embodiment, a system includes a nanoporous gold structure and a plurality of oxide particles deposited on the nanoporous gold structure; the oxide particles are characterized by a crystalline phase. In another embodiment, a method includes depositing oxide nanoparticles on a nanoporous gold support to form an active structure and functionalizing the deposited oxide nanoparticles.

  17. Structure-activity relationship of CuO/MnO2 catalysts in CO oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Kun; Qian, Zhaoxia; Hua, Qing; Jiang, Zhiquan; Huang, Weixin

    2013-05-01

    A series of CuO/MnO2 catalysts with different CuO loadings were synthesized by the incipient wetness impregnation method. The catalysts were characterized by N2 adsorption-desorption isotherms, powder X-ray diffraction, X-ray photoelectron spectroscopy, H2-temperature programmed reduction, CO-temperature programmed reduction and scanning electron microscope. The CuO/MnO2 catalysts with CuO loading of 1-40% exhibit almost the same catalytic performance toward CO oxidation while those with higher CuO loadings exhibit a much poorer catalytic activity. The structural characterization results demonstrate that the CuO-MnO2 interface is the active site for CO oxidation in CuO/MnO2 catalysts and CO oxidation over CuO/MnO2 probably follows the interfacial reaction mechanism in which CO chemisorbed on CuO reacts with oxygen species on MnO2 at the CuO-MnO2 interface.

  18. Mechanochemical activation of iron ore-based catalysts for the hydrogenation of brown coal

    SciTech Connect

    Kuznetsov, P.N.; Kuznetsova, L.I.; Kartseva, N.V.; Chumakov, V.G.

    1998-12-31

    Genesis of iron based catalysts on mechanical treatment in a planetary mill was investigated. Methods for achieving satisfactory mixing of catalyst on coal were surveyed. The preferred method was to conduct mechanochemical activation in the presence of sulfur and water additives, application of activated catalyst to coal followed by drying of the contact produced.

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

    SciTech Connect

    Not Available

    2011-02-01

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

  20. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

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

  1. Iron-containing mesoporous aluminosilicate: a highly active and reusable heterogeneous catalyst for hydroarylation of styrenes.

    PubMed

    Haldar, Satyajit; Koner, Subratanath

    2010-09-03

    Hydroarylation of various styrene derivatives has been successfully carried out in excellent yield using Fe-Al-MCM-41 catalyst. The C-H functionalization using solid heterogeneous catalyst provides a straightforward access to a series of important 1,1-diarylalkane products. The catalyst can be recovered and reused at least three times without any significant loss in its catalytic activity.

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

    SciTech Connect

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

  4. Evaluation of photocatalytic activities of supported catalysts on NaX zeolite or activated charcoal.

    PubMed

    de Brites-Nóbrega, Fernanda F; Polo, Aldino N B; Benedetti, Angélica M; Leão, Mônica M D; Slusarski-Santana, Veronice; Fernandes-Machado, Nádia R C

    2013-12-15

    This study aimed to evaluate the photocatalytic activity of ZnO and Nb2O5 catalysts, both supported on NaX zeolite and activated charcoal (AC). The synergistic effect between oxide and support and the influence of solution pH (3, 7 and 9) on photocatalytic degradation of reactive blue 5G (C.I. 222) were analyzed. The catalysts Nb2O5/NaX, Nb2O5/AC and ZnO/NaX, ZnO/AC with 5 and 10% (wt%) were prepared by wet impregnation. The results showed that the catalysts exhibit quite different structural and textural properties. The synergic effect between ZnO and NaX support was higher than that with the activated charcoal, showing that these catalysts were more efficient. The most photoactive catalyst was 10% ZnO/NaX which showed 100% discoloration of the dye solution at pH 3, 7 and 9 after 0.5, 5 and 2h of irradiation, respectively. The hydrolytic nature of zeolite favored the formation of surface hydroxyl radicals, which increased the activity of the photocatalyst. Thus, catalysts supported on NaX zeolite are promising for use in photocatalysis.

  5. The Effect of Exposed Facets of Ceria to the Nickel Species in Nickel-Ceria Catalysts and Their Performance in a NO + CO Reaction.

    PubMed

    Tang, Ke; Liu, Wei; Li, Jing; Guo, Jinxin; Zhang, Jingcai; Wang, Shuping; Niu, Shengli; Yang, Yanzhao

    2015-12-09

    CeO2 rods with {110} facets and cubes with {100} facets were utilized as catalyst supports to probe the effect of crystallographic facets on the nickel species and the structure-dependent catalytic performance. Various analysis methods (ex and in situ XRD, TEM, Raman, XPS, TPR, TPD) were used to investigate the structural forms of the catalysts, and these results indicated that the deposition of nickel species resulted in the formation of two main active types of the catalyst components: NiO strongly or weakly interacted with the surface and Ni-Ce-O solid solution. Notably, the states and distribution ratio of nickel species were related to the shape of CeO2. It was found that CeO2 rods had more active sites to coordinate with nickel species to form a strong interaction with NiO on the surface and a more stable construction when compared to cubes. Furthermore, the nickel-ceria catalysts with rod shape were more active towards NO oxidation with complete conversion below 191 °C, but for cube shape, complete conversion occurred above 229 °C (e.g., for nickel loading of ∼5%, the complete conversion temperature was 154 °C for the rod shape and 229 °C for the cube shape). On the basis of the analysis of the catalysts structure, the superior catalytic activity was due to a combination of surface structures of NiO (mainly strongly interacting with the surface) and nickel ions Ni(2+) in the Ni-Ce-O bulk phase.

  6. Magnetic iron species highly dispersed over silica: use as catalysts for removal of pollutants in water.

    PubMed

    Freitas, Victor A A; Maia, Laura A; Belardinelli, Rolando E; Ardisson, Jose D; Pereira, Márcio C; Oliveira, Luiz C A

    2016-04-04

    Fe2O3-SiO2 composites were prepared by impregnation (sample FeIMP) or doping (sample FeDOP) in the structure of porous silica. The dye removal capacity of the materials was investigated through adsorption and oxidation studies of methylene blue and rhodamine B. N2 adsorption/desorption measurements on FeIMP and FeDOP resulted in specific areas of 27 and 235 m(2) g(-1), respectively. Mössbauer spectroscopy and XRD data detected hematite and maghemite as the iron phases in the samples FeIMP and FeDOP, respectively. Adsorption isotherms and kinetic studies of the dyes were better fitted in DKR model for FeDOP, where the process follows a pseudo-second order with the interparticle diffusion step being the rate-limiting step. On the other hand, FeIMP has better fit in the Langmuir model. Photocatalytic activity was observed in FeDOP under UV irradiation by the presence of reaction-hydroxylated intermediates for MB (m/z = 301) and RhB (m/z = 459). However, the photocatalytic activity was strongly influenced by the adsorption affinity between dye/catalyst. Photogenerated holes are the species responsible for the dye degradation when the adsorption is too strong, while hydroxyl radical action will be favored when the adsorption is not vigorous as detected by ESI-MS. Graphical Abstract Action of photogenerated holes and free electrons into the photocatalytically mechanism of methylene blue degradation over a semiconductor.

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

    SciTech Connect

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

    2014-12-17

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

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

    DOE PAGES

    Marx, Vanessa M.; Sullivan, Alexandra H.; Melaimi, Mohand; ...

    2014-12-17

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

  9. When Inert Becomes Active: A Fascinating Route for Catalyst Design.

    PubMed

    Lyalin, Andrey; Gao, Min; Taketsugu, Tetsuya

    2016-10-01

    In this Personal Account, we review the work of our group in the area of environmental and energy-related nanocatalysis over the past seven years. We focus on understanding the fundamental mechanisms that control the properties of atomic clusters and nanoparticles - a form of matter that is intermediate between atoms and their bulk counterpart. The emphasis is on the theoretical design of effective catalysts based on cheap and abundant elements. The main idea that stands behind our work is that even catalytically inactive or completely inert materials can be functionalized at the nanoscale via the size, structure, morphology, and support effects. Such an approach opens up new ways to design catalytically active systems based on materials never before considered as catalysts. In particular, we demonstrate that hexagonal boron nitride (h-BN), which has been traditionally considered an inert material, can be functionalized and become active for a number of catalytic reactions involving oxygen activation, oxidation by molecular oxygen, and the oxygen reduction reaction.

  10. Stability issues in Pd-based catalysts: the role of surface Pt in improving the stability and oxygen reduction reaction (ORR) activity.

    PubMed

    Singh, R K; Rahul, R; Neergat, M

    2013-08-21

    Carbon-supported Pd and Pd3Co catalysts have been electrochemically characterized in 0.1 M HClO4 solution and we found that both catalysts were unstable. On repeated potential cycling, the electrochemical surface area of the catalysts decreases and the oxygen reduction reaction (ORR) activity suffers. To stabilize surface Pd atoms of both Pd and Pd3Co catalysts, we deposited Pt using adsorbed hydrogen on the catalytically active Pd sites. The Pt : Pd ratio of Pt-coated Pd and Pt-coated Pd3Co catalysts suggests half-a-monolayer coverage of Pt (two hydrogen atoms required for reducing a Pt(2+) ion). The Pt : Pd ratio of Pt-coated Pd3Co catalyst obtained from the simple geometrical hard sphere model, energy-dispersive X-ray spectroscopy (EDS) line scan and bulk EDS agrees very well with that calculated from the hydrogen desorption (H(des)) charge of Pd3Co. At the same time, the Pt : Pd ratio of Pt-coated Pd calculated from the H(des) charge of Pd catalyst is significantly lower than the ratio obtained from the other methods. Thus, the Pt : Pd ratio of the Pt-coated Pd catalyst estimated from the H(des) region of Pd is an underestimation of the composition. This suggests that Pd forms an electrochemically inactive species from the H(upd) region itself and Co in Pd3Co seems to stabilize Pd against oxidation by delaying the formation of electrochemically inactive species to higher potentials above the H(upd) region. The voltammograms along with the peroxide formation characteristics of the catalysts support the above observations. The deposited Pt on the surface of the Pd and Pd3Co catalysts masks active Pd sites from the electrochemical environment and even partial coverage with Pt improves the stability and ORR activity of the catalysts when compared to that of the respective Pt-free counterparts.

  11. Gold catalysts for pure hydrogen production in the water-gas shift reaction: activity, structure and reaction mechanism.

    PubMed

    Burch, Robbie

    2006-12-21

    indicated but the possible role of special sites (e.g., edge sites) on the gold clusters cannot be excluded. These may be important for CO oxidation but the fact that water has to be activated in the water gas shift reaction may point towards a more dominant role for the interfacial sites. The mechanism of the water gas shift reaction on gold and other low temperature catalysts has been widely investigated but little agreement exists. However, it is shown that a single "universal" model is consistent with much of the experimental literature. In this, it is proposed that the dominant surface intermediate is a function of reaction conditions. For example, as the temperature is increased the dominant species changes from a carbonate or carboxylate species, to a formate species and eventually at high temperatures to a mechanism that is characteristic of a redox process. Similar changes in the dominant intermediate are observed with changes in the gas composition. Overall, it is shown that reported variations in the kinetics, structure and reaction mechanism for the water gas shift reaction on gold catalysts can now be understood and rationalised.

  12. Activation processes and polyethylene formation on a phillips model catalyst studied by laser ablation, laser desorption, and static secondary ion mass spectrometry.

    PubMed

    Aubriet, Frédéric; Muller, Jean-François; Poleunis, Claude; Bertrand, Patrick; Di Croce, Pascal G; Grange, Paul

    2006-03-01

    Since the discovery of the Phillips catalysts, there still is much uncertainty concerning their activation, their molecular structure, the nature of the active chromium sites, and the polymerization mechanisms. Surface techniques are not easy to be used for such study according to the nonconductive behavior of the support. Therefore, model Phillips catalyst is elaborated by spin coating a trivalent chromium precursor on a silicon wafer. The surface characterization of this model catalyst is conducted by laser ablation mass spectrometry (LA-MS), laser desorption/ionization mass spectrometry (LDI-MS), and static secondary ion mass spectrometry (s-SIMS), at different steps of its preparation. To validate our approach, a comparison is also made between the model and the real Philips catalyst. Moreover, the model catalyst efficiency for polyethylene synthesis is evaluated and allows us to discuss the validity of the mechanisms previously proposed to explain the catalytic process. The characterization of Phillips model catalyst by mass spectrometry allows us to better understand the activation processes of such catalyst. Depending on the activation temperature, chromium oxide species are formed and anchored at the support surface. They consist mainly in mono-chromium sites at high temperature. The chromium valence is hexavalent. This model catalyst is active for the polymerization of ethylene. A pseudo-oligomer molecular weight distribution is observed by LA-MS, whereas s-SIMS allows us to elucidate the anchorage of the polymer at activate chromium surface sites.

  13. Graphitic carbon nitride induced activity enhancement of OMS-2 catalyst for pollutants degradation with peroxymonosulfate

    NASA Astrophysics Data System (ADS)

    Li, Jun; Fang, Jia; Gao, Long; Zhang, Jingwen; Ruan, Xinchao; Xu, Aihua; Li, Xiaoxia

    2017-04-01

    Low valent manganese species and surface oxygen vacancies in OMS-2 play an important role in catalytic reactions, and it is highly desirable and challenging to develop a feasible strategy of increasing the Mn(II) and Mn(III) species concentration in the oxide. Herein, the OMS-2/g-C3N4 hybrids (OMS-2/CN) were prepared by a facile refluxing approach. It was found that the MnOx precursor from the reaction of KMnO4 and MnSO4 was transformed into OMS-2 nanofibers with the formation of more Mn(II) and Mn(III) species in OMS-2 and the destruction and oxidation of g-C3N4. The hybrids exhibited higher efficiency for pollutants degradation in the presence of PMS than the pure OMS-2 or g-C3N4. There was a linear correlation between the specific initial rate and the ratio of Mn(II + III)/Mn(IV). Mechanism investigation indicated that high active manganese species or caged radicals were produced through the oxidation of Mn(II) and Mn(III) by PMS and contributed to the degradation reaction. During five consecutive cycles, the catalyst exhibited good reusability and stability. Therefore, the OMS-2/CN hybrids are promising catalysts for wastewater treatment with PMS as the oxidant.

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

    DTIC Science & Technology

    2016-09-12

    Irreversible Catalyst Activation Enables Hyperpolarization and Water Solubility for NMR Signal Amplification by Reversible Exchange Milton L. Truong...Supporting Information ABSTRACT: Activation of a catalyst [IrCl(COD)(IMes)] (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; COD = cyclooctadiene...for signal amplification by reversible exchange (SABRE) was monitored by in situ hyperpolarized proton NMR at 9.4 T. During the catalyst -activation

  15. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

    PubMed

    Hung, Chang-Mao

    2009-07-30

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

  16. Highly active and efficient catalysts for alkoxycarbonylation of alkenes

    NASA Astrophysics Data System (ADS)

    Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

    2017-01-01

    Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000 TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.

  17. Highly active and efficient catalysts for alkoxycarbonylation of alkenes

    PubMed Central

    Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

    2017-01-01

    Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h−1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product. PMID:28120947

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

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

    2015-02-01

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

  20. Substrate specificity of an actively assembling amyloid catalyst.

    PubMed

    Heier, Jason L; Mikolajczak, Dorian J; Böttcher, Christoph; Koksch, Beate

    2017-01-01

    In the presence of Zn(2+) , the catalytic, amyloid-forming peptide Ac-IHIHIQI-NH2 , was found to exhibit enhanced selectivity for hydrophobic p-nitrophenyl ester substrates while in the process of self-assembly. As opposed to the substrate p-nitrophenyl acetate, which was more effectively hydrolyzed with Ac-IHIHIQI-NH2 in its fully fibrillar state, the hydrophobic substrate Z-L-Phe-ONp was converted with a second-order rate constant more than 11-times greater when the catalyst was actively assembling. Under such conditions, Z-L-Phe-ONp hydrolysis proceeded at a greater velocity than the more hydrophilic and otherwise more labile ester Boc-L-Asn-ONp. When assembling, the catalyst also showed increased selectivity for the L-enantiomer of Z-Phe-ONp. These findings suggest the occurrence of increased interactions of hydrophobic moieties of the substrate with exposed hydrophobic surfaces of the assembling peptides and present valuable features for future de novo design consideration.

  1. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide.

    PubMed

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

    2016-10-01

    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.

  2. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    NASA Astrophysics Data System (ADS)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are

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

    PubMed Central

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

    2013-01-01

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

  4. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts.

    PubMed

    Strasser, Peter; Koh, Shirlaine; Anniyev, Toyli; Greeley, Jeff; More, Karren; Yu, Chengfei; Liu, Zengcai; Kaya, Sarp; Nordlund, Dennis; Ogasawara, Hirohito; Toney, Michael F; Nilsson, Anders

    2010-06-01

    Electrocatalysis will play a key role in future energy conversion and storage technologies, such as water electrolysers, fuel cells and metal-air batteries. Molecular interactions between chemical reactants and the catalytic surface control the activity and efficiency, and hence need to be optimized; however, generalized experimental strategies to do so are scarce. Here we show how lattice strain can be used experimentally to tune the catalytic activity of dealloyed bimetallic nanoparticles for the oxygen-reduction reaction, a key barrier to the application of fuel cells and metal-air batteries. We demonstrate the core-shell structure of the catalyst and clarify the mechanistic origin of its activity. The platinum-rich shell exhibits compressive strain, which results in a shift of the electronic band structure of platinum and weakening chemisorption of oxygenated species. We combine synthesis, measurements and an understanding of strain from theory to generate a reactivity-strain relationship that provides guidelines for tuning electrocatalytic activity.

  5. Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

    PubMed

    Bernicke, Michael; Ortel, Erik; Reier, Tobias; Bergmann, Arno; Ferreira de Araujo, Jorge; Strasser, Peter; Kraehnert, Ralph

    2015-06-08

    Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) .

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

    SciTech Connect

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

    1994-10-01

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

  7. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGES

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

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

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

    PubMed

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

    2013-11-13

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

  9. Laser-activated gold catalysts for liquid-phase growth of cadmium selenide nanowires.

    PubMed

    Huang, C; Mao, J; Chen, X M; Yang, J; Du, X W

    2015-02-07

    A laser-activated-catalyst (LAC) technique was developed to grow CdSe nanowires in liquid medium at room temperature. The gold catalysts dispersed in the precursor solution were activated by a pulsed laser so as to decompose the precursor and catalyse the nanowire growth simultaneously. The LAC technique can achieve accurate positioning of nanowires, which is beneficial for device fabrication.

  10. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity.

    PubMed

    Stibingerova, Iva; Voltrova, Svatava; Kocova, Sarka; Lindale, Matthew; Srogl, Jiri

    2016-01-15

    A new type of robust, heterogeneous, modular Pd catalyst with metal embedded in the gel matrix is presented. The regulatory element of its catalytic activity has been introduced via chemical changes in the gel. The concept is illustrated in a series of Suzuki-Miyaura cross-coupling reactions. The demonstrated catalyst activity variations depend on the structure of the gel.

  11. CO2 copolymers from epoxides: catalyst activity, product selectivity, and stereochemistry control.

    PubMed

    Lu, Xiao-Bing; Ren, Wei-Min; Wu, Guang-Peng

    2012-10-16

    systems were also very efficient in catalyzing the terpolymerization of cyclohexene oxide, propylene oxide and CO(2). The resulting terpolymer had a single glass-transition temperature and a single thermolysis peak. This Account also provides a thorough mechanistic understanding of the high activities, excellent selectivities, and unprecedented stereochemical control of these Co(III)-based catalysts in the production of CO(2) copolymers . The catalysis occurs through a cooperative monometallic mechanism, in which the Lewis acidic Co(III) ion serves as electrophile to activate then epoxide and the nucleophilic counterion or cocatalyst serves as a nucleophile to initiate polymer-chain growth. The high activity and excellent regioselectivity observed in the epoxide ring-opening reactions results from epoxide activation through the moderate electrophilicity of the Co(III) ion, the fast insertion of CO(2) into the Co-O bond, and the facile dissociation of the propagating carboxylate species from the central metal ion. The reversible intra- or intermolecular Co-O bond formation and dissociation helps to stabilize the active Co(III) species against reversion to the inactive Co(II) ion. We also describe our laboratory's recent preparation of the first crystalline CO(2)-based polymer via highly stereospecific copolymerization of CO(2) and meso-cyclohexene oxide and the selective synthesis of perfectly alternating polycarbonates from the coupling of CO(2) with epoxides bearing an electron-withdrawing group.

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

    DOEpatents

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

    2001-01-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-10-22

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

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

    PubMed Central

    2011-01-01

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

  17. Mechanism of activation of a hafnium pyridyl-amide olefin polymerization catalyst: ligand modification by monomer.

    PubMed

    Froese, Robert D J; Hustad, Phillip D; Kuhlman, Roger L; Wenzel, Timothy T

    2007-06-27

    We have investigated the olefin polymerization mechanism of hafnium catalysts supported by a pyridyl-amide ligand with an ortho-metalated naphthyl group. Ethylene-alpha-olefin copolymers from these catalysts have broad molecular weight distributions that can be fit to a bimodal distribution. We propose a unique mechanism to explain this behavior involving monomer modification of the catalyst, which generates multiple catalyst species when multiple monomers are present. More specifically, we present evidence that the hafnium alkyl cation initially undergoes monomer insertion into the Hf-naphthyl bond, which permanently modifies the ligand to generate new highly active olefin polymerization catalysts. Under ethylene/octene copolymerization conditions, a plurality of new catalysts is formed in relative proportion to the respective monomer concentrations. Due to the asymmetry of the metal complex, two "ethylene-inserted" and eight "octene-inserted" isomers are possible, but it is a useful approximation to consider only one of each in the polymerization behavior. Consequently, gel permeation chromatography data for the polymers can be fit to a bimodal distribution having a continuous shift from a predominantly low molecular weight fraction to predominantly higher molecular weight fraction as [octene]/[ethylene] is increased. Theoretical calculations show that such insertions into the Hf-aryl bond have lower barriers than corresponding insertions into the Hf-alkyl bond. The driving forces for this insertion into the Hf-aryl bond include elimination of an eclipsing H-H interaction and formation of a stabilizing Hf-arene interaction. These new "monomer-inserted catalysts" have no beta-agostic interaction, very weak olefin binding, and olefin-insertion transition states which differ on the two sides by more than 4 kcal/mol. Thus, the barrier to site epimerization is very low and high polymerization rates are possible even when the chain wags prior to every insertion

  18. Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

    2016-12-01

    One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

  19. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

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

  20. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

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

  1. Molybdenum phosphosulfide: an active, acid-stable, earth-abundant catalyst for the hydrogen evolution reaction.

    PubMed

    Kibsgaard, Jakob; Jaramillo, Thomas F

    2014-12-22

    Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non-noble-metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed-metal alloy catalysts are well-known, MoP|S represents a more uncommon mixed-anion catalyst where synergistic effects between sulfur and phosphorus produce a high-surface-area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water-splitting cells.

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

    PubMed

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

    2014-10-06

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

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

    SciTech Connect

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

    2010-09-15

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

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

    SciTech Connect

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

    2011-04-20

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

  5. Electrocatalytic activity of PtAu/C catalysts for glycerol oxidation.

    PubMed

    Jin, Changchun; Sun, Chao; Dong, Rulin; Chen, Zhidong

    2012-01-01

    The electrocatalytic oxidation of glycerol on PtAu/C catalysts has been investigated by cyclic voltammetry. PtAu bimetallic nanoparticles are prepared by chemical reduction. Carbon-supported PtAu catalysts are found to exhibit high electrocatalytic activity for the oxidation of glycerol in alkaline solution in terms of oxidation potential and current density as well as stability, and PtAu/C catalysts with different Pt:Au composition ratios show no much difference in catalytic activity. In acidic solution, PtAu/C catalysts exhibit similar to Pt/C catalysts in activity, but the advantage of the PtAu/C catalysts in terms of per unit mass of platinum is still obvious. The PtAu/C catalysts, in a wide Pt:Au ratio range, show a remarkable enhancement in the mass specific activity of platinum with decreasing platinum content in both alkaline and acidic solutions. This is of significance for reducing the usage of platinum and indicates that though platinum acts as main active sites, gold also plays an important role in the function of PtAu/C catalysts.

  6. Remaining activity determination of the resid desulfurization catalyst in a commerical plant

    SciTech Connect

    Yung-Ji Tarng; Sheng-Yang Ju

    1996-12-31

    The objective of this paper is to present a method to determine the remaining catalyst activity of the resid desulfurization plant. Using the daily available operating data, we can establish a performance curve which is a temperature versus days on stream curve. By the use of the performance curve, we can in situ predict how much the catalyst life remains. With the knowledge of the catalyst life remaining, plant engineers are able to control the operating conditions to meet the specified run length of the catalyst suggested by the catalyst venders and refinery planning department. There are five heavy oil desulfurization (RDS) plants in Chinese Petroleum Corporation (CPC) to produce the low sulfur fuel oil and low metal content feed stocks for the downstream processes. In general four or five reactors are connected in series for the reacting system and catalysts of various types are loaded in each reactor. 3 refs., 1 fig., 4 tabs.

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

    SciTech Connect

    Li, Baitao Zhu, Yanrun; Jin, Xiaojing

    2015-01-15

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

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

    SciTech Connect

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

    2014-10-01

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

  9. Effects of various poisoning compounds on the activity and stereospecificity of heterogeneous Ziegler–Natta catalyst

    PubMed Central

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

    2008-01-01

    A TiCl4/ethylbenzoate/MgCl2 Ziegler–Natta catalyst was pretreated with chemically different poisoning compounds to investigate their effects on the catalyst activity and stereospecificity for propylene polymerization. The poisoning power on the activity was in the order of methanol > acetone > ethyl acetate. A kinetic analysis using the stopped-flow method revealed that addition of the poisoning materials decreased the activity through the reduction of the number of active sites, whereas the catalyst isospecificity was hardly affected by these materials. PMID:27877969

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

    SciTech Connect

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

    2015-01-01

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

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

    DOE PAGES

    Cullen, David A.; Lopez-Haro, Miguel; Bayle-Guillemaud, Pascale; ...

    2015-01-01

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

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

    DOEpatents

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

    1983-02-08

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

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

    SciTech Connect

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

    2014-07-23

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

  14. Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques.

    PubMed

    Kramm, Ulrike I; Lefèvre, Michel; Larouche, Nicholas; Schmeisser, Dieter; Dodelet, Jean-Pol

    2014-01-22

    The aim of this work is to clarify the origin of the enhanced PEM-FC performance of catalysts prepared by the procedures described in Science 2009, 324, 71 and Nat. Commun. 2011, 2, 416. Catalysts were characterized after a first heat treatment in argon at 1050 °C (Ar) and a second heat treatment in ammonia at 950 °C (Ar + NH3). For the NC catalysts a variation of the nitrogen precursor was also implemented. (57)Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, neutron activation analysis, and N2 sorption measurements were used to characterize all catalysts. The results were correlated to the mass activity of these catalysts measured at 0.8 V in H2/O2 PEM-FC. It was found that all catalysts contain the same FeN4-like species already found in INRS Standard (Phys. Chem. Chem. Phys. 2012, 14, 11673). Among all FeN4-like species, only D1 sites, assigned to FeN4/C, and D3, assigned to N-FeN2+2 /C sites, were active for the oxygen reduction reaction (ORR). The difference between INRS Standard and the new catalysts is simply that there are many more D1 and D3 sites available in the new catalysts. All (Ar + NH3)-type catalysts have a much larger porosity than Ar-type catalysts, while the maximum number of their active sites is only slightly larger after a second heat treatment in NH3. The large difference in activity between the Ar-type catalysts and the Ar + NH3 ones stems from the availability of the sites to perform ORR, as many sites of the Ar-type catalysts are secluded in the material, while they are available at the surface of the Ar + NH3-type catalysts.

  15. Recovery of Alkylation Activity in Deactivated USY Catalyst Using Supercritical Fluids: A Comparison of Light Hydrocarbons

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2004-05-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical fluids (SCF). A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical fluids over the catalyst bed. A comparison of reactivation fluids on catalyst activity recovery is reported. Fluids examined included helium, propane, n-butane, isobutane, n-pentane, and isopentane. Phases studied included gas, liquid, and supercritical. As much as 82% of the fresh catalyst activity was recovered when employing supercritical isobutane. The ability of the fluid to facilitate a hydride reaction with the adsorbed deactivating high-molecular weight carbocations was indicated as an important property necessary to attain high levels of catalyst activity recovery. Activity recovery utilizing supercritical fluids that enhance reactivation by both reacting with and desorbing fouling compounds appears to be a promising technique to advance solid catalyst alkylation.

  16. Generation of reactive oxygen species and oxidative stress in Escherichia coli and Staphylococcus aureus by a novel semiconductor catalyst

    NASA Astrophysics Data System (ADS)

    Chow, K. L.; Mak, N. K.; Wong, M. H.; Zhou, X. F.; Liang, Y.

    2011-03-01

    The objective of this study was to investigate antimicrobial mechanisms of a new catalytic material (charge transfer auto oxidation-reduction type catalyst, CT catalyst) that may have great potential for application in water/wastewater treatment. Generation of reactive oxygen species (ROS) in bacteria-free solution, induction of ROS and oxidative damage in bacteria (including E. coli and S. aureus) were examined for the CT catalyst. The results showed that significantly higher ( p < 0.05, via t-test) amount of hydroxyl radicals was generated by the CT catalyst compared with the control, particularly after 6 h of contact time that more than twice of the amount of the control was produced. The generation of ROS in the bacteria was greater under higher pH and temperature levels, which closely related with the oxidative damage in cells. The results indicated that CT catalyst induced oxidative damage in the bacteria might serve as an important mechanism interpreting the anti-microbial function of the CT catalyst.

  17. On Shape Normalization for Non-Uniformly Active Catalyst Pellets. III.

    DTIC Science & Technology

    1981-10-01

    ON SHAPE NORMALIZATION FOR NON-UNIFORMLY ACTIVE CATALYST PELLET--ETC(U) OCT Al M4 MORBIDELLI . A VARMA DAA629 RI C 001 UNCLASSIFIED MRC-TSR-2289 NL 7...RESEARCH CENTRR ON SHAPE NORMALIZATION FOR NON-UNIFORMLY ACTIVE CATALYST PELLETS - III M. Morbidelli and A. Varma Technical Summary Report #2289 October...lies with N4RC, and not with the authors of this report. ON SHAPE NORMALIZATION FOR NON-UNIFORMLY ACTIVE CATALYST PELLETS - III M. Morbidelli and A

  18. High activity redox catalysts synthesized by chemical vapor impregnation.

    PubMed

    Forde, Michael M; Kesavan, Lokesh; Bin Saiman, Mohd Izham; He, Qian; Dimitratos, Nikolaos; Lopez-Sanchez, Jose Antonio; Jenkins, Robert L; Taylor, Stuart H; Kiely, Christopher J; Hutchings, Graham J

    2014-01-28

    The use of precious metals in heterogeneous catalysis relies on the preparation of small nanoparticles that are stable under reaction conditions. To date, most conventional routes used to prepare noble metal nanoparticles have drawbacks related to surface contamination, particle agglomeration, and reproducibility restraints. We have prepared titania-supported palladium (Pd) and platinum (Pt) catalysts using a simplified vapor deposition technique termed chemical vapor impregnation (CVI) that can be performed in any standard chemical laboratory. These materials, composed of nanoparticles typically below 3 nm in size, show remarkable activity under mild conditions for oxidation and hydrogenation reactions of industrial importance. We demonstrate the preparation of bimetallic Pd-Pt homogeneous alloy nanoparticles by this new CVI method, which show synergistic effects in toluene oxidation. The versatility of our CVI methodology to be able to tailor the composition and morphology of supported nanoparticles in an easily accessible and scalable manner is further demonstrated by the synthesis of Pdshell-Aucore nanoparticles using CVI deposition of Pd onto preformed Au nanoparticles supported on titania (prepared by sol immobilization) in addition to the presence of monometallic Au and Pd nanoparticles.

  19. Ultrasound-assisted Micro-emulsion Synthesis of a Highly Active Nano-particle Catalyst

    DTIC Science & Technology

    2010-03-01

    Ultrasound-assisted Micro -emulsion Synthesis of a Highly Active Nano -particle Catalyst by Rongzhong Jiang and Charles Rong ARL-TR-5114...ARL-TR-5114 March 2010 Ultrasound-assisted Micro -emulsion Synthesis of a Highly Active Nano -particle Catalyst Rongzhong Jiang and...TYPE DRI 3. DATES COVERED (From - To) 2009 to 2010 4. TITLE AND SUBTITLE Ultrasound-assisted Micro -emulsion Synthesis of a Highly Active Nano

  20. Revealing the nature of the active site on the carbon catalyst for C-H bond activation.

    PubMed

    Sun, XiaoYing; Li, Bo; Su, Dangsheng

    2014-09-28

    A reactivity descriptor for the C-H bond activation on the nanostructured carbon catalyst is proposed. Furthermore the calculations reveal that the single ketone group can be an active site in ODH reaction.

  1. Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

    NASA Technical Reports Server (NTRS)

    Shah, Pinakin M.

    1990-01-01

    An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

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

    PubMed

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

    2013-11-06

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

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

    SciTech Connect

    2009-03-01

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

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

    SciTech Connect

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

    1993-02-01

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

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

    SciTech Connect

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

    1993-02-01

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

  6. High activity, high yield tin modified platinum-iridium catalysts, and reforming process utilizing such catalysts

    SciTech Connect

    Baird, W.C. Jr.; Swan, G.A. III; Boyle, J.P.

    1993-06-22

    A process is described for improving the octane quality of a naphtha which comprises reforming said naphtha at reforming conditions wherein said reforming conditions are defined as follows: over a catalyst which includes from about 0.1 percent to about 1.0 percent platinum, from about 0.1 percent to about 1.0 percent iridium, and from about 0.02 percent to about 0.4 percent tin, wherein each of said metals is composited with and uniformly dispersed throughout an inorganic oxide support.

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

    SciTech Connect

    Cronauer, D.; Chemical Engineering

    2006-05-12

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

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

    PubMed Central

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-01-01

    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. PMID:28335231

  9. Porous bimetallic PdNi catalyst with high electrocatalytic activity for ethanol electrooxidation.

    PubMed

    Feng, Yue; Bin, Duan; Yan, Bo; Du, Yukou; Majima, Tetsuro; Zhou, Weiqiang

    2017-05-01

    Porous bimetallic PdNi catalysts were fabricated by a novel method, namely, reduction of Pd and Ni oxides prepared via calcining the complex chelate of PdNi-dimethylglyoxime (PdNi-dmg). The morphology and composition of the as-prepared PdNi were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Furthermore, the electrochemical properties of PdNi catalysts towards ethanol electrooxidation were also studied by electrochemical impedance spectrometry (EIS), cyclic voltammetry (CV) and chronoamperometry (CA) measurement. In comparison with porous Pd and commercial Pd/C catalysts, porous structural PdNi catalysts showed higher electrocatalytic activity and durability for ethanol electrooxidation, which may be ascribed to Pd and Ni property, large electroactive surface area and high electron transfer property. The Ni exist in the catalyst in the form of the nickel hydroxides (Ni(OH)2 and NiOOH) which have a high electron and proton conductivity enhances the catalytic activity of the catalysts. All results highlight the great potential application of the calcination-reduction method for synthesizing high active porous PdNi catalysts in direct ethanol fuel cells.

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

    PubMed

    Shang, Huishan; Pan, Kecheng; Zhang, Lu; Zhang, Bing; Xiang, Xu

    2016-06-04

    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 Ni(2+) 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.

  11. Enhancing oxygen reduction reaction activity of Pt-shelled catalysts via subsurface alloying.

    PubMed

    Cheng, Daojian; Qiu, Xiangguo; Yu, Haiyan

    2014-10-14

    Despite remarkable efforts have been put into the field of Pt-shelled catalysts containing an atomically thin Pt surface layer for the oxygen reduction reaction (ORR) in the last decade, further development of new Pt-shelled catalysts is still necessary. Here, a new set of Pt-shelled catalysts by subsurface alloying with early transition metals such as Mn and Fe is predicted to be a good candidate for the ORR by using density functional theory (DFT) calculations. Trends in oxygen reduction activity of Pt-alloy catalysts are determined with calculations of oxygen binding by using the slab and cluster models. It is found that the subsurface alloys by the incorporation of submonolayer M (M = Mn and Fe) into Pt(111) in the slab model result in the enhancement of ORR activity, compared with the well-known Pt(111)-skin-M, pure Pt, and Pt3M alloy catalysts. For the cluster model, the Pt12Mn and Pt12Fe clusters are also found to be the optimal catalysts for the ORR. It is expected that this work can open up new opportunities for enhancing the ORR activity of Pt-alloy catalysts by subsurface alloying.

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

    SciTech Connect

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

    2012-07-06

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

  13. Activated carbon and tungsten oxide supported on activated carbon catalysts for toluene catalytic combustion.

    PubMed

    Alvarez-Merino, M A; Ribeiro, M F; Silva, J M; Carrasco-Marín, F; Maldonado-Hódar, F J

    2004-09-01

    We have used activated carbon (AC) prepared from almond shells as a support for tungsten oxide to develop a series of WOx/AC catalysts for the catalytic combustion of toluene. We conducted the reaction between 300 and 350 degrees C, using a flow of 500 ppm of toluene in air and space velocity (GHSV) in the range 4000-7000 h(-1). Results show that AC used as a support is an appropriate material for removing toluene from dilute streams. By decreasing the GHSV and increasing the reaction temperature AC becomes a specific catalyst for the total toluene oxidation (SCO2 = 100%), but in less favorable conditions CO appears as reaction product and toluene-derivative compounds are retained inside the pores. WOx/AC catalysts are more selective to CO2 than AC due to the strong acidity of this oxide; this behavior improves with increased metal loading and reaction temperature and contact time. The catalytic performance depends on the nonstoichiometric tungsten oxide obtained during the pretreatment. In comparison with other supports the WOx/AC catalysts present, at low reaction temperatures, higher activity and selectivity than WO, supported on SiO2, TiO2, Al2O3, or Y zeolite. This is due to the hydrophobic character of the AC surface which prevents the adsorption of water produced from toluene combustion thus avoiding the deactivation of the active centers. However, the use of WOx/AC system is always restricted by its gasification temperature (around 400 degrees C), which limits the ability to increase the conversion values by increasing reaction temperatures.

  14. Atomic scale simulations of the interactions of plasma species on nickel catalyst surfaces

    NASA Astrophysics Data System (ADS)

    Somers, Wesley

    The increased greenhouse gas concentrations compared to the pre-industrial values have led to an enhanced greenhouse effect and, as a consequence, global warming. One of the possibilities to mitigate the climate change is to increase the energy efficiency of industrial processes. This is particularly interesting for the methane reforming processes, since CH4 (and CO2 in the case of dry reforming) is converted into syngas, a valuable chemical mixture of H2 and CO. These processes have a large energy cost under conventional conditions, due to the high temperatures that are required. A promising alternative to the conventional procedure is the use of plasma catalysis, i.e. the combination of plasma technology and catalysis. However, this technology is very complex and there is little fundamental knowledge on the operative interaction mechanisms between plasma and catalyst. Therefore, reactive molecular dynamics (MD) simulations are used in this doctoral study to investigate the interactions of plasma species on different nickel catalyst surfaces. The plasma species under study are CH, radicals (x={1,2,3}) and vibrationally excited CH4. These particles impinge on a total of six different nickel surfaces, to study the influence of crystallinity on the reactivity. At a temperature of 400 K, different reaction mechanisms are observed, dependent on the nickel surface. The reactivity of impinging CH2 and CH radicals is high, however little H2 is formed at this temperature. A temperature study within the range of 400 K -1600 K showed that high H2 yields are obtained at temperatures above 1400 K. However, at these temperatures the crystallinity of the nickel surface is reduced due to the continuous C-diffusion into the surface. Therefore, the role of the surface structure seems to become limited. Afterwards, the motion of vibrationally excited CH4 is included in the MD simulations. This is done by first calculating the normal coordinates of the vibrational modes. These are

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

    SciTech Connect

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

    2016-06-30

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

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

    PubMed Central

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

    2016-01-01

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

  17. Enhanced activity and selectivity of carbon nanofiber supported Pd catalysts for nitrite reduction.

    PubMed

    Shuai, Danmeng; Choe, Jong Kwon; Shapley, John R; Werth, Charles J

    2012-03-06

    Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment.

  18. CO oxidation on nanoporous gold: A combined TPD and XPS study of active catalysts

    SciTech Connect

    Röhe, Sarah; Frank, Kristian; Schaefer, Andreas; Wittstock, Arne; Zielasek, Volkmar; Rosenauer, Andreas; Bäumer, Marcus

    2012-11-30

    Disks of nanoporous gold (np-Au), produced by leaching of silver from AgAu alloy and prepared as active catalysts for CO oxidation in a continuous-flow reactor, were investigated in detail by x-ray photoelectron spectroscopy and temperature-programmed desorption spectroscopy in ultra-high vacuum. Np-Au exhibits several oxygen species on and in the surface: Chemisorbed oxygen (Oact), probably generated at residual silver sites at the surface, is readily available after np-Au preparation and consumed by CO oxidation. It can be replenished on activated np-Au by exposure to O2. In addition, strongly bound oxygen, probably at subsurface sites, is present as a major species and not consumed by CO oxidation. Pronounced CO desorption at temperatures above 200 K observed after exposing np-Au to CO at 105 K indicates an additional, more stable type of CO binding sites on np-Au as compared to pure gold. Only CO at these binding sites is consumed by oxidation reaction with Oact. In conclusion, we propose that the presence of strongly bound subsurface oxygen stabilizes CO adsorption on np-Au, thereby being as crucial for the observed catalytic activity of np-Au as residual silver.

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

    PubMed

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

    2016-04-13

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

  20. Acetylation of glycerol to biofuel additives over sulfated activated carbon catalyst.

    PubMed

    Khayoon, M S; Hameed, B H

    2011-10-01

    Oxygenated fuel additives can be produced by acetylation of glycerol. A 91% glycerol conversion with a selectivity of 38%, 28% and 34% for mono-, di- and triacetyl glyceride, respectively, was achieved at 120 °C and 3 h of reaction time in the presence of a catalyst derived from activated carbon (AC) treated with sulfuric acid at 85 °C for 4h to introduce acidic functionalities to its surface. The unique catalytic activity of the catalyst, AC-SA5, was attributed to the presence of sulfur containing functional groups on the AC surface, which enhanced the surface interaction between the glycerol molecule and acyl group of the acetic acid. The catalyst was reused in up to four consecutive batch runs and no significant decline of its initial activity was observed. The conversion and selectivity variation during the acetylation is attributed to the reaction time, reaction temperature, catalyst loading and glycerol to acetic acid molar ratio.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  2. An Iridium(IV) Species, [Cp*Ir(NHC)Cl]+, Related to a Water-Oxidation Catalyst

    SciTech Connect

    Brewster, Timothy P.; Blakemore, James D.; Schley, Nathan D.; Incarvito, Christopher D.; Hazari, Nilay; Brudvig, Gary W.; Crabtree, Robert H.

    2011-02-08

    The Ir precatalyst (3) contains both a Cp* and a κ2C2,C2'-1,3-diphenylimidazol-2-ylidene ligand, a C-C chelate, where one C donor is the NHC and the other is a cyclometalated N-phenyl wingtip group. The structure of 3 was confirmed by X-ray crystallography. Like our other recently described Cp*Ir catalysts, this compound is a precursor to a catalyst that can oxidize water to dioxygen. Electrochemical characterization of the new compound shows that it has a stable iridium(IV) oxidation state, [Cp*IrIV(NHC)Cl]+, in contrast with the unstable Ir(IV) state seen in our previous cyclometalated [Cp*IrIV(2-pyridyl-2'-phenyl)Cl] catalyst. The new iridium(IV) species has been characterized by EPR spectroscopy and has a rhombic symmetry, a consequence of the ligand environment. These results both support previous studies which suggest that Cp*Ir catalysts can be advanced through the relevant catalytic cycle(s) in one-electron steps and help clarify the electrochemical behavior of this class of water-oxidation catalysts.

  3. Surface Chemistry and Properties of Oxides as Catalyst Supports

    SciTech Connect

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

    2015-01-01

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

  4. Functional Species Encapsulated in Nitrogen-Doped Porous Carbon as a Highly Efficient Catalyst for the Oxygen Reduction Reaction.

    PubMed

    Song, Li; Wang, Tao; Ma, Yiou; Xue, Hairong; Guo, Hu; Fan, Xiaoli; Xia, Wei; Gong, Hao; He, Jianping

    2017-03-08

    The scarcity, high cost, and poor stability of precious metal-based electrocatalysts have stimulated the development of novel non-precious metal catalysts for the oxygen reduction reaction (ORR) for use in fuel cells and metal-air batteries. Here, we fabricated in situ a hybrid material (Co-W-C/N) with functional species (tungsten carbide and cobalt nanoparticles) encapsulated in an N-doped porous carbon framework, through a facile multi-constituent co-assembly method combined with subsequent annealing treatment. The unique structure favors the anchoring active nanoparticles and facilitates mass transfer steps. The homogenously distributed carbide nanoparticles and adjacent Co-N-C sites lead to the electrocatalytic synergism for the ORR. The existence of Co and W can promote the graphitization of the carbon matrix. Benefiting from its structural and material superiority, the Co-W-C/N electrocatalyst exhibits excellent electrocatalytic activity (with a half-wave potential of 0.774 V vs. reversible hydrogen electrode (RHE)), high stability (96.3 % of the initial current remaining after 9000 s of continuous operation), and good immunity against methanol in alkaline media.

  5. Monolayer binary active phase (Mo-V) and (Cr-V) supported on titania catalysts for the selective catalytic reduction (SCR) of NO by NH3.

    PubMed

    Bourikas, Kyriakos; Fountzoula, Christine; Kordulis, Christos

    2004-11-23

    Monolayer catalysts containing binary active phases (VOx-CrOx, VOx-MoOx) were prepared by simultaneous deposition of the corresponding transition metal-oxo species on the TiO2 (anatase) surface using the equilibrium deposition filtration technique. The prepared samples contained various amounts of each transition metal but almost the same total metal loading. They were characterized by atomic absorption spectroscopy, N2 adsorption, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and tested for the selective catalytic reduction of NO by NH3 in the temperature range 250-450 degrees C. It was found that the transition-metal ionic species used for the preparation of these catalysts compete for the same surface sites of the TiO2 carrier upon co-deposition. Small amounts of the second phase (Mo- or Cr-oxo phase) are sufficient in order to promote the catalytic activity at relatively high temperatures, in contrast to what happens in the corresponding industrial catalysts prepared by conventional methods. An electronic interaction between V- and Cr-oxo species favored at a V/Cr atomic ratio around 3 is probably responsible for the relatively high catalytic performance of the corresponding TiCrV catalyst. The activity of the studied catalysts is well correlated with the intensity of a DRS absorption band that appeared at ca. 400 nm, which is considered as a measure of the magnitude of interactions exerted between the monolayer transition metal-oxo species and the TiO2 carrier. This correlation is independent of the transition metals combination used and follows the same linear relationship found previously for single-active-phase catalysts.

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2014-08-28

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

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

    PubMed

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

    2015-12-07

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

  9. Alkene epoxidations catalysed by Mo(VI) supported on imidazole-containing polymers I. Synthesis, characterisation, and activity of catalysts in the epoxidation of cyclohexene

    SciTech Connect

    Miller, M.M.; Sherrington, D.C.

    1995-04-01

    Polystyrene resins functionalised with hydroxylpropyl aminomethyl pyridine, pyridyl imidazole, and carboxybenzimidazole, polyglycidyl methacrylate resins functionalised with aminomethyl pyridine and pyridyl imidazole, and polybenzimidazole resin have all been loaded with Mo(VI). The resulting polymer metal complexes have been activated by treatment with t-butylhydroperoxide, then used as catalysts in the liquid-phase epoxidation of cyclohexene using t-butylhydroperoxide. Polymers containing the imidazole group were particularly active, and unlike the other species did not require preactivation to induce high activity. The complexes formed with the imidazole-containing polymers appear to be monometallic species, whereas the other polymer ligands yield oxybridged bimetallic species. This accounts for the major difference in activity recorded. Possible structures for the catalysts are proposed based on information in the literature. 30 refs., 10 figs., 6 tabs.

  10. Characterization and catalytic activity of Cu Co spinel thin films catalysts

    NASA Astrophysics Data System (ADS)

    Stefanov, P.; Avramova, I.; Stoichev, D.; Radic, N.; Grbic, B.; Marinova, Ts.

    2005-05-01

    The Cu-Co mixed oxide catalysts were prepared on a La 2O 3/ZrO 2/SS support by thermal decomposition of nitrate precursors. The catalyst samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectrum (XPS) and Brunauer-Emmet-Teller (BET) surface area. The XPS data indicated the formation of some amount of CuO together with the Cu-Co spinel after annealing at 550 °C. The Cu-Co/ZrO 2/SS thin film catalysts were tested for three-way catalytic performance and showed moderate activity.

  11. Texas Endangered Species Activity Book.

    ERIC Educational Resources Information Center

    Jackson, Kathleen Marie; Campbell, Linda

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

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

    DOEpatents

    Wright, Randy B.

    1992-01-01

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

  13. Low-temperature conversion of methane to methanol on CeOx/Cu2O catalysts: Water controlled activation of the C–H Bond

    DOE PAGES

    Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.; ...

    2016-10-10

    Here, an inverse CeO2/Cu2O/Cu(111) catalyst is able to activate methane at room temperature producing C, CHx fragments and COx species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CHx fragments. At a temperature of 450 K, in the presence of water, a CH4 → CH3OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CHx fragments, and generating centers on which methane can directly interact to yield methanol.

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

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

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

    PubMed

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

    2013-08-01

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

  16. Surface properties of pillared acid-activated bentonite as catalyst for selective production of linear alkylbenzene

    NASA Astrophysics Data System (ADS)

    Faghihian, Hossein; Mohammadi, Mohammad Hadi

    2013-01-01

    Acid-activated and pillared montmorillonite were prepared as novel catalysts for alkylation of benzene with 1-decene for production of linear alkylbenzene. The catalysts were characterized by X-ray diffraction, FT-IR spectroscopy, N2 adsorption isotherms, temperature programmed desorption of NH3, scanning electron microscopy and elemental and thermal analysis techniques. It was found that acid-activation of clays prior to pillaring increased the porosity, total specific surface area, total pore volume and surface acidity of the catalysts. Optimization of the reaction conditions was performed by varying catalyst concentration (0.25-1.75 wt%), reactants ratio (benzene to 1-decene of 8.75, 12 and 15) and temperature (115-145 °C) in a batch slurry reactor. Under optimized conditions more than 98% conversion of 1-decene, and complete selectivity for monoalkylbenzenes were achieved.

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

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

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

    PubMed Central

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

    2015-01-01

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

  19. Relations between coke deposition and activity of HDS catalysts. [Hydrodesulfurization (HDS)

    SciTech Connect

    Brito, J.; Golding, R.; Severino, F.; Laine, J.

    1982-09-01

    Coke deposition due to degradation of 1,3-butadiene at 400 degrees C was examined employing supported molybdate hydrocracking catalysts, with and without promoters and with and without presulfiding. Initial hydrodesulfurization activity behavior of the catalysts was also examined. Coke deposition was found to increase as a function of catalyst composition and the type of diluting gas (He or H/sub 2/). With oxide catalysts, such as MoO/sub 3/ and NiO-MoO/sub 3/, the deposition of coke on the non-impregnated support is not affected by the type of diluting gas. It was also found that the supported MoO/sub 3/ catalyst produced more coke than the support alone in either H/sub 2/ or He atmospheres at all deposition times. Coke formation on sulfide catalysts showed a similar behavior to that of the oxide catalysts. The quantity of coke, however, was significantly smaller in all cases except on the support. (JMT)

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

    SciTech Connect

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

    2009-01-01

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

  1. Iron phthalocyanine supported on amidoximated PAN fiber as effective catalyst for controllable hydrogen peroxide activation in oxidizing organic dyes.

    PubMed

    Han, Zhenbang; Han, Xu; Zhao, Xiaoming; Yu, Jiantao; Xu, Hang

    2016-12-15

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H2O2 activation. The amidoxime groups greatly helped to anchor Iron(II) phthalocyanine molecules onto the fiber through coordination interaction, which has been confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy analyses. Electron spin resonance studies indicate that the catalytic process of physically anchored Iron(II) phthalocyanine performed via a hydroxyl radical pathway, while the catalyst bonded Iron(II) phthalocyanine through coordination effect could selectively catalyze the H2O2 decomposition to generate high-valent iron-oxo species. This may result from the amidoxime groups functioning as the axial fifth ligands to favor the heterolytic cleavage of the peroxide OO bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H2O2. In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity.

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

    EPA Science Inventory

    Vanadium phosphorus oxide (VPO) has been prepared using ultrasound and microwave irradiation methods and compared with the catalyst prepared by conventional method for both the phase composition and activity for hydrocarbon oxidation. It is found that ultrasound irradiation metho...

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

    PubMed

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

    2004-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

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

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

    SciTech Connect

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

    2011-03-24

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

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

    SciTech Connect

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

    2010-01-01

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

  7. Iridium Ziegler-type hydrogenation catalysts made from [(1,5-COD)Ir(mu-O2C8H15)](2) and AlEt3: spectroscopic and kinetic evidence for the Ir(n) species present and for nanoparticles as the fastest catalyst.

    PubMed

    Alley, William M; Hamdemir, Isil K; Wang, Qi; Frenkel, Anatoly I; Li, Long; Yang, Judith C; Menard, Laurent D; Nuzzo, Ralph G; Ozkar, Saim; Johnson, Kimberly A; Finke, Richard G

    2010-09-06

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

  8. Catalyst-free activation of peroxides under visible LED light irradiation through photoexcitation pathway.

    PubMed

    Gao, Yaowen; Li, Yixi; Yao, Linyu; Li, Simiao; Liu, Jin; Zhang, Hui

    2017-05-05

    Catalysts are known to activate peroxides to generate active radicals (i.e., hydroxyl radical (OH) and sulfate radical (SO4(-))) under certain conditions, but the activation of peroxides in the absence of catalysts under visible light irradiation has been rarely reported. This work demonstrates a catalyst-free activation of peroxides for the generation of OH and/or SO4(-) through photoexcited electron transfer from organic dyes to peroxides under visible LED light irradiation, where Rhodamine B (RhB) and Eosin Y (EY) were selected as model dyes. The formation of OH and/or SO4(-) in the reactions and the electron transfer from the excited dyes to peroxides were validated via electron paramagnetic resonance (EPR), photoluminescence (PL) spectra and cyclic voltammetry (CV). The performance of the peroxide/dye/Vis process was demonstrated to be altered depending on the target substrate. Meanwhile, the peroxide/dye/Vis process was effective for simultaneous decolorization of dyes and production of active radicals under neutral even or basic conditions. The findings of this study clarified a novel photoexcitation pathway for catalyst-free activation of peroxides under visible light irradiation, which could avoid the secondary metal ion (dissolved or leached) pollution from the metal-based catalysts and expand the application range of the peroxide-based catalytic process.

  9. Structure-Activity Relationship Studies of Cyclopropenimines as Enantioselective Brønsted Base Catalysts

    PubMed Central

    Bandar, Jeffrey S.; Barthelme, Alexandre P.; Mazori, Alon Y.; Lambert, Tristan H.

    2015-01-01

    We recently demonstrated that chiral cyclopropenimines are viable Brønsted base catalysts in enantioselective Michael and Mannich reactions. Herein, we describe a series of structure-activity relationship studies that provide an enhanced understanding of the effectiveness of certain cyclopropenimines as enantioselective Brønsted base catalysts. These studies underscore the crucial importance of dicyclohexylamino substituents in mediating both reaction rate and enantioselectivity. In addition, an unusual catalyst CH···O interaction, which provides both ground state and transition state organization, is discussed. Cyclopropenimine stability studies have led to the identification of new catalysts with greatly improved stability. Finally, additional demonstrations of substrate scope and current limitations are provided herein. PMID:26504512

  10. TiO2 nanotubes supported NiW hydrodesulphurization catalysts: Characterization and activity

    NASA Astrophysics Data System (ADS)

    Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K.

    2013-01-01

    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.

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

    PubMed

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

    2016-04-19

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

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

    SciTech Connect

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

    1992-11-01

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

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

    SciTech Connect

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

    1992-01-01

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

  14. Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

    NASA Astrophysics Data System (ADS)

    Albayati, Talib M.; Doyle, Aidan M.

    2015-02-01

    Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

  15. SO{sub 2} oxidation in a periodically operated trickle bed: Comparison of activated carbon catalysts

    SciTech Connect

    Lee, Joong Kee; Hudgins, R.R.; Silveston, P.L.

    1996-12-31

    Catalytic activities of two different activated carbons, BPL{trademark} and Centaur{trademark} catalysts (Calgon Carbon Corp.), were compared in a periodically operated trickle-bed reactor for SO{sub 2} oxidation by varying the cycle period and split. In an effort to characterize the carbon surface, differential thermogravimetric analysis and TPD were used to observe oxygen functional groups. The Centaur catalyst, which appears to have a more suitable density of oxygen functional groups, has the higher catalytic activity for SO{sub 2} oxidation. 8 refs., 8 figs., 1 tab.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    PubMed

    Shul'pin, Georgiy B

    2013-09-28

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

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

    SciTech Connect

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

    2015-09-16

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

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

    DOE PAGES

    Islam, A. E.; Zakharov, D.; Stach, E. A.; ...

    2015-09-16

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  1. Highly active Ni/Y-doped ZrO2 catalysts for CO2 methanation

    NASA Astrophysics Data System (ADS)

    Takano, H.; Kirihata, Y.; Izumiya, K.; Kumagai, N.; Habazaki, H.; Hashimoto, K.

    2016-12-01

    The catalytic methanation of CO2 was carried out on Ni catalysts supported on Y-doped ZrO2 with various Y3+ concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO2, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO2 show higher catalytic activity than the catalyst on Y-free ZrO2 with a monoclinic ZrO2 phase. The catalytic activity is also dependent upon the Y3+ concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO2 phase. Y3+ doping into ZrO2 introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH4 formation.

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

    PubMed

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

    2016-06-08

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

  3. Rationalizing current strategies to protect N-heterocyclic carbene-based ruthenium catalysts active in olefin metathesis from C-H (de)activation.

    PubMed

    Poater, Albert; Bahri-Laleh, Naeimeh; Cavallo, Luigi

    2011-06-21

    Defending second generation Ru-catalysts in olefin metathesis from C-H (de)activation reactions requires precise catalyst design strategies. Computer simulations are used here to rationalize precisely the role of the currently used catalyst structural modifications, and the way these modifications cooperate.

  4. High-activity PtRuPd/C catalyst for direct dimethyl ether fuel cells.

    PubMed

    Li, Qing; Wen, Xiaodong; Wu, Gang; Chung, Hoon T; Gao, Rui; Zelenay, Piotr

    2015-06-22

    Dimethyl ether (DME) has been considered as a promising alternative fuel for direct-feed fuel cells but lack of an efficient DME oxidation electrocatalyst has remained the challenge for the commercialization of the direct DME fuel cell. The commonly studied binary PtRu catalyst shows much lower activity in DME than methanol oxidation. In this work, guided by density functional theory (DFT) calculation, a ternary carbon-supported PtRuPd catalyst was designed and synthesized for DME electrooxidation. DFT calculations indicated that Pd in the ternary PtRuPd catalyst is capable of significantly decreasing the activation energy of the CO and CH bond scission during the oxidation process. As evidenced by both electrochemical measurements in an aqueous electrolyte and polymer-electrolyte fuel cell testing, the ternary catalyst shows much higher activity (two-fold enhancement at 0.5 V in fuel cells) than the state-of-the-art binary Pt50 Ru50 /C catalyst (HiSPEC 12100).

  5. The role of surface reactions on the active and selective catalyst design for bioethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Serrano-Lotina, A.; Rodríguez, L.; Brey, J. J.; Daza, L.

    In order to study the role of surface reactions involved in bioethanol steam reforming mechanism, a very active and selective catalyst for hydrogen production was analysed. The highest activity was obtained at 700 °C, temperature at which the catalyst achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. It also exhibited a very high hydrogen production efficiency, higher than 4.5 mol H 2 per mol of EtOH fed. The catalyst was operated at a steam to carbon ratio (S/C) of 4.8, at 700 °C and atmospheric pressure. No by-products, such as ethylene or acetaldehyde were observed. In order to consider a further application in an ethanol processor, a long-term stability test was performed under the conditions previously reported. After 750 h, the catalyst still exhibited a high stability and selectivity to hydrogen production. Based on the intermediate products detected by temperature programmed desorption and reaction (TPD and TPR) experiments, a reaction pathway was proposed. Firstly, the adsorbed ethanol is dehydrogenated to acetaldehyde producing hydrogen. Secondly, the adsorbed acetaldehyde is transformed into acetone via acetic acid formation. Finally, acetone is reformed to produce hydrogen and carbon dioxide, which were the final reaction products. The promotion of such reaction sequence is the key to develop an active, selective and stable catalyst, which is the technical barrier for hydrogen production by ethanol reforming.

  6. Investigation on the structure-activity relationship of BaO promoting Pd/CeO2-ZrO2 catalysts for CO, HC and NOx conversions.

    PubMed

    Lin, Jiansong; Yang, Linyan; Wang, Ting; Zhou, Renxian

    2017-03-15

    Four different synthetic routes (co-precipitation, oxidation-precipitation, citric acid sol-gel and reversed microemulsion) are adopted to prepare barium modified Pd/CeO2-ZrO2 catalysts and their catalytic activity towards CO, HC and NOx conversions is studied. The surface and bulk properties of these catalysts are characterized via XRD, N2 adsorption, XPS, UV-Raman, H2-TPR, and in situ DRIFTS. The catalyst prepared via the co-precipitation method exhibits the optimum three-way catalytic behavior, which is mainly due to its superior redox ability, whereas the oxidation-precipitation synthesis renders the catalyst with the best homogeneity and thermal resistance. However, for the catalyst prepared via the sol-gel route, its worst NOx reduction capacity is verified by the scarce appearance of negatively charged Pd(0)-N[double bond, length as m-dash]O(δ-) species, which is related to the faster dissociation of NO based on in situ DRIFTS, and the abundance of surface CO-Pd(+) species reveals its unsatisfactory deep oxidizability of the HC reactant.

  7. Reforming catalysts

    SciTech Connect

    Givens, E.N.; Plank, C.J.; Rosinski, E.J.

    1980-03-04

    Crystalline aluminosilicate zeolites are mixed with conventional reforming catalysts to produce new catalytic compositions with high catalytic activity and selectivity and excellent aging characteristics. These new catalytic compositions may be utilized alone or in conjunction with conventional reforming catalysts. The acidic activity of the total catalyst system is controlled within defined limits. When so controlled the utility of these catalyst systems in reforming hydrocarbon mixtures is to reduce the C1 and C2 concentrations in reformer gas product, while increasing the C3 and C4 concentrations and maintaining high liquid yield at high octane numbers.

  8. Acid activated montmorillonite as catalysts in methyl esterification reactions of lauric acid.

    PubMed

    Zatta, Leandro; Ramos, Luiz Pereira; Wypych, Fernando

    2012-01-01

    The catalytic activity of acid activated montmorillonite in the esterification of free fatty acids (FFA) is reported. Standard Montmorillonite (MMT) type STx-1 provided by the Clay Mineral Society repository was activated using phosphoric, nitric and sulphuric acids under different conditions and the resulting materials were characterized and evaluated as catalysts in the methyl esterification of lauric acid. Blank reactions carried out in the absence of any added catalyst presented conversions of 32.64, 69.79 and 79.23%, for alcohol:lauric acid molar ratios of 60:1, 12:1 and 6:1, respectively. In the presence of the untreated clay and using molar ratios of 12:1 and 6:1 with 12% of catalyst, conversions of 70.92 and 82.30% were obtained, respectively. For the acid activated clays, conversions up to 93.08% of lauric acid to methyl laurate were obtained, much higher than those observed for the thermal conversion or using untreated montmorillonite. Relative good correlations were observed between the catalytic activity and the development of acid sites and textural properties of the resulting materials. Therefore, a simple acid activation was able to improve the catalytic activity and produce clay catalysts that are environmental friendly, cost effective, noncorrosive and reusable.

  9. Engineering the Activity and Lifetime of Heterogeneous Catalysts for Carbon Nanotube Growth via Substrate Ion Beam Bombardment (Postprint)

    DTIC Science & Technology

    2014-07-31

    AFRL-RX-WP-JA-2014-0159 ENGINEERING THE ACTIVITY AND LIFETIME OF HETEROGENEOUS CATALYSTS FOR CARBON NANOTUBE GROWTH VIA SUBSTRATE ION BEAM...July 2014 4. TITLE AND SUBTITLE ENGINEERING THE ACTIVITY AND LIFETIME OF HETEROGENEOUS CATALYSTS FOR CARBON NANOTUBE GROWTH VIA SUBSTRATE ION BEAM...the growth of vertically aligned carbon nanotubes from iron catalysts with a density, height, and quality equivalent to those grown on conventional

  10. Development of a supported tri-metallic catalyst and evaluation of the catalytic activity in biomass steam gasification.

    PubMed

    Li, Jianfen; Xiao, Bo; Yan, Rong; Xu, Xiaorong

    2009-11-01

    A supported tri-metallic catalyst (nano-Ni-La-Fe/gamma-Al(2)O(3)) was developed for tar reduction and enhanced hydrogen production in biomass steam gasification, with focuses on preventing coke deposition and sintering effects to lengthen the lifetime of developed catalysts. The catalyst was prepared by deposition-precipitation method and characterized by various analytical approaches. Following that, the activity of catalysts in biomass steam gasification was investigated in a bench-scale combined fixed bed reactor. With presence of the catalyst, the content of hydrogen in gas products was increased to over 10 vol.%, the tar removal efficiency reached 99% at 1073 K, and more importantly the coke deposition on the catalyst surfaces and sintering effects were avoided, leading to a long lifetime of catalysts.

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

    SciTech Connect

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

    2000-04-01

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

  12. Results of catalyst testing using iron-based catalysts

    SciTech Connect

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

    1993-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  14. Evaluation of tungsten hexachloride as a ROMP active catalyst precursor for self-healing polymers

    NASA Astrophysics Data System (ADS)

    Kamphaus, Jason M.

    Self-healing polymers and composites have been demonstrated via a microencapsulated healing agent and catalytic trigger within the matrix material. The microcapsules are ruptured by a propagating crack and healing agent is released into the crack plane by capillary action. Contact with the catalyst initiates a chemical reaction and the resulting solid polymer bonds the crack faces together. Initial work using the microcapsule/catalytic trigger concept focused on the ring-opening-metathesis-polymerization (ROMP) of endo-dicyclopentadiene with Grubbs' catalyst. Monotonic fracture recovery in excess of 90% and extended fatigue life have been reported. A novel self-healing system based on the ROMP active catalyst tungsten (VI) chloride (WCl6) shows great promise for addressing the limitations of Grubbs' catalyst, specifically the high cost and low thermal stability. The healing chemistry utilizes WCl6 in solid phase and exo-dicyclopentadiene (exo-DCPD) monomer. The exo-DCPD monomer is the same molecule as used in previously self-healing materials, but is a different isomer and exhibits much higher ROMP reactivity and kinetics. The effect of two different initiators, phenylacetylene and 1-decyne, was explored, as well as an alternative monomer, 5-ethylidene-2-norbornene (ENB). Three catalyst forms (as-received, recrystallized, and wax-protected) were investigated to address the known sensitivity of WCl6 to moisture and amine curing agents. Fracture experiments were performed to evaluate the healing efficiency of each catalyst type. A tapered double cantilever beam (TDCB) specimen geometry was used to evaluate the virgin and healed fracture toughness of the material. Fracture recovery of ca. 90% was achieved in both the recrystallized and as-received WCl6 cases at 12 wt% catalyst loading. The wax-protected form of the catalyst gives healing efficiencies of ca. 50% at only 4 wt% overall catalyst loading. In situ samples achieved healing efficiencies of up to 30% for

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  16. Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

    NASA Astrophysics Data System (ADS)

    Ahmed, Muthanna J.

    2012-02-01

    The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

  17. Catalytic activity in individual cracking catalyst particles imaged throughout different life stages by selective staining.

    PubMed

    Buurmans, Inge L C; Ruiz-Martínez, Javier; Knowles, William V; van der Beek, David; Bergwerff, Jaap A; Vogt, Eelco T C; Weckhuysen, Bert M

    2011-09-18

    Fluid catalytic cracking (FCC) is the major conversion process used in oil refineries to produce valuable hydrocarbons from crude oil fractions. Because the demand for oil-based products is ever increasing, research has been ongoing to improve the performance of FCC catalyst particles, which are complex mixtures of zeolite and binder materials. Unfortunately, there is limited insight into the distribution and activity of individual zeolitic domains at different life stages. Here we introduce a staining method to visualize the structure of zeolite particulates and other FCC components. Brønsted acidity maps have been constructed at the single particle level from fluorescence microscopy images. By applying a statistical methodology to a series of catalysts deactivated via industrial protocols, a correlation is established between Brønsted acidity and cracking activity. The generally applicable method has clear potential for catalyst diagnostics, as it determines intra- and interparticle Brønsted acidity distributions for industrial FCC materials.

  18. Catalytic activity in individual cracking catalyst particles imaged throughout different life stages by selective staining

    NASA Astrophysics Data System (ADS)

    Buurmans, Inge L. C.; Ruiz-Martínez, Javier; Knowles, William V.; van der Beek, David; Bergwerff, Jaap A.; Vogt, Eelco T. C.; Weckhuysen, Bert M.

    2011-11-01

    Fluid catalytic cracking (FCC) is the major conversion process used in oil refineries to produce valuable hydrocarbons from crude oil fractions. Because the demand for oil-based products is ever increasing, research has been ongoing to improve the performance of FCC catalyst particles, which are complex mixtures of zeolite and binder materials. Unfortunately, there is limited insight into the distribution and activity of individual zeolitic domains at different life stages. Here we introduce a staining method to visualize the structure of zeolite particulates and other FCC components. Brønsted acidity maps have been constructed at the single particle level from fluorescence microscopy images. By applying a statistical methodology to a series of catalysts deactivated via industrial protocols, a correlation is established between Brønsted acidity and cracking activity. The generally applicable method has clear potential for catalyst diagnostics, as it determines intra- and interparticle Brønsted acidity distributions for industrial FCC materials.

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

    PubMed

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

    2015-03-05

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

  20. Enhanced Oxygen Reduction Activity In Acid By Tin-Oxide Supported Au Nanoparticle Catalysts

    SciTech Connect

    Baker,W.; Pietron, J.; Teliska, M.; Bouwman, P.; Ramaker, D.; Swider-Lyons, K.

    2006-01-01

    Gold nanoparticles supported on hydrous tin-oxide (Au-SnO{sub x}) are active for the four-electron oxygen reduction reaction in an acid electrolyte. The unique electrocatalytic of the Au-SnO is confirmed by the low amount of peroxide detected with rotating ring-disk electrode voltammetry and Koutecky-Levich analysis. In comparison, 10 wt % Au supported on Vulcan carbon and SnO{sub x} catalysts both produce significant peroxide in the acid electrolyte, indicating only a two-electron reduction reaction. Characterization of the Au-SnO{sub x} catalyst reveals a high-surface area, amorphous support with 1.7 nm gold metal particles. The high catalytic activity of the Au-SnO is attributed to metal support interactions. The results demonstrate a possible path to non-Pt catalysts for proton exchange membrane fuel cell cathodes.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  2. Niobium-silica catalysts for the selective epoxidation of cyclic alkenes: the generation of the active site by grafting niobocene dichloride.

    PubMed

    Tiozzo, Cristina; Bisio, Chiara; Carniato, Fabio; Gallo, Alessandro; Scott, Susannah L; Psaro, Rinaldo; Guidotti, Matteo

    2013-08-28

    Niobium-containing silica materials obtained by deposition via liquid-phase grafting or dry impregnation of niobocene(iv) dichloride are active and selective catalysts in the epoxidation of alkenes in the presence of aqueous hydrogen peroxide. The generation of the catalytically-active Nb species was followed step-by-step, and investigated using a combined DR-UV-Vis, NIR, Raman, XRD, XANES and EXAFS analyses. At the end of the grafting procedure, the nature of the surface active species can be described as an oxo-Nb(v) site, tripodally grafted onto the silica surface in close proximity to other Nb(v) centres. The liquid-phase methodology provides a better dispersion of the metal sites onto the siliceous support than the dry-impregnation approach. The niobium-silica catalysts were then tested in the epoxidation of cyclohexene and 1-methylcyclohexene, as model substrates.

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

    PubMed

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

    2015-03-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

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

    PubMed

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

    2016-02-01

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

  6. Scale-Activity Relationship of MnOx-FeOy Nanocage Catalysts Derived from Prussian Blue Analogues for Low-Temperature NO Reduction: Experimental and DFT Studies.

    PubMed

    Yan, Lijun; Liu, Yangyang; Zha, Kaiwen; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

    2017-01-25

    Size effects have been recognized to promote the catalytic activity and selectivity of metal oxide particles. So far, limited works and studies are conducted to investigate the size effect of metal oxide with the tailored shape in the selective catalytic reduction of NOx with NH3 (NH3-SCR). Herein, the MnOx-FeOy nanocage catalysts with varied scales (0.25, 0.5, 1, and 2 μm) were synthesized via a Prussian blue analogue (PBA)-derived method and used for NH3-SCR of NO. By preforming a series of the activity tests over the nanocages with different scales, the NH3-SCR activity of 0.5 μm MnOx-FeOy nanocage catalysts exhibits the highest deNOx activity in the temperature range of 80-200 °C owing to more preferable physical and chemical properties. It has been demonstrated that there is a strong interaction among Mn and Fe cations in the 0.5 μm MnOx-FeOy nanocages. Moreover, the H2-TPR and XPS analysis prove 0.5 μm nanocages exhibit excellent redox properties, which contribute to the higher conservation of NOx. Through the DFT studies, it is also demonstrated that the 0.5 μm MnOx-FeOy nanocage catalysts could provide more preferable electronic charge, which gives rise to the varied adsorption behavior of the NH3 species and NOx species compared to the nanocages with other scales. The in situ DRIFTs were also employed to evaluate the adsorption status of NH3 with NOx species over MnOx-FeOy nanocage catalysts with varied scales. Finally, the scale-activity relationship of the MnOx-FeOy nanocage catalysts and their corresponding activities are also established. The deep insight into the scale-activity relationship of the PBA-derived MnOx-FeOy nanocage catalyst paves the way for developing and designing highly efficient Mn-based catalyst at lower temperature.

  7. Biopolymer-stabilized Pt nanoparticles colloid: a highly active and recyclable catalyst for biphasic catalysis

    NASA Astrophysics Data System (ADS)

    Wang, Yujia; Shen, Yueyue; Qiu, Yunfei; Zhang, Ting; Liao, Yang; Zhao, Shilin; Ma, Jun; Mao, Hui

    2016-10-01

    Noble metal nanoparticles are promising candidates to replace conventional bulk counterparts owing to their high activity and selectivity. To enable catalyst recovery, noble metal nanoparticles are often supported onto solid matrices to prepare heterogeneous catalyst. Although recycle of noble metal nanoparticles is realized by heterogenization, a loss of activity is usually encountered. In the present investigation, Pt nanoparticles with tunable particle size (1.85-2.80 nm) were facilely prepared by using polyphenols as amphiphilic stabilizers. The as-prepared Pt nanoparticles colloid solution could be used as highly active catalyst in aqueous-organic biphasic catalysis. The phenolic hydroxyls of polyphenols could constrain Pt nanoparticles in aqueous phase, and simultaneously, the aromatic scaffold of polyphenols ensured effective interactions between substrates and Pt nanoparticles. As a consequence, the obtained polyphenols-stabilized Pt nanoparticles exhibited high activity and cycling stability in biphasic hydrogenation of a series of unsaturated compounds. Compared with conventional heterogeneous Pt-C and Pt-Al2O3 catalysts, polyphenols-stabilized Pt nanoparticles showed obvious advantage both in activity and cycling stability.

  8. Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR.

    PubMed

    Chang, Huazhen; Ma, Lei; Yang, Shijian; Li, Junhua; Chen, Liang; Wang, Wei; Hao, Jiming

    2013-11-15

    A series of CeO2 catalysts prepared with sulfate (S) and nitrate (N) precursors by hydrothermal (H) and precipitation (P) methods were investigated in selective catalytic reduction of NOx by NH3 (NH3-SCR). The catalytic activity of CeO2 was significantly affected by the preparation methods and the precursor type. CeO2-SH, which was prepared by hydrothermal method with cerium (IV) sulfate as a precursor, showed excellent SCR activity and high N2 selectivity in the temperature range of 230-450 °C. Based on the results obtained by temperature-programmed reduction (H2-TPR), transmission infrared spectra (IR) and thermal gravimetric analysis (TGA), the excellent performance of CeO2-SH was correlated with the surface sulfate species formed in the hydrothermal reaction. These results indicated that sulfate species bind with Ce(4+) on the CeO2-SH catalyst, and the specific sulfate species, such as Ce(SO4)2 or CeOSO4, were formed. The adsorption of NH3 was promoted by these sulfate species, and the probability of immediate oxidation of NH3 to N2O on Ce(4+) was reduced. Accordingly, the selective oxidation of NH3 was enhanced, which contributed to the high N2 selectivity in the SCR reaction. However, the location of sulfate on the CeO2-SP catalyst was different. Plenty of sulfate species were likely deposited on CeO2-SP surface, covering the active sites for NO oxidation, which resulted in poor SCR activity in the test temperature range. Moreover, the resistance to alkali metals, such as Na and K, was improved over the CeO2-SH catalyst.

  9. Steam dealkylation of aromatic hydrocarbons. II. Role of the support and kinetic pathway of oxygenated species in toluene steam dealkylation over group VIII metal catalysts. [Catalyst support comparison

    SciTech Connect

    Duprez, D.; Pereira, P.; Miloudi, A.; Maurel, R.

    1982-05-01

    The role of support in steam dealkylation (SDA) is studied on a series of Group VIII metal catalysts supported on alumina, silica, and titania. When possible turnover frequencies are given on the basis of the free metal fraction during the reaction, the values are generally constant with time-on-steam and represent the actual turnover frequency of the catalysts. Metals can be classified into two groups, namely, support-sensitive metals (Pt,Rh,Pd) and support-insensitive metals (Ni,Co,Ru and to a certain extent Ir). Support sensitivity is related to the oxidizability of the metallic surface. For metals of the first group, the reaction is probably governed by a noncompetitive mechanism in which the metal coverage by the oxygenated species is negligible. Kinetic derivation leads to a rate law where there is at once intervention of the support site concentration and of the specific perimeter of the metal/support interface. One can thus explain the support effect for this metal group and the slight sensitivity to the crystallite size observed in the Rh/Al/sub 2/O/sub 3/ series. For metals of the second group, a competitive mechanism probably takes place on the metal. Kinetic derivation leads to a rate law independent of the support site concentration and accounting for the slight negative order with respect to toluene as previously reported. The conspicuous parallelism between the selectivities of the various metals in SDA, in hydrodealkylation , and in hydrogenolysis is also discussed. In addition to the metal, the support and the crystallite size are determining factors of the selectivity to benzene in SDA.

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

    SciTech Connect

    Rivera Latas, F.J.

    1986-01-01

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

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

    PubMed

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

    2016-08-17

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

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

    PubMed

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  14. Distribution of molybdenum oxidation states in reduced Mo/TiO sub 2 catalysts: Correlation with benzene hydrogenation activity

    SciTech Connect

    Quincy, R.B.; Houalla, M.; Proctor, A.; Hercules, D.M. )

    1990-02-22

    A 5 wt % MoO{sub 3}/TiO{sub 2} catalyst was reduced in hydrogen at various temperatures to produce a surface with average Mo oxidation states between +6 and 0. The changes in molybdenum oxidation states as a function of the extent of reduction were monitored by gravimetric analyses and x-ray photoelectron spectroscopy (XPS, ESCA), and the results were correlated with benzene hydrogenation activity. ESCA Mo 3d{sub 5/2} binding energy values for the various Mo oxidation states on a 5 wt % MoO{sub 3}/TiO{sub 2} catalyst show a shift of 5.1 eV between Mo{sup +6} (232.7 eV) and Mo{sup 0} (227.6 eV). The benzene hydrogenation activity was found to depend strongly on the extent of reduction of the Mo phase. Comparison of benzene hydrogenation activity with the distribution of Mo oxidation states determined by ESCA suggests that molybdenum ions with an oxidation state of +2 are the most active species.

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

    PubMed

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

    2014-03-14

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

  16. Preparation, characterization, and activity of α-Ti(HPO4)2 supported metallocene catalysts

    NASA Astrophysics Data System (ADS)

    Shi, Yasai; Yuan, Yuan; Xu, Qinghong; Yi, Jianjun

    2016-10-01

    A series of heterogeneous catalysts by loading metallocenes on surface of α-Ti(HPO4)2, a kind of solid acid, has been synthesized. Polymerization of alkenes, including ethylene and propylene, based on participation of the heterogeneous catalysts were studied and the results were compared to metallocenes supported on silica gel, α-Zr(HPO4)2 and clay. Higher catalytic activity, larger polymer molecular weight and narrow distribution of polymer molecular weight were obtained. Acidic strength of the support and its influence to metallocenes were studied to discover intrinsic factors in the polymerizations.

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

    PubMed

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

    2003-09-19

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

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

    EPA Science Inventory

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

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

    ERIC Educational Resources Information Center

    Seen, Andrew J.

    2004-01-01

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

  20. SOx Tolerant Pt/TiO2 Catalysts for CO Oxidation and the Effect of TiO2 Supports on Catalytic Activity.

    PubMed

    Taira, Kenji; Nakao, Kenji; Suzuki, Kimihito; Einaga, Hisahiro

    2016-09-06

    We developed a new technique for mitigating catalyst deactivation caused by SO2 in exhaust gases. A series of 0.1 wt %-Pt/TiO2 catalysts with different surface, crystal, and pore structures were prepared and tested for CO oxidation activity in the presence of SO2 and H2O. The order of the CO oxidation activity under the influence of SO2 was much different from that in the absence of SO2. Catalysts with a high ratio of larger pores exhibited higher catalytic activity under the influence of SO2 and H2O in the temperature range of 250-300 °C, whereas other parameters, such as BET surface area and crystal structure of the TiO2 support, had minor effects on the CO oxidation activity. The oxidation state of Pt differed significantly depending on the kind of TiO2 support. Some catalysts were less active without H2 reduction pretreatment due to the presence of oxidized Pt species.

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

    PubMed

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

    2011-01-01

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

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

    DOEpatents

    Wright, R.B.

    1992-01-14

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

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

    SciTech Connect

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

    2013-01-01

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

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

    SciTech Connect

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

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  6. Electrochemical catalyst recovery method

    DOEpatents

    Silva, Laura J.; Bray, Lane A.

    1995-01-01

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

  7. Electrochemical catalyst recovery method

    DOEpatents

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

    1995-05-30

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

  8. A simple and convenient approach for preparing core-shell-like silica@nickel species nanoparticles: highly efficient and stable catalyst for the dehydrogenation of 1,2-cyclohexanediol to catechol.

    PubMed

    Chen, Bao-Hui; Liu, Wei; Li, An; Liu, Ya-Juan; Chao, Zi-Sheng

    2015-01-21

    A simple and convenient approach denoted as gel-deposition-precipitation (G-D-P) for the preparation of core-shell-like silica@nickel species nanoparticles was studied systematically. Core-shell-like silica@nickel species nanoparticles consisted of a Si-rich core and a Ni-rich shell. The G-D-P process included two steps: one was the deposition-precipitation of nickel over the gelled colloidal silica particle, generating core-shell-like silica@nickel species nanoparticles, and the other was the aging period. It was found that the nickel phyllosilicate layer was formed mainly during the aging period and served as the protective cover to resist against aggregation of the nanoparticles, which could be utilized for regulating the dispersion of nickel over the silica@nickel species nanoparticles. In the present paper, the silica@nickel species nanoparticles were used as the catalysts for preparing catechol via dehydrogenation of 1,2-cyclohexanediol. Their catalytic activity and long-term stability were compared to those of a catalyst prepared by a conventional deposition-precipitation (D-P) approach. The higher activity and better stability of the title reaction over the silica@nickel species nanoparticles catalyst prepared by G-D-P than those over the catalyst prepared by D-P could be due to the higher dispersion of metallic nickel stabilized by the layers of nickel phyllosilicates. Moreover, it was found that the dehydrogenation of 1,2-cyclohexanediol to catechol was a structurally sensitive reaction.

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

    DOE PAGES

    Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.; ...

    2016-06-30

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  11. Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

    PubMed

    Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

    2014-12-01

    Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation.

  12. Catalyst suppliers consolidate further, offer more catalysts

    SciTech Connect

    Rhodes, A.K.

    1995-10-02

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

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

    PubMed

    Buchneva, Olga; Gallo, Alessandro; Rossetti, Ilenia

    2012-11-05

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

  14. Collagen degrading activity associated with Mycobacterium species

    PubMed Central

    Masso, F; Paez, A; Varela, E; d Diaz; Zenteno, E; Montano, L

    1999-01-01

    BACKGROUND—The mechanism of Mycobacterium tuberculosis penetration into tissues is poorly understood but it is reasonable to assume that there is a contribution from proteases capable of disrupting the extracellular matrix of the pulmonary epithelium and the blood vessels. A study was undertaken to identify and characterise collagen degrading activity of M tuberculosis.
METHODS—Culture filtrate protein extract (CFPE) was obtained from reference mycobacterial strains and mycobacteria isolated from patients with tuberculosis. The collagen degrading activity of CFPE was determined according to the method of Johnson-Wint using 3H-type I collagen. The enzyme was identified by the Birkedal-Hansen and Taylor method and its molecular mass determined by SDS-PAGE and Sephacryl S-300 gel filtration chromatography using an electroelution purified enzyme.
RESULTS—CFPE from Mycobacterium tuberculosis strain H37Rv showed collagenolytic activity that was four times higher than that of the avirulent strain H37Ra. The 75 kDa enzyme responsible was divalent cation dependent. Other mycobacterial species and those isolated from patients with tuberculosis also had collagen degrading activity.
CONCLUSIONS—Mycobacterium species possess a metalloprotease with collagen degrading activity. The highest enzymatic activity was found in the virulent reference strain H37Rv.

 PMID:10212111

  15. Enhanced electrocatalytic activity of CoTMPP-based catalysts for PEMFCs by plasma treatment

    NASA Astrophysics Data System (ADS)

    Savastenko, N. A.; Brüser, V.; Brüser, M.; Anklam, K.; Kutschera, S.; Steffen, H.; Schmuhl, A.

    In this work, we developed a methodology of plasma-enhanced preparation of CoTMPP (tetramethoxyphenylporphyrin)-based electrocatalysts. A series of CoTMPP-based electrocatalysts were deposited on the porous gas diffusion substrate (titanium fibre felt) using plasma-enhanced impregnation method. Impregnated 1.5 mg cm -2 CoTMPP/Ti catalysts were treated by dielectric barrier discharge (DBD) plasma in Ar or N 2 atmosphere. Additionally, the pretreatment methods were utilized to improve the adhesion of CoTMPP on the diffusion layer surface. The plasma pretreatment methods included the a-C:H-layers deposition followed by an Ar:O 2 radio frequency (RF) plasma functionalization. The latter approach led to the formation of specific oxygen surface groups that influenced the catalysts activity. Obtained catalysts were compared in terms of activity, stability and structure. The catalytic activity for hydrogen peroxide (H 2O 2) reduction was tested in a proton exchange membrane fuel cell (PEMFC) using hydrogen peroxide on the cathode side. Surface elemental analysis and structure of catalysts were examined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Our contribution shows the potential of a plasma treatment in the preparation of electrocatalysts for hydrogen peroxide reduction reaction in a PEMFC. Under the conditions of this study, improvement of the PEMFC performance up to 30% was achievable by a deposition of CoTMPP on the titanium diffusion substrate followed by plasma treatment. The large differences in catalytic activity of CoTMPP/Ti were observed, depending on the plasma treatment applied to the catalysts during their preparation.

  16. An assessment of hydrocarbon species in the methanol-to-hydrocarbon reaction over a ZSM-5 catalyst.

    PubMed

    Suwardiyanto; Howe, Russell F; Gibson, Emma K; Catlow, C Richard A; Hameed, Ali; McGregor, James; Collier, Paul; Parker, Stewart F; Lennon, David

    2017-02-14

    A ZSM-5 catalyst is examined in relation to the methanol-to-hydrocarbon (MTH) reaction as a function of reaction temperature and time-on-stream. The reaction profile is characterised using in-line mass spectrometry. Furthermore, the material contained within a catch-pot downstream from the reactor is analysed using gas chromatography-mass spectrometry. For a fixed methanol feed, reaction conditions are selected to define various stages of the reaction coordinate: (i) initial methanol adsorption at a sub-optimum reaction temperature (1 h at 200 °C); (ii) initial stages of reaction at an optimised reaction temperature (1 h at 350 °C); (iii) steady-state operation at an optimised reaction temperature (3 days at 350 °C); and (iv) accelerated ageing (3 days at 400 °C). Post-reaction, the catalyst samples are analysed ex situ by a combination of temperature-programmed oxidation (TPO) and spectroscopically by electron paramagnetic resonance (EPR), diffuse-reflectance infrared and inelastic neutron scattering (INS) spectroscopies. The TPO measurements provide an indication of the degree of 'coking' experienced by each sample. The EPR measurements detect aromatic radical cations. The IR and INS measurements reveal the presence of retained hydrocarbonaceous species, the nature of which are discussed in terms of the well-developed 'hydrocarbon pool' mechanism. This combination of experimental evidence, uniquely applied to this reaction system, establishes the importance of retained hydrocarbonaceous species in effecting the product distribution of this economically relevant reaction system.

  17. The activation characteristics of the decomposition of H2O2 on palladium-carbon catalysts

    NASA Astrophysics Data System (ADS)

    Lapko, V. F.; Gerasimyuk, I. P.; Kuts', V. S.; Tarasenko, Yu. A.

    2010-06-01

    The kinetics of catalytic decomposition of H2O2 on palladium-carbon catalysts with various deposited metal distributions in carrier (active carbon) porous granules was studied. The activation parameters ( E a and A 0) of the process were calculated by the Arrhenius equation. A determining factor for the catalytic process was found to be the entropy factor ( A 0), which characterized the formation and dissociation of activated transition complexes. A quantum-chemical study of the electronic structure of palladium-carbon catalysts showed the occurrence of electron density transfer from the carbon matrix to metal clusters and collectivization of their electronic systems. This increased the donor-acceptor ability of the synthesized materials and, as a consequence, their catalytic activity.

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

    PubMed Central

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

    2014-01-01

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

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

    SciTech Connect

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

    1995-12-31

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

  20. Generation and remote delivery of plasma activated species

    NASA Astrophysics Data System (ADS)

    Maguire, Paul; Mahony, Charles; Kelsey, Colin; Rutherford, David; Mariotti, Davide; Macias-Montero, Manuel; Perez-Martin, Fatima; Diver, Declan

    2016-09-01

    Plasma interactions with microdroplets offer new opportunities to deliver active chemical agents and nanoparticles to remote substrates downstream with many potential applications from cancer theranostics and wound healing in biomedicine, gentle food decontamination and seed germination in plasma agriculture to catalyst production and photonic structures fabrication, among others. We demonstrate plasma-liquid based pristine nanomaterials synthesis in flight and subsequent delivery up to 120mm from the atmospheric pressure plasma source. Monosized and non-aggregating metal nanoparticles are formed in the rf plasma in less than 100us, representing an increase in precursor reduction rate that is many (>4) orders of magnitude faster than that observed with standard colloidal chemistry or via high energy radiolytic techniques. Also the collection and purification limitations of the latter are avoided. Plasma activated liquid including OH radicals and H2O2 are transported over 120mm and have demonstrated high efficacy bacterial decontamination. These results will be compared with charge species and radical transport from the rf plasma without microdroplets. Reaction models based on high solvated surface electron concentrations will be presented. Funding from EPSRC acknowledged (Grants EP/K006088/1 and EP/K006142/1).

  1. A new copper species based on an azo-compound utilized as a homogeneous catalyst for water oxidation.

    PubMed

    Yu, Wei-Bin; He, Qing-Ya; Ma, Xiu-Fang; Shi, Hua-Tian; Wei, Xianwen

    2015-01-07

    A new azo-complex [(L)Cu(II)(NO3)] [L = (E)-3-(pyridin-2-yldiazenyl)naphthalen-2-ol (HL)], was prepared via a one-pot synthetic method at 60 °C and was structurally characterized by IR, EA, PXRD and single crystal X-ray diffraction. In addition, TGA studies indicated that the complex was stable in air. The redox properties were determined by cyclic voltammetry, which revealed that the complex could be utilized as a catalyst for water oxidation under mild conditions. Subsequently, the complex was employed as a catalyst to take part in water oxidation reaction in the presence of a Ce(IV) salt utilized as an oxidant at pH 11 in PBS (Phosphate Buffered Saline) solution. The results suggested that the catalyst exhibited a high stability and activity toward water oxidation reaction under these conditions with an initial TOF of 4.0 kPa h(-1). Calculation methodology was performed to study the mechanism of the reaction, which revealed that in this catalytic process, the initial oxidation of Cu(II) to Cu(III) occurred by the formation of an intermediate "Cu(III)-O-O-Cu(III)". The formation of this intermediate, resulted in a release of oxygen and closing of the catalytic cycle.

  2. Stability and activity of molybdenum carbide catalysts for the oxidative reforming of methane

    NASA Astrophysics Data System (ADS)

    Lamont, David Charles

    Molybdenum carbide catalysts have been studied for oxidative reforming, in particular, the effect on reforming activity of the method by which they were synthesized, their stability under conditions of varying mass transfer, and the measurement of their inherent reaction kinetics. These catalysts show promise as possible alternatives to both conventional supported nickel catalysts, as well as to the rare and expensive noble metal catalysts. Samples of Mo 2C were synthesized in house and compared to a commercial sample of Mo2C for the CO2 (dry) reforming of methane. It was found that high surface areas, previously thought to be important for activity, were not a property of the Mo2C, but instead were attributable to large amounts of excess carbon. This carbon had a detrimental effect on catalyst stability under dry reforming conditions, because it enhanced deposition of refractory carbon via methane cracking. The commercial sample of Mo 2C, while of low surface area and containing no excess carbon, behaved more stably over time. In another investigation, Mo2C was studied for its stability under varying mass transfer conditions, because of evidence showing that the Mo2C can undergo redox chemistry at reforming conditions. Under dry reforming conditions, it was found that some feed mixtures are net oxidizing, but that oxidation in the presence of such feed mixtures could be prevented by operating under mass transfer limited conditions, which resulted in sufficiently high partial pressures of CO and H2 in the catalyst boundary layer. Similar stability was achieved by co-feeding CO to the catalyst bed, which allowed for stable operation under conditions that were not mass transfer limited. Using this approach, measurements of the intrinsic reaction kinetics of Mo2C for dry reforming were successfully achieved. These results pointed to a strong dependence of dry reforming rate on both CH4 and CO2 partial pressures, as well as evidence for a reaction mechanism unique from

  3. Characterization and HDS activity of Mo/TiO sub 2 and Ni(Co)-Mo/TiO sub 2 catalysts

    SciTech Connect

    Quincy, R.B.; Houalla, M.; Hercules, D.M.

    1987-04-01

    A series of Mo/TiO{sub 2} catalysts ranging from 1 to 15 wt% MoO{sub 3} was prepared by incipient wetness impregnation. The catalysts were characterized by laser Raman spectroscopy (LRS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS, ESCA), and gravimetric analysis. The Mo interaction species and MoO{sub 3} were identified and quantitated by Raman spectroscopy. The Mo interaction species increased with Mo loading up to 6 wt% MoO{sub 3} and leveled off at higher Mo loadings. MoO{sub 3} is detected at 7.5 wt% MoO{sub 3}/TiO{sub 2} and increased linearly with further Mo additions. The molybdenum speciation determined from Raman data is shown to correlate with ESCA and XRD measurements. The reduction characteristics of molybdenum on titania depend on Mo loading, and a lower average Mo oxidation state is found for Mo/TiO{sub 2} than previously reported for comparable loadings of Mo/Al{sub 2}O{sub 3} catalysts. Correlation between structure and thiophene hydrodesulfurization activity is presented for the Mo/TiO{sub 2} series. The influence of nickel (cobalt) addition on the surface structure and the reactivity of the Mo/TiO{sub 2} catalysts is also examined.

  4. Metal catalysts supported on activated carbon fibers for removal of polycyclic aromatic hydrocarbons from incineration flue gas.

    PubMed

    Lin, Chiou-Liang; Cheng, Yu-Hsiang; Liu, Zhen-Shu; Chen, Jian-Yuan

    2011-12-15

    The aim of this research was to use metal catalysts supported on activated carbon fibers (ACFs) to remove 16 species of polycyclic aromatic hydrocarbons (PAHs) from incineration flue gas. We tested three different metal loadings (0.11 wt%, 0.29 wt%, and 0.34 wt%) and metals (Pt, Pd, and Cu), and two different pretreatment solutions (HNO(3) and NaOH). The results demonstrated that the ACF-supported metal catalysts removed the PAHs through adsorption and catalysis. Among the three metals, Pt was most easily adsorbed on the ACFs and was the most active in oxidation of PAHs. The mesopore volumes and density of new functional groups increased significantly after the ACFs were pretreated with either solutions, and this increased the measured metal loading in HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs. These data confirm that improved PAH removal can be achieved with HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs.

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

    DOE PAGES

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; ...

    2015-06-11

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

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

    SciTech Connect

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

    2015-06-11

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

  7. Synthesis of active carbon-based catalysts by chemical vapor infiltration for nitrogen oxide conversion.

    PubMed

    Busch, Martin; Bergmann, Ulf; Sager, Uta; Schmidt, Wolfgang; Schmidt, Frank; Notthoff, Christian; Atakan, Burak; Winterer, Markus

    2011-09-01

    Direct reduction of nitrogen oxides is still a challenge. Strong efforts have been made in developing noble and transition metal catalysts on microporous support materials such as active carbons or zeolites. However, the required activation energy and low conversion rates still limit its breakthrough. Furthermore, infiltration of such microporous matrix materials is commonly performed by wet chemistry routes. Deep infiltration and homogeneous precursor distribution are often challenging due to precursor viscosity or electrostatic shielding and may be inhibited by pore clogging. Gas phase infiltration, as an alternative, can resolve viscosity issues and may contribute to homogeneous infiltration of precursors. In the present work new catalysts based on active carbon substrates were synthesized via chemical vapor infiltration. Iron oxide nano clusters were deposited in the microporous matrix material. Detailed investigation of produced catalysts included nitrogen oxide adsorption, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Catalytic activity was studied in a recycle flow reactor by time-resolved mass spectrometry at a temperature of 423 K. The infiltrated active carbons showed very homogeneous deposition of iron oxide nano clusters in the range of below 12 to 19 nm, depending on the amount of infiltrated precursor. The specific surface area was not excessively reduced, nor was the pore size distribution changed compared to the original substrate. Catalytic nitrogen oxides conversion was detected at temperatures as low as 423 K.

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

    SciTech Connect

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

    2015-01-12

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

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

    DOE PAGES

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; ...

    2015-01-12

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

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

    EPA Science Inventory

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

  11. The Biginelli reaction with an imidazolium-tagged recyclable iron catalyst: kinetics, mechanism, and antitumoral activity.

    PubMed

    Ramos, Luciana M; Guido, Bruna C; Nobrega, Catharine C; Corrêa, José R; Silva, Rafael G; de Oliveira, Heibbe C B; Gomes, Alexandre F; Gozzo, Fábio C; Neto, Brenno A D

    2013-03-25

    The present work describes the synthesis, characterization, and application of a new ion-tagged iron catalyst. The catalyst was employed in the Biginelli reaction with impressive performance. High yields have been achieved when the reaction was carried out in imidazolium-based ionic liquids (BMI⋅PF6, BMI⋅NTf2, and BMI⋅BF4), thus showing that the ionic-liquid effects play a role in the reaction. Moreover, the ion-tagged catalyst could be recovered and reused up to eight times without any noticeable loss in activity. Mechanistic studies performed by using high-resolution electrospray-ionization quadrupole-time-of-flight mass (HR-EI-QTOF) spectrometry and kinetic experiments indicate only one reaction pathway and rule out the other two possibilities under the development conditions. The theoretical calculations are in accordance with the proposed mechanism of action of the iron catalyst. Finally, the 37 dihydropyrimidinone derivatives, products of the Biginelli reaction, had their cytotoxicity evaluated in assays against MCF-7 cancer cell linages with encouraging results of some derivatives, which were virtually non-toxic against healthy cell linages (fibroblasts).

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

    PubMed

    Yadav, Bholu Ram; Garg, Anurag

    2016-01-01

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

  13. Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

    SciTech Connect

    Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

    2016-11-18

    Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.

  14. Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

    DOE PAGES

    Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; ...

    2016-11-18

    Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent tomore » good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.« less

  15. Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

    PubMed Central

    Mo, Jingke; Kang, Zhenye; Retterer, Scott T.; Cullen, David A.; Toops, Todd J.; Green, Johney B.; Mench, Matthew M.; Zhang, Feng-Yuan

    2016-01-01

    Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices. PMID:28138516

  16. Ni-, Pd-, or Pt-catalyzed ethylene dimerization: a mechanistic description of the catalytic cycle and the active species.

    PubMed

    Roy, Dipankar; Sunoj, Raghavan B

    2010-03-07

    Two key mechanistic possibilities for group 10 transition metal [M(eta(3)-allyl)(PMe(3))](+) catalyzed (where M = Ni(II), Pd(II) and Pt(II)) ethylene dimerization are investigated using density functional theory methods. The nature of the potential active catalysts in these pathways is analyzed to gain improved insights into the mechanism of ethylene dimerization to butene. The catalytic cycle is identified as involving typical elementary steps in transition metal-catalyzed C-C bond formation reactions, such as oxidative insertion as well as beta-H elimination. The computed kinetic and thermodynamic features indicate that a commonly proposed metal hydride species (L(n)M-H) is less likely to act as the active species as compared to a metal-ethyl species (L(n)M-CH(2)CH(3)). Of the two key pathways considered, the active species is predicted to be a metal hydride in pathway-1, whereas a metal alkyl complex serves as the active catalyst in pathway-2. A metal-mediated hydride shift from a growing metal alkyl chain to the ethylene molecule, bound to the metal in an eta(2) fashion, is predicted to be the preferred route for the generation of the active species. Among the intermediates involved in the catalytic cycle, metal alkyls with a bound olefin are identified as thermodynamically stable for all three metal ions. In general, the Ni-catalyzed pathways are found to be energetically more favorable than those associated with Pd and Pt catalysts.

  17. Characterization of catalysts with metal-support effects and of the species adsorbed on their surfaces

    NASA Astrophysics Data System (ADS)

    Vannice, M. A.

    1985-06-01

    The influence of crystallite size and the support on heats of adsorption of H2, CO, and O2 on Pt and Pd are reported. Isothermal, integral heats of adsorption have been measured for H2 and CO adsorption on Pt and Pd dispersed on four supports, SiO2, Al2O3, and SiO2-Al2O3. These values were determined at 215K and 300 to 320K. Results are presented. For support Pt the heats of adsorption were highest on Pt/SiO2 and lowest on Pt/TiO2. However, a clear trend existed between heats of adsorption and Pt exposed with large Pt crystallites having the highest values. The Pd catalysts exhibited behavior different than those for the Pt catalysts in two major aspects. First, the heats of adsorption values tended to increase somewhat as crystallite sizes became very small. Second, the high temperature reduction step did not decrease the heats of adsorption values as significantly for Pd/TiO2.

  18. Oxyhydrochlorination catalyst

    DOEpatents

    Taylor, Charles E.; Noceti, Richard P.

    1992-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

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

    SciTech Connect

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

    2015-07-02

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

  1. Examination of the activity and durability of PEMFC catalysts in liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Takahashi, Ikuma; Kocha, Shyam S.

    Widespread research in the field of fuel cells necessitates easily verifiable and reproducible benchmarks for characterizing properties such as electrochemical area (ECA), oxygen reduction reaction (ORR) specific and mass activity (i s, i m) as well as durability of electrocatalysts. Ex situ characterization of electrocatalysts deposited as thin-film rotating disk electrodes (TF-RDE) in liquid electrolytes as well as in their original dry powder state has been conducted. Commercially available Pt on carbon support (Pt/C) catalyst serving as a baseline benchmark and heat treated Pt/C and Pt-alloy/C catalysts were investigated as examples of higher activity and durability materials. A detailed description of the preparation and optimization of catalyst inks, measurement protocols, and analysis of ORR kinetic parameters and durability rates are provided to form a basis for consistent screening and benchmarking of new and improved catalysts for proton exchange membrane fuel cells (PEMFCs). Preparation of highly-dispersed ink slurries formulated using various water-isopropanol mixtures and deposited as TF-RDEs were demonstrated to significantly affect the magnitude of measured ECA and activity. The ECA, i s and i m for the baseline Pt/C were determined to be 100 m 2 g -1, 292 μA cm -2 Pt and 266 mA mg -1 Pt in 0.1 M HClO 4 at 25 °C and 10 mV s -1. Strong adsorption of anions on Pt/C in sulfuric acid was shown to have a deleterious effect on its activity and durability. Related ORR kinetic parameters such as the activation energy (Δ H = 38 kcal mol -1) as well as the experimental reaction order (m ∼ 0.75) with respect to oxygen were determined to provide a basis for converting literature results to a common pressure and temperature.

  2. Structure and nuclearity of active sites in Fe-zeolites: comparison with iron sites in enzymes and homogeneous catalysts.

    PubMed

    Zecchina, Adriano; Rivallan, Mickaël; Berlier, Gloria; Lamberti, Carlo; Ricchiardi, Gabriele

    2007-07-21

    Fe-ZSM-5 and Fe-silicalite zeolites efficiently catalyse several oxidation reactions which find close analogues in the oxidation reactions catalyzed by homogeneous and enzymatic compounds. The iron centres are highly dispersed in the crystalline matrix and on highly diluted samples, mononuclear and dinuclear structures are expected to become predominant. The crystalline and robust character of the MFI framework has allowed to hypothesize that the catalytic sites are located in well defined crystallographic positions. For this reason these catalysts have been considered as the closest and best defined heterogeneous counterparts of heme and non heme iron complexes and of Fenton type Fe(2+) homogeneous counterparts. On this basis, an analogy with the methane monooxygenase has been advanced several times. In this review we have examined the abundant literature on the subject and summarized the most widely accepted views on the structure, nuclearity and catalytic activity of the iron species. By comparing the results obtained with the various characterization techniques, we conclude that Fe-ZSM-5 and Fe-silicalite are not the ideal samples conceived before and that many types of species are present, some active and some other silent from adsorptive and catalytic point of view. The relative concentration of these species changes with thermal treatments, preparation procedures and loading. Only at lowest loadings the catalytically active species become the dominant fraction of the iron species. On the basis of the spectroscopic titration of the active sites by using NO as a probe, we conclude that the active species on very diluted samples are isolated and highly coordinatively unsaturated Fe(2+) grafted to the crystalline matrix. Indication of the constant presence of a smaller fraction of Fe(2+) presumably located on small clusters is also obtained. The nitrosyl species formed upon dosing NO from the gas phase on activated Fe-ZSM-5 and Fe-silicalite, have been analyzed

  3. Zirconia supported catalysts for bioethanol steam reforming: Effect of active phase and zirconia structure

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Rodríguez, L.; Sanz, J. L.; Daza, L.

    Three new catalysts have been prepared in order to study the active phase influence in ethanol steam reforming reaction. Nickel, cobalt and copper were the active phases selected and were supported on zirconia with monoclinic and tetragonal structure, respectively. To characterize the behaviour of the catalysts in reaction conditions a study of catalytic activity with temperature was performed. The highest activity values were obtained at 973 K where nickel and cobalt based catalysts achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. Nickel supported on tetragonal zirconia exhibited the highest hydrogen production efficiency, higher than 4.5 mol H 2/mol EtOH fed. The influence of steam/carbon (S/C) ratio on product distribution was another parameter studied between the range 3.2-6.5. Nickel supported on tetragonal zirconia at S/C = 3.2 operated at 973 K without by-product production such as ethylene or acetaldehyde. In order to consider a further application in an ethanol processor, a long-term reaction experiment was performed at 973 K, S/C = 3.2 and atmospheric pressure. After 60 h, nickel supported on tetragonal zirconia exhibited high stability and selectivity to hydrogen production.

  4. Phytochemistry and biological activities of Phlomis species.

    PubMed

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

    2009-09-07

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

  5. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries

    NASA Astrophysics Data System (ADS)

    Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki; Nakanishi, Haruyuki; Goodenough, John B.; Shao-Horn, Yang

    2011-07-01

    The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ*-orbital (eg) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ* orbital and metal-oxygen covalency on the competition between O22-/OH- displacement and OH- regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

  6. Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Grimaud, Alexis; Demortiere, Arnaud; Saubanere, Matthieu; Dachraoui, Walid; Duchamp, Martial; Doublet, Marie-Liesse; Tarascon, Jean-Marie

    2017-01-01

    The oxygen evolution reaction (OER) is of prime importance in multiple energy storage devices; however, deeper mechanistic understanding is required to design enhanced electrocatalysts for the reaction. Current understanding of the OER mechanism based on oxygen adsorption on a metallic surface site fails to fully explain the activity of iridium and ruthenium oxide surfaces, and the drastic surface reconstruction observed for the most active OER catalysts. Here we demonstrate, using La2LiIrO6 as a model catalyst, that the exceptionally high activity found for Ir-based catalysts arises from the formation of active surface oxygen atoms that act as electrophilic centres for water to react. Moreover, with the help of transmission electron microscopy, we observe drastic surface reconstruction and iridium migration from the bulk to the surface. Therefore, we establish a correlation between surface activity and surface stability for OER catalysts that is rooted in the formation of surface reactive oxygen.

  7. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries.

    PubMed

    Suntivich, Jin; Gasteiger, Hubert A; Yabuuchi, Naoaki; Nakanishi, Haruyuki; Goodenough, John B; Shao-Horn, Yang

    2011-06-12

    The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

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

    PubMed

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

    2016-01-15

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

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

    PubMed

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

    2016-05-04

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

  10. Dry reforming of methane on a highly-active Ni-CeO2 catalyst: Effects of metal-support interactions on C–H bond breaking

    DOE PAGES

    Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.; ...

    2016-05-04

    Ni-CeO2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV onmore » Ni/CeO2–x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C1s XPS region. As a result, the reforming of methane proceeds in a clean and efficient way.« less

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

    PubMed

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

    2016-06-20

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  13. Activated carbon fibers impregnated with Pd and Pt catalysts for toluene removal.

    PubMed

    Liu, Zhen-Shu; Chen, Jian-Yuan; Peng, Yu-Hui

    2013-07-15

    Few studies have investigated the use of activated carbon fibers (ACFs) impregnated with noble metals for the catalytic oxidation of volatile organic compounds (VOCs). This study determined the removal efficiency of toluene as a function of time over ACF-supported metal catalysts. Two catalysts (Pt and Pd), five reaction temperatures (120, 150, 200, 250, and 300°C), and three oxygen contents (6%, 10%, and 21%) were investigated to determine the removal of toluene. To study the effects of the characteristics of the catalysts on toluene removal, the composition and morphology of the ACFs were analyzed using the BET, XPS, ICP, and FE-SEM. The results showed that the 0.42%Pd/ACFs showed greater activity for toluene removal than did 2.68%Pt/ACFs at a reaction temperature of 200°C and an oxygen content of 10%. The main removal mechanism of toluene over the 2.68%Pt/ACFs at reaction temperatures less than 200°C was adsorption. The long-term catalytic activity of the 2.68%Pt/ACFs for toluene removal at a reaction temperature of 250°C and an oxygen content of 10% could be obtained. Furthermore, toluene removal over the 2.68%Pt/ACFs at 200°C could be enhanced with increasing oxygen content.

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

    SciTech Connect

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

    2011-10-15

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

  15. Design of a high activity and selectivity alcohol catalyst

    SciTech Connect

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

    1992-02-07

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

  16. Catalytic activity of titania zirconia mixed oxide catalyst for dimerization eugenol

    NASA Astrophysics Data System (ADS)

    Tursiloadi, S.; Kristiani, A.; Jenie, S. N. Aisyiyah; Laksmono, J. A.

    2017-01-01

    Clove oil has been found to possess antibacterial, antifungal, antiviral, antitumor, antioxidant and insecticidal properties. The major compound of clove oil is eugenol about 49-87%. Eugenol as phenolic compounds exhibits antioxidant and antimicrobial activities. The derivative compound of eugenol, dieugenol, show antioxidant potency better than parent eugenol. A series of TiO2-ZrO2 mixed oxides (TZ) with various titanium contents from 0 to 100wt%, prepared by using sol gel method were tested their catalytic activity for dimerization eugenol, Their catalytic activity show that these catalysts resulted a low yield of dimer eugenol, dieugenol, about 2-9 % and the purity is more than 50%.

  17. Mechanism-Guided Development of a Highly Active Bis-Thiourea Catalyst for Anion-Abstraction Catalysis.

    PubMed

    Kennedy, C Rose; Lehnherr, Dan; Rajapaksa, Naomi S; Ford, David D; Park, Yongho; Jacobsen, Eric N

    2016-10-05

    We describe the rational design of a linked, bis-thiourea catalyst with enhanced activity relative to monomeric analogs in a representative enantioselective anion-abstraction reaction. Mechanistic insights guide develop-ment of this linking strategy to favor substrate activation though the intramolecular cooperation of two thiourea sub-units while avoiding nonproductive aggregation. The resulting catalyst platform overcomes many of the practical limitations that have plagued hydrogen-bond donor catalysis and enables use of catalyst loadings as low as 0.05 mol %. Computational analyses of possible anion-binding modes provide detailed insight into the precise mechanism of anion-abstraction catalysis with this pseudo-dimeric thiourea.

  18. Titanium cobalt nitride supported platinum catalyst with high activity and stability for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2015-06-01

    We describe a facile route to the development of novel robust non-carbon titanium cobalt nitride (Ti0.9Co0.1N) used as a support for Pt, and the catalyst exhibits high activity and stability for the oxygen reduction reaction (ORR). XRD and TEM results show that the synthesized Ti0.9Co0.1N is formed as a single-phase solid solution with high purity. The XPS measurements verified the strong metal/support interaction between Pt nanoparticles (NPs) and the Ti0.9Co0.1N support. Most importantly, Ti0.9Co0.1N supported Pt catalyst (Pt/Ti0.9Co0.1N) exhibits a much higher mass activity and durability than that of the commercial JM Pt/C electrocatalyst for ORR. The accelerated durability test (ADT) reveals that the novel Ti0.9Co0.1N support can dramatically enhance the durability of the catalyst and maintain the electrochemical surface area (ECSA) of Pt. Pt/Ti0.9Co0.1N shows great improvement in ECSA preservation, with only 35% of the initial ECSA drop even after 10 000 ADT cycles. The experimental data indicate that the electronic structure of Pt can be modified by Co doping, and there exists a strong interaction between Pt and the Ti0.9Co0.1N support, both of them are playing an important role in improving the activity and durability of the Pt/Ti0.9Co0.1N catalyst.

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

    EPA Science Inventory


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



  20. Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases.

    PubMed

    Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao; Chen, Zhuqi; Wu, Kangbing; Yin, Guochuan

    2015-06-07

    Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like Zn(2+) through a plausible chloride or OTf(-) bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

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

    SciTech Connect

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

    2015-04-02

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

  2. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  3. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells.

    PubMed

    Setzler, Brian P; Zhuang, Zhongbin; Wittkopf, Jarrid A; Yan, Yushan

    2016-12-06

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW(-1) in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    PubMed

    Mohanta, Jagdeep; Satapathy, Smithsagar; Si, Satyabrata

    2016-02-03

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

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2015-04-09

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

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

    PubMed

    Baran, Talat; Inanan, Tülden; Menteş, Ayfer

    2016-07-10

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

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

    SciTech Connect

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

    2015-10-13

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

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

    DOE PAGES

    Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; ...

    2015-10-13

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

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

    PubMed Central

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

    2015-01-01

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

  12. Synthesis and catalytic activity of heterogeneous rare-earth metal catalysts coordinated with multitopic Schiff-base ligands.

    PubMed

    Sun, Yilin; Wu, Guangming; Cen, Dinghai; Chen, Yaofeng; Wang, Limin

    2012-08-28

    Four multitopic Schiff-base ligand precursors were synthesized via condensation of 4,4'-diol-3,3'-diformyl-1,1'-diphenyl or 1,3,5-tris(4-hydroxy-5-formylphenyl)benzene with 2,6-diisopropylaniline or 2,6-dimethylaniline. Amine elimination reactions of Ln[N(SiMe(3))(2)](3) (Ln = La, Nd, Sm or Y) with these multitopic ligand precursors gave ten heterogeneous rare-earth metal catalysts. These heterogeneous rare-earth metal catalysts are active for intramolecular hydroalkoxylation of alkynols, and the catalytic activities are influenced by the ligand and metal ion. The recycling experiment on the most active heterogeneous catalyst showed the catalyst has a good reusability.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  14. A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Application of Quantitative Structure Activity/Selectivity Relationships

    PubMed Central

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

    2011-01-01

    While the synthetic utility of asymmetric phase transfer catalysis continues to expand, the number of proven catalyst types and design criteria remains limited. At the origin of this scarcity is a lack in understanding of how catalyst structural features affect the rate and enantioselectivity of phase transfer catalyzed reactions. Described in this paper is the development of quantitative structure-activity relationships (QSAR) and -selectivity relationships (QSSR) for the alkylation of a protected glycine imine with libraries of quaternary ammonium ion catalysts. Catalyst descriptors including ammonium ion accessibility, interfacial adsorption affinity, and partition coefficient were found to correlate meaningfully with catalyst activity. The physical nature of the descriptors was rationalized through differing contributions of the interfacial and extraction mechanisms to the reaction under study. The variation in the observed enantioselectivity was rationalized employing a comparative molecular field analysis (CoMFA) using both the steric and electrostatic fields of the catalysts. A qualitative analysis of the developed model reveals preferred regions for catalyst binding to afford both configurations of the alkylated product. PMID:21446723

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

    SciTech Connect

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

    2015-06-04

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

  16. Nanostructured catalysts for organic transformations.

    PubMed

    Chng, Leng Leng; Erathodiyil, Nandanan; Ying, Jackie Y

    2013-08-20

    The development of green, sustainable and economical chemical processes is one of the major challenges in chemistry. Besides the traditional need for efficient and selective catalytic reactions that will transform raw materials into valuable chemicals, pharmaceuticals and fuels, green chemistry also strives for waste reduction, atomic efficiency and high rates of catalyst recovery. Nanostructured materials are attractive candidates as heterogeneous catalysts for various organic transformations, especially because they meet the goals of green chemistry. Researchers have made significant advances in the synthesis of well-defined nanostructured materials in recent years. Among these are novel approaches that have permitted the rational design and synthesis of highly active and selective nanostructured catalysts by controlling the structure and composition of the active nanoparticles (NPs) and by manipulating the interaction between the catalytically active NP species and their support. The ease of isolation and separation of the heterogeneous catalysts from the desired organic product and the recovery and reuse of these NPs further enhance their attractiveness as green and sustainable catalysts. This Account reviews recent advances in the use of nanostructured materials for catalytic organic transformations. We present a broad overview of nanostructured catalysts used in different types of organic transformations including chemoselective oxidations and reductions, asymmetric hydrogenations, coupling reactions, C-H activations, oxidative aminations, domino and tandem reactions, and more. We focus on recent research efforts towards the development of the following nanostructured materials: (i) nanostructured catalysts with controlled morphologies, (ii) magnetic nanocomposites, (iii) semiconductor-metal nanocomposites, and (iv) hybrid nanostructured catalysts. Selected examples showcase principles of nanoparticle design such as the enhancement of reactivity, selectivity

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

    SciTech Connect

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

    2012-10-05

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

  18. Wet hydrogen peroxide catalytic oxidation of phenol with FeAC (iron-embedded activated carbon) catalysts.

    PubMed

    Liou, Rey-May; Chen, Shih-Hsiung; Huang, Cheng-Hsien; Hung, Mu-Ya; Chang, Jing-Song; Lai, Cheng-Lee

    2010-01-01

    This investigation aims at exploring the catalytic oxidation activity of iron-embedded activated carbon (FeAC) and the application for the degradation of phenol in the wet hydrogen peroxide catalytic oxidation (WHPCO). FeAC catalysts were prepared by pre-impregnating iron in coconut shell with various iron loadings in the range of 27.5 to 46.5% before they were activated. The FeAC catalysts were characterised by measuring their surface area, pore distribution, functional groups on the surface, and X-ray diffraction patterns. The effects of iron loading strongly inhibited the pore development of the catalyst but benefited the oxidation activity in WHPCO. It was found that the complete conversion of phenol was observed with all FeAC catalysts in oxidation. High level of chemical oxygen demand (COD) abatement can be achieved within the first 30 minutes of oxidation. The iron embedded in the activated carbon showed good performance in the degradation and mineralisation of phenol during the oxidation due to the active sites as iron oxides formed on the surface of the activated carbon. It was found that the embedding irons were presented in gamma-Fe(2)O(3), alpha-Fe(2)O(3), and alpha-FeCOOH forms on the activated carbon. The aging tests on FeAC catalysts showed less activity loss, and less iron leaching was found after four oxidation runs.

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

    SciTech Connect

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

    2010-01-01

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

  20. Catalyst dispersion and activity under conditions of temperature- staged liquefaction. Technical progress report, July--September 1991

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

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

    DOEpatents

    Muzio, Lawrence J.; Smith, Randall A.

    2009-12-22

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

  2. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Technical progress report, October--December 1991

    SciTech Connect

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

    1992-02-01

    The general objectives of this research are (1) to investigate the use of highly dispersed catalysts for the pretreatment of coal by mild hydrogenation, (2) to identify the active forms of the catalysts under reaction conditions and (3) to clarify the mechanisms of catalysis. The ultimate objective is to ascertain if mild catalytic hydrogenation resulting in very limited or no coal solubilization is an advantageous pretreatment for the transformation of coal into transportable fuels. The experimental program will focus upon the development of effective methods of impregnating coal with catalysts, evaluating the conditions under which the catalysts are most active and establishing the relative impact of improved impregnation on conversion and product distributions obtained from coal hydrogenation.

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

    NASA Astrophysics Data System (ADS)

    Yik, Edwin Shyn-Lo

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

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

    PubMed

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

    2015-11-15

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

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

    SciTech Connect

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

    2015-11-20

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

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

    DOE PAGES

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; ...

    2015-11-20

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

  7. Comparison of the Activity and the Stability in CO Oxidation of Au-Cu Catalysts Supported on TiO2 in Anatase or Rutile Phase.

    PubMed

    Zanella, Rodolfo; Bokhimi, Xim; Maturano, Viridiana; Morales, Antonio

    2015-09-01

    Au-Cu catalysts supported on anatase or rutile phases were prepared by deposition-precipitation method. The titania polymorph used as the support determined the catalytic behavior. For the Au-Cu/rutile catalysts, the metallic phase had smaller dimensions than for the Au-Cu/anatase catalysts. The catalysts supported on anatase, however, were more active and stable than those supported on rutile. A systematic study of the catalytic activity for CO oxidation as a function of the temperature of activation and the aging time was performed. The catalytic properties were correlated with the properties of the catalysts analyzed with X-ray powder diffraction, refinement of the crystalline structures with the Rietveld method, and transmission electron microscopy. When the support was anatase, a pretreatment at 400 degrees C in air led to the most active catalysts, whereas when the support was rutile, a pretreatment between 200 and 300 degrees C in air led to the most active catalysts; activation under hydrogen generated less active catalysts. The Au-Cu catalysts activated in air were more active for the oxidation of CO than the respective monometallic gold catalysts, indicating a promoting effect between gold and copper to catalyze this reaction.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  9. Highly active chromium-based selective ethylene tri-/tetramerization catalysts supported by PNPO phosphazane ligands.

    PubMed

    Zhou, Yusheng; Wu, Hongfei; Xu, Sheng; Zhang, Xuejun; Shi, Min; Zhang, Jun

    2015-05-28

    Novel Cr(iii) catalysts supported by PNPO phosphazane ligands of the type Ph2PN(R)P(Ph)OAr have been prepared, all of which, upon activation with MMAO-3A, are highly active in ethylene tri-/tetramerization with considerable selectivity. The effect of ligand substitution on the catalytic performance has been examined. The Cr precatalyst supported by the PNPO phosphazane ligand with an N-cyclohexyl achieved high activity of 316.7 kg (g Cr h(-1))(-1) and a high total selectivity of 85.1% towards valuable 1-hexene (45.7%) and 1-octene (39.4%) using chlorobenzene as the solvent at 35 bar and 40 °C. In methylcyclohexane, the precatalyst supported by [Ph2PN((i)Pr)P(Ph)OPh] exhibited a higher 1-octene selectivity (54.0%) with a considerable activity of 73.3 kg (g Cr h(-1))(-1) at 35 bar and 40 °C. With the fine-tuned ligand backbone, such a PNPO phosphazane-based catalyst system provides a mode for precise understanding of the impact of ligand variations on catalytic performance.

  10. Ring-expanding olefin metathesis: a route to highly active unsymmetrical macrocyclic oligomeric co-salen catalysts for the hydrolytic kinetic resolution of epoxides.

    PubMed

    Zheng, Xiaolai; Jones, Christopher W; Weck, Marcus

    2007-02-07

    In the presence of the third generation Grubbs catalyst, the ring-expanding olefin metathesis of a monocyclooct-4-en-1-yl functionalized salen ligand and the corresponding Co(II)(salen) complex at low monomer concentrations results in the exclusive formation of macrocyclic oligomeric structures with the salen moieties being attached in an unsymmetrical, flexible, pendent manner. The TOF-MALDI mass spectrometry reveals that the resulting macrocyclic oligomers consist predominantly of dimeric to tetrameric species, with detectable traces of higher homologues up to a decamer. Upon activation under aerobic and acidic conditions, these Co(salen) macrocycles exhibit extremely high reactivities and selectivities in the hydrolytic kinetic resolution (HKR) of a variety of racemic terminal epoxides under neat conditions with very low catalyst loadings. The excellent catalytic properties can be explained in terms of the new catalyst's appealing structural features, namely, the flexible oligomer backbone, the unsymmetrical pendent immobilization motif of the catalytic sites, and the high local concentration of Co(salen) species resulting from the macrocyclic framework. This ring-expanding olefin metathesis is suggested to be a simple way to prepare tethered metal complexes that are endowed with key features--(i) a high local concentration of metal complexes and (ii) a flexible, single point of attachment to the support--that facilitate rapid and efficient catalysis when a bimetallic transition state is required.

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

    SciTech Connect

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

    2008-01-01

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

  12. Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction.

    PubMed

    Scheuermann, Gil M; Rumi, Luigi; Steurer, Peter; Bannwarth, Willi; Mülhaupt, Rolf

    2009-06-17

    Pd(2+)-exchanged graphite oxide and chemically derived graphenes therefrom were employed as supports for Pd nanoparticles. The influence of catalyst preparation, carbon functionalization, and catalyst morphology on the catalytic activity in the Suzuki-Miyaura coupling reactions was investigated. The catalysts were characterized by means of spectroscopy (FT-IR, solid-state (13)C NMR, AAS, XPS), X-ray scattering (WAXS), surface area analysis (BET, methylene blue adsorption), and electron microscopy (TEM, ESEM). In contrast to the conventional Pd/C catalyst, graphite oxide and graphene-based catalysts gave much higher activities with turnover frequencies exceeding 39,000 h(-1), accompanied by very low palladium leaching (<1 ppm).

  13. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

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

    ERIC Educational Resources Information Center

    Schug, Mark C.; Shaw, Jane S.

    1997-01-01

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

  15. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction.

    PubMed

    Seitz, Linsey C; Dickens, Colin F; Nishio, Kazunori; Hikita, Yasuyuki; Montoya, Joseph; Doyle, Andrew; Kirk, Charlotte; Vojvodic, Aleksandra; Hwang, Harold Y; Norskov, Jens K; Jaramillo, Thomas F

    2016-09-02

    Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrOx/SrIrO3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO3 or anatase IrO2 motifs. The IrOx/SrIrO3 catalyst outperforms known IrOx and ruthenium oxide (RuOx) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.

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

    PubMed

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

    2013-08-28

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

  17. Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

    PubMed

    Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

    2015-06-04

    We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

  18. Modeling CO and N2 adsorption at Cr surface species of Phillips catalyst by hybrid density functionals: effect of Hartree-Fock exchange percentage.

    PubMed

    Damin, Alessandro; Vitillo, Jenny G; Ricchiardi, Gabriele; Bordiga, Silvia; Lamberti, Carlo; Groppo, Elena; Zecchina, Adriano

    2009-12-31

    In this article, we present a computational study of the structure and vibrational properties of the species formed by the interaction between Cr sites of Phillips catalyst and probe molecules (CO, N(2)). The vibrational properties of these surface species, intensively investigated in the past, form a very rich and ideal set of experimental data to test computational approaches. By adopting the X(4)Si(2)O(3)Cr (X = H, OH, F) cluster as a simplified model of the ([triple bond]SiO)(2)Cr(II) species present at the surface of the real catalyst, we found that the B3LYP hybrid functional (containing 20% of Hartree-Fock exchange), when applied to this model, is unable to reproduce with reasonable accuracy the currently available experimental data (principally coming from IR spectroscopy). Better agreement is obtained when the percentage of Hartree-Fock exchange is increased (up to 35-40%).

  19. Modeling CO and N2 Adsorption at Cr Surface Species of Phillips Catalyst by Hybrid Density Functionals: Effect of Hartree-Fock Exchange Percentage

    NASA Astrophysics Data System (ADS)

    Damin, Alessandro; Vitillo, Jenny G.; Ricchiardi, Gabriele; Bordiga, Silvia; Lamberti, Carlo; Groppo, Elena; Zecchina, Adriano

    2009-07-01

    In this article, we present a computational study of the structure and vibrational properties of the species formed by the interaction between Cr sites of Phillips catalyst and probe molecules (CO, N2). The vibrational properties of these surface species, intensively investigated in the past, form a very rich and ideal set of experimental data to test computational approaches. By adopting the X4Si2O3Cr (X = H, OH, F) cluster as a simplified model of the (≡SiO)2Cr(II) species present at the surface of the real catalyst, we found that the B3LYP hybrid functional (containing 20% of Hartree-Fock exchange), when applied to this model, is unable to reproduce with reasonable accuracy the currently available experimental data (principally coming from IR spectroscopy). Better agreement is obtained when the percentage of Hartree-Fock exchange is increased (up to 35-40%).

  20. Enhanced Activity and Stability of Pt catalysts on Functionalized Graphene Sheets for Electrocatalytic Oxygen Reduction

    SciTech Connect

    Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chong M.; Lin, Yuehe; Wang, Yong; Aksay, Ilhan A.; Liu, Jun

    2009-04-30

    Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets.

  1. Gold nanoparticles-graphene hybrids as active catalysts for Suzuki reaction

    SciTech Connect

    Li, Yang; Fan, Xiaobin; Qi, Junjie; Ji, Junyi; Wang, Shulan; Zhang, Guoliang; Zhang, Fengbao

    2010-10-15

    Graphene was successfully modified with gold nanoparticles in a facile route by reducing chloroauric acid in the presence of sodium dodecyl sulfate, which is used as both a surfactant and reducing agent. The gold nanoparticles-graphene hybrids were characterized by high-resolution transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction and energy X-ray spectroscopy. We demonstrate for the first time that the gold nanoparticles-graphene hybrids can act as efficient catalysts for the Suzuki reaction in water under aerobic conditions. The catalytic activity of gold nanoparticles-graphene hybrids was influenced by the size of the gold nanoparticles.

  2. Determination of the active center in calcium-nickel phosphate dehydrogenation catalyst

    SciTech Connect

    Attali, S.; Vigouroux, B.; Lenzi, M.; Pescia, J.

    1980-06-01

    Determination of the active center in calcium-nickel phosphate dehydrogenation catalyst, used industrially in the dehydrogenation of butenes to butadiene, showed that a stable trivalent nickel ion is involved. Apparently, electrons generated in the first (oxidation) step of the reaction are eliminated by reducing the trivalent to divalent nickel which is reoxidized by protons. The results were obtained by propanol dehydration-dehydrogenation on calcium-nickel phosphate (Ca/sub 8/Ni(PO/sub 4//sub )/6) calcined at 400/sup 0/-900/sup 0/C and by ESR spectroscopy.

  3. Physico-Chemical Property and Catalytic Activity of a CeO2-Doped MnO(x)-TiO2 Catalyst with SO2 Resistance for Low-Temperature NH3-SCR of NO(x).

    PubMed

    Shin, Byeongkil; Chun, Ho Hwan; Cha, Jin-Sun; Shin, Min-Chul; Lee, Heesoo

    2016-05-01

    The effects of CeO2 addition on the catalytic activity and the SO2 resistance of CeO2-doped MnO(x)-TiO2 catalysts were investigated for the low-temperature selective catalytic reduction (SCR) with NH3 of NO(x) emissions in marine applications. The most active catalyst was obtained from 30 wt% CeO2-MnO(x)-TiO2 catalyst in the whole temperature range of 100-300 degrees C at a low gas hourly space velocity (GHSV) of 10,000 h(-)1, and its de-NO(x) efficiency was higher than 90% over 250 degrees C. The enhanced catalytic activity may contribute to the dispersion state and catalytic acidity on the catalyst surface, and the highly dispersed Mn and Ce on the nano-scaled TiO2 catalyst affects the increase of Lewis and Brønsted acid sites. A CeO2-rich additive on MnO(x)-TiO2 could provide stronger catalytic acid sites, associated with NH3 adsorption and the SCR performance. As the results of sulfur resistance in flue gas that contains SO2, the de-NO(x) efficiency of MnO(x)-TiO2 decreased by 15% over 200 degrees C, whereas that of 30 wt% ceria-doped catalyst increased by 14-21% over 150 degrees C. The high SO2 resistance of CeO2-MnO(x)-TiO2 catalysts that resulted from the addition of ceria suppressed the formation of Mn sulfate species, which led to deactivation on the surface of nano-catalyst.

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

    PubMed

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

    2016-02-28

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

  5. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    PubMed

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1).

  6. Nanoporous and highly active silicon carbide supported CeO₂-catalysts for the methane oxidation reaction.

    PubMed

    Hoffmann, Claudia; Biemelt, Tim; Lohe, Martin R; Rümmeli, Mark H; Kaskel, Stefan

    2014-01-29

    CeOx @SiO2 nanoparticles are used for the first time for the generation of porous SiC materials with tailored pore diameter in the mesopore range containing encapsulated and catalytically active CeO2 nanoparticles. The nanocasting approach with a preceramic polymer and subsequent pyrolysis is performed at 1300 °C, selective leaching of the siliceous part results in CeOx /SiC catalysts with remarkable characteristics like monodisperse, spherical pores and specific surface areas of up to 438 m(2) ·g(-1) . Porous SiC materials are promising supports for high temperature applications. The catalysts show excellent activities in the oxidation of methane with onset temperatures of the reaction 270 K below the onset of the homogeneous reaction. The synthesis scheme using core-shell particles is suited to functionalize silicon carbide with a high degree of stabilization of the active nanoparticles against sintering in the core of the template even at pyrolysis temperatures of 1300 °C rendering the novel synthesis principle as an attractive approach for a wide range of catalytic reactions.

  7. Catalyst mixtures

    DOEpatents

    Masel, Richard I.; Rosen, Brian A.

    2017-02-14

    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.

  8. Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal-Organic Framework Catalysts.

    PubMed

    Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2016-05-04

    A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O (InPF-16), [In(popha)(2,2'-bipy)]⋅3 H2 O (InPF-17), [In3 (OH)3 (popha)2 (4,4'-bipy)]⋅4 H2 O (InPF-18), [In2 (popha)2 (4,4'-bipy)2 ]⋅3 H2 O (InPF-19), [In(OH)(Hpopha)]⋅0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]⋅4 H2 O (InPF-21) (InPF=indium polymeric framework, H3 popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.

  9. Hydrogenation of CO2 to methanol using copper/zinc oxide-based catalyst: Effect of active metal ratio

    NASA Astrophysics Data System (ADS)

    Zabidi, Noor Asmawati Mohd; Tasfy, Sara; Shaharun, Maizatul Shima

    2016-11-01

    Effects of Cu:Zn ratio on the catalytic performance of synthesized SBA-15 supported Cu/ZnO-based (CZS) catalyst for the hydrogenation of CO2 to methanol was investigated in a fixed bed reactor. The physicochemical properties of the synthesized CZS catalyst in terms of textural properties, morphological and reducibility are presented. Methanol productivity was found to be influenced by the ratio of Cu and Zn in the catalyst formulation. Methanol selectivity of 92.1 % and CO2 conversion of 14.2 % was achieved over CZS catalyst with active metal ratio of 70 %Cu:30% Zn in CO2 hydrogenation reaction performed at 250°C, 2.25 MPa, and H2/CO2 ratio of 3.

  10. Effect of gamma irradiation on the texture, acidity and catalytic activity of silica-aluminium and silica-magnesia catalysts

    NASA Astrophysics Data System (ADS)

    Youssef, A. M.; Samra, S. E.; Ahmed, Awad I.

    The textural properties of non-irradiated and γ-irradiated silica-aluminium and silica-magnesia catalysts were determined from nitrogen adsorption. The acidities of these catalysts were measured by the chemisorption of pyridine. Cracking of cumene and dehydration of isopropanol were investigated on non-irradiated and γ-irradiated catalysts. Irradiation with γ-rays enhanced sintering, i.e. decreased the surface area and increased pore size. For silica-magnesia, γ-irradiation enhanced crystallization of Forsterite and Enstatite. The surface acidity decreased upon γ-irradiation and consequently the activity of the catalysts towards cracking of cumene and dehydration of isopropanol was reduced. The former reaction is structure-sensitive, while the latter is structure-insensitive.

  11. Strategy to eliminate catalyst hot-spots in the partial oxidation of methane: enhancing its activity for direct hydrogen production by reducing the reactivity of lattice oxygen.

    PubMed

    Wen, Cun; Liu, Yi; Guo, Yun; Wang, Yanqin; Lu, Guanzhong

    2010-02-14

    Hydrogen can be produced over Er(2)O(3) in methane oxidation (oxygen/methane = 26). The reactivity of lattice oxygen in the catalyst plays a main role in the conversion of surface hydroxyl species to hydrogen or water. Adding a rare earth element into a catalyst can reduce the reactivity of lattice oxygen, resulting in increased hydrogen production, to eliminate catalyst hot-spots.

  12. Activity of Cu{sup 2+} ions on the tetrahedral and octahedral sites of spinel oxide catalysts for CO oxidation

    SciTech Connect

    Ghose, J.; Murthy, K.S.R.C.

    1996-09-01

    In studies of CO oxidation on substituted copper chromite spinel oxide catalyst decreases as the Cu{sup 2+} content of the catalyst decreases, either by substitution with a divalent ion, i.e., Cu{sub 1-x} Mg{sub x} [Cr{sub 2}]O{sub 4}, or by reduction of Cu{sup 2+} to Cu{sup 1+}. Crystallographic studies have shown that Cu[Cr{sub 2}]O{sub 4} changes from normal to partially inverse when Cr{sup 3+} is replaced by Al{sup 3+}. Thus, in aluminum-substituted copper chromite catalysts, copper is present on both tetrahedral and octahedral sites of the spinel lattice, i.e., Cu{sub 1-x}Al{sub x} [Cu{sub x}Cr{sub 2-(x+y)}Al{sub y}]O{sub 4}. ESCA studies have shown that upon Al substitution some of the tetrahedral Cu{sup 2+} ions are reduced to Cu{sup 1+} and this causes a reduction in the catalytic activity of the catalysts. The present work was taken up to compare the activity of Cu{sup 2+} on tetrahedral sites with that on octahedral sites of the spinel oxide catalysts. For this, CO oxidation studies were carried out on the inverse spinel CuFe{sub 2}O{sub 4} and on the normal spinel CuRh{sub 2}O{sub 4} catalysts. 7 refs., 1 fig.

  13. Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

    PubMed

    Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

    2013-01-01

    Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

  14. Composite catalyst surfaces: Effect of inert and active heterogeneities on pattern formation

    SciTech Connect

    Baer, M.; Bangia, A.K.; Kevrekidis, I.G.; Haas, G.; Rotermund, H.H.; Ertl, G.

    1996-12-05

    Spatiotemporal dynamics in reaction-diffusion systems can be altered through the properties (reactivity, diffusivity) of the medium in which they occur. We construct active heterogeneous media (composite catalytic surfaces with inert as well as active illusions) using microelectronics fabrication techniques and study the spatiotemporal dynamics of heterogeneous catalytic reactions on these catalysts. In parallel, we perform simulations as well as numerical stability and bifurcation analysis of these patterns using mechanistic models. At the limit of large heterogeneity `grain size` (compared to the wavelength of spontaneously arising structures) the interaction patterns with inert or active boundaries dominates (e.g., pinning, transmission, and boundary breakup of spirals, interaction of pulses with corners, `pacemaker` effects). At the opposite limit of very small or very finely distributed heterogeneity, effective behavior is observed (slight modulation of pulses, nearly uniform oscillations, effective spirals). Some representative studies of transitions between the two limits are presented. 48 refs., 11 figs.

  15. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation.

  16. Active sites and mechanisms for H₂O₂ decomposition over Pd catalysts.

    PubMed

    Plauck, Anthony; Stangland, Eric E; Dumesic, James A; Mavrikakis, Manos

    2016-04-05

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2 We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O-O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O-O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity.

  17. Carbon-Based Microbial-Fuel-Cell Electrodes: From Conductive Supports to Active Catalysts.

    PubMed

    Li, Shuang; Cheng, Chong; Thomas, Arne

    2017-02-01

    Microbial fuel cells (MFCs) have attracted considerable interest due to their potential in renewable electrical power generation using the broad diversity of biomass and organic substrates. However, the difficulties in achieving high power densities and commercially affordable electrode materials have limited their industrial applications to date. Carbon materials, which can exhibit a wide range of different morphologies and structures, usually possess physiological activity to interact with microorganisms and are therefore fast-emerging electrode materials. As the anode, carbon materials can significantly promote interfacial microbial colonization and accelerate the formation of extracellular biofilms, which eventually promotes the electrical power density by providing a conductive microenvironment for extracellular electron transfer. As the cathode, carbon-based materials can function as catalysts for the oxygen-reduction reaction, showing satisfying activities and efficiencies nowadays even reaching the performance of Pt catalysts. Here, first, recent advancements on the design of carbon materials for anodes in MFCs are summarized, and the influence of structure and surface functionalization of different types of carbon materials on microorganism immobilization and electrochemical performance is elucidated. Then, synthetic strategies and structures of typical carbon-based cathodes in MFCs are briefly presented. Furthermore, future applications of carbon-electrode-based MFC devices in the energy, environmental, and biological fields are discussed, and the emerging challenges in transferring them from laboratory to industrial scale are described.

  18. Active sites and mechanisms for H2O2 decomposition over Pd catalysts

    PubMed Central

    Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

    2016-01-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  19. Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

    PubMed Central

    Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

    2010-01-01

    We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639

  20. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and the solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will be performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing.

  1. Fine particle clay catalysts for coal liquefaction

    SciTech Connect

    Olson, E.S.

    1991-01-01

    The efficient production of environmentally acceptable distillate fuels requires catalysts for hydrogenation and cleavage of the coal macromolecules and removal of oxygen, nitrogen, and sulfur heteroatoms. The goal of the proposed research is to develop new catalysts for the direct liquefaction of coal. This type of catalyst consists of fine clay particles that have been treated with reagents which form pillaring structures between the aluminosilicate layers of the clay. The pillars not only hold the layers apart but also constitute the active catalytic sites for hydrogenation of the coal and solvent used in the liquefaction. The pillaring catalytic sites are composed of pyrrhotite, which has been previously demonstrated to be active for coal liquefaction. The pyrrhotite sites are generated in situ by sulfiding the corresponding oxyiron species. The size of the catalyst will be less than 40 nm in order to promote intimate contact with the coal material. Since the clays and reagents for pillaring and activating the clays are inexpensive, the catalysts can be discarded after use, rather than regenerated by a costly process. The proposed work will evaluate methods for preparing the fine particle iron-pillared clay dispersions and for activating the particles to generate the catalysts. Characterization studies of the pillared clays and activated catalysts will performed. The effectiveness of the pillared clay dispersion for hydrogenation and coal liquefaction will be determined in several types of testing. 5 refs., 1 tab.

  2. Simultaneous removal of NO x and SO2 by low-temperature selective catalytic reduction over modified activated carbon catalysts

    NASA Astrophysics Data System (ADS)

    Liu, Ye; Ning, Ping; Li, Kai; Tang, Lihong; Hao, Jiming; Song, Xin; Zhang, Guijian; Wang, Chi

    2017-03-01

    A series of modified porous activated carbon (AC) catalysts prepared by impregnation were investigated for the low-temperature (≤250°C) selective catalytic reduction (SCR) of NO x with NH3 with simultaneous removal of SO2. The effects of various preparation conditions and reaction conditions on NO and SO2 conversions were observed, such as support type, active components, copper loading, calcination temperature and presence of H2O and O2. The modified AC catalysts were characterized by BET, XRD, TG and TPX methods. The activity test results showed that the optimal catalyst is 15% Cu/WCSAC which can provide 52% NO conversion and 68% SO2 conversion simultaneously at 175°C with a space velocity of 30000 h‒1, and the optimal calcination temperature was 500°C. The presence of H2O could inhibit NO conversion and promote the SO2 conversion. The effect of O2 (0-5%) was evaluated, and the NO and SO2 conversions were best when the concentration of O2 was 3%. Research demonstrated that Cu/WCSAC catalyst was a kind of potential catalysts due to the amorphous phase, high specific areas and high active ability.

  3. Sport Fields as Potential Catalysts for Physical Activity in the Neighbourhood

    PubMed Central

    Cutumisu, Nicoleta; Spence, John C.

    2012-01-01

    Physical activity is associated with access to recreational facilities such as sports fields. Because it is not clear whether objectively- or subjectively-assessed access to facilities exerts a stronger influence on physical activity, we investigated the association between the objective and perceived accessibility of sport fields and the levels of self-reported physical activity among adults in Edmonton, Canada. A sample of 2879 respondents was surveyed regarding their socio-demographics, health status, self-efficacy, levels of physical activity, as well as their perceptions of built environment in relation to physical activity. Neighbourhood-level data were obtained for each respondent based on their residence. Accessibility to facilities was assessed using the enhanced Two-Step Floating Catchment Area method. Geographic Information Systems were employed. A logistic regression was performed to predict physical activity using individual- and neighbourhood-level variables. Women, older individuals, and individuals with higher educational attainment were less likely to be physically active. Also, individuals with higher self-efficacy and higher objectively-assessed access to facilities were more likely to be physically active. Interventions that integrate provision of relevant programs for various population groups and of improved recreational facilities may contribute to sport fields becoming catalysts for physical activity by generating movement both on the site and in the neighbourhood. PMID:22470293

  4. Characterization of Deactivated Bio-oil Hydrotreating Catalysts

    SciTech Connect

    Wang, Huamin; Wang, Yong

    2015-10-06

    Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various complimentary analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and x-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.

  5. Reaction of deuterium with olefins on nickel catalysts: evidence for adsorbed vinylic species

    SciTech Connect

    Mintsa-Eya, V.; Hilaire, L.; Choplin, A.; Touroude, R.; Gault, F.G.

    1983-08-01

    The interaction of deuterium with 1,2-dimethylcyclopentene, 2,3-dimethylcyclopentene, 1-methyl-2-methylenecyclopentane, 1,2-dimethylcyclobutene, 1-methyl-2-methylenecyclobutane, bicyclo(2,2,1)heptene, but-1-ene, and cis-but-2-ene was studied from -85 to 50/sup 0/C on nickel films in a static apparatus and on Ni/pumice in a flow system. Unexpected d/sub 3/ and d/sub 4/ molecules were obtained in the deuteration of bicyclo(2,2,1)heptene. The position of the double bond in the ring of the other cycloolefins was the main factor governing their behavior: in the deuteration of 1,2-dimethylcycloalkenes, the saturated products, especially the trans somers, were much more exchanged and the percentage of trans was lower than when the starting material consisted of the olefins with the double bond in 2,3 or exocyclic positions. The hyperfine distribution, obtained by microwave analysis, of the exchanged d/sub 1/ but-1-ene, revealed that the major part of the deuterium was introduced on C/sub 2/; the cis-trans isomerization was much faster than the double bond migration with the introduction of zero or one deuterium atom while the isomerized but-1-ene showed a multiple exchange up to d/sub 4/; in the isomerized d/sub 1/ but-1-ene, the deuterium atom was distributed on the three carbon atoms C/sub 1/, C/sub 2/, C/sub 3/. Most of these results clearly show that the classical Horiuti-Polanyi mechanism is not the only one taking part in the reactions. The introduction of other intermediaries, sigma-vinylic, sigma-vinylic ..pi..-olefinic, and sigma-vinylic ..pi..-allylic species, provides a coherent explanation for all our findings. It is shown that nickel and iron behave in a very similar way. 5 tables.

  6. Structural Descriptors of Zeolitic-Imidazolate Frameworks Are Keys to the Activity of Fe-N-C Catalysts.

    PubMed

    Armel, Vanessa; Hindocha, Sheena; Salles, Fabrice; Bennett, Stephen; Jones, Deborah; Jaouen, Frédéric

    2017-01-11

    Active and inexpensive catalysts for oxygen reduction are crucially needed for the widespread development of polymer electrolyte fuel cells and metal-air batteries. While iron-nitrogen-carbon materials pyrolytically prepared from ZIF-8, a specific zeolitic imidazolate framework (ZIF) with sodalite topology, have shown enhanced activities toward oxygen reduction in acidic electrolyte, the rational design of sacrificial metal-organic frameworks toward this application has hitherto remained elusive. Here, we report for the first time that the oxygen reduction activity of Fe-N-C catalysts positively correlates with the cavity size and mass-specific pore volume in pristine ZIFs. The high activity of Fe-N-C materials prepared from ZIF-8 could be rationalized, and another ZIF structure leading to even higher activity was identified. In contrast, the ORR activity is mostly unaffected by the ligand chemistry in pristine ZIFs. These structure-property relationships will help identifying novel sacrificial ZIF or porous metal-organic frameworks leading to even more active Fe-N-C catalysts. The findings are of great interest for a broader application of the class of inexpensive metal-nitrogen-carbon catalysts that have shown promising activity also for the hydrogen evolution (Co-N-C) and carbon dioxide reduction (Fe-N-C and Mn-N-C).

  7. Preparation and characterization of nano-sized Pt-Ru/C catalysts and their superior catalytic activities for methanol and ethanol oxidation.

    PubMed

    Şen, Selda; Şen, Fatih; Gökağaç, Gülsün

    2011-04-21

    Carbon-supported PtRu nanoparticles (Ru/Pt: 0.25) were prepared by three different methods; simultaneous reduction of PtCl(4) and RuCl(3) (catalyst I) and changing the reduction order of PtCl(4) and RuCl(3) (catalysts II and III) to enhance the performance of the anodic catalysts for methanol and ethanol oxidation. Structure, microstructure and surface characterizations of all the catalysts were carried out by X-ray diffraction (XRD), transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results of the XRD analysis showed that all catalysts had a face-centered cubic (fcc) structure with different and smaller lattice parameters than that of pure platinum, showing that the Ru incorporates into the Pt fcc structure by different ratios in all the catalysts. The typical particle sizes of all catalysts were in the range of 2-3 nm. The most active and stable catalyst for methanol and ethanol oxidation is catalyst III, in which a large amount (more than 90%) of PtRu alloy formation was observed. It has been found that this catalyst is about 8.0 and 33.4 times more active at ∼0.60 V towards the methanol and ethanol oxidation reactions, respectively, compared to the commercial Pt catalyst.

  8. Nonactivated and activated biochar derived from bananas as alternative cathode catalyst in microbial fuel cells.

    PubMed

    Yuan, Haoran; Deng, Lifang; Qi, Yujie; Kobayashi, Noriyuki; Tang, Jiahuan

    2014-01-01

    Nonactivated and activated biochars have been successfully prepared by bananas at different thermotreatment temperatures. The activated biochar generated at 900°C (Biochar-act900) exhibited improved oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performances in alkaline media, in terms of the onset potential and generated current density. Rotating disk electron result shows that the average of 2.65 electrons per oxygen molecule was transferred during ORR of Biochar-act900. The highest power density of 528.2 mW/m(2) and the maximum stable voltage of 0.47 V were obtained by employing Biochar-act900 as cathode catalyst, which is comparable to the Pt/C cathode. Owning to these advantages, it is expected that the banana-derived biochar cathode can find application in microbial fuel cell systems.

  9. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition.

    PubMed

    Reddy Enakonda, Linga; Zhou, Lu; Saih, Youssef; Ould-Chikh, Samy; Lopatin, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

    2016-08-09

    Activation of Fe2 O3 -Al2 O3 with CH4 (instead of H2 ) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx -free H2 . In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2 O3 by CH4 proceeds in three steps: Fe2 O3 →Fe3 O4 →FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3 C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes.

  10. Replacing tin in lactide polymerization: design of highly active germanium-based catalysts.

    PubMed

    Guo, Jia; Haquette, Pierre; Martin, Juliette; Salim, Karine; Thomas, Christophe M

    2013-12-16

    Most germane: Hexacoordinate germanium(IV) species exhibit unprecedented activities, yet controlled behavior, as initiators for the ring-opening polymerization of rac-lactide to form polylactide polymers.

  11. Ligand Exchange-Mediated Activation and Stabilization of a Re-Based Olefin Metathesis Catalyst by Chlorinated Alumina.

    PubMed

    Gallo, Alessandro; Fong, Anthony; Szeto, Kai C; Rieb, Julia; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Peters, Baron; Scott, Susannah L

    2016-10-05

    Extensive chlorination of γ-Al2O3 results in the formation of highly Lewis acidic surface domains depleted in surface hydroxyl groups. Adsorption of methyltrioxorhenium (MTO) onto these chlorinated domains serves to activate it as a low temperature, heterogeneous olefin metathesis catalyst and confers both high activity and high stability. Characterization of the catalyst reveals that the immobilized MTO undergoes partial ligand exchange with the surface, whereby some Re sites acquire a chloride ligand from the modified alumina while donating an oxo ligand to the support. More specifically, Re LIII-edge EXAFS and DFT calculations support facile ligand exchange between MTO and Cl-Al2O3 to generate [CH3ReO2Cl(+)] fragments that interact with a bridging oxygen of the support via a Lewis acid-base interaction. According to IR and solid-state NMR, the methyl group remains intact, and does not evolve spontaneously to a stable methylene tautomer. Nevertheless, the chloride-promoted metathesis catalyst is far more active and productive than MTO/γ-Al2O3, easily achieving a TON of 100 000 for propene metathesis in a flow reactor at 10 °C (compared to TON < 5000 for the nonchlorinated catalyst). Increased activity is a consequence of both a larger fraction of active sites and a higher intrinsic activity for the new sites. Increased stability is tentatively attributed to a stronger interaction between MTO and chlorinated surface regions, as well as extensive depletion of the Brønsted acidic surface hydroxyl population. The reformulated catalyst represents a major advance for Re-based metathesis catalysts, whose widespread use has thus far been severely hampered by their instability.

  12. Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO2 supports

    DOE PAGES

    Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; ...

    2016-01-18

    In this study, we investigated the impact of ZrO2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO2 and SiO2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO2 surface area and improve sulfur tolerance, a Pd support with ZrO2-dispersed onto SiO2 was studied. The physicochemical properties of the catalysts were examined using ICP, N2 sorption, XRD, SEM, TEM, and NH3-, CO2-, and NOx-TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppmmore » CO, 500 ppm NO, 1000 ppm C3H6, 4% O2, 5% H2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO2-containing catalysts showed considerably higher CO and C3H6 oxidation activity than Pd/SiO2 under the reaction conditions studied.« less

  13. Potassium effects on activated-carbon-supported iron catalysts for Fischer-Tropsch synthesis

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; Dady B. Dadyburjor

    2007-08-15

    The effect of potassium on the activity, selectivity, and distribution of products (hydrocarbons and oxygenates) was studied over iron catalysts supported on activated carbon (AC) for Fischer-Tropsch synthesis (FTS). This is part of a wider study on the incremental effects of components (including the support) of a multicomponent (Fe-Cu-Mo-K/AC) FTS catalyst. The range of potassium loading used was 0-2 wt%. A fixed-bed reactor was used under the conditions of 260-300{sup o}C, 300 psig, and 3 Nl/g cat/h, using syngas with a H{sub 2}/CO molar feed ratio of 0.9. Both FTS and water-gas shift activities increase after the addition of 0.9 wt % potassium, whereas an opposite trend is observed with the addition of 2 wt % potassium. This is shown to be the result of interaction between the decrease of both the activation energy (E{sub a}) and the pre-exponental factor (k{sub 0}) with the amount of potassium promoter added. Detectable hydrocarbons up to C{sub 34} and oxygenates up to C{sub 5} are formed on the Fe/AC catalysts with or without potassium. The potassium promoter significantly suppresses formation of methane and methanol and shifts selectivities to higher-molecular-weight hydrocarbons (C{sub 5+}) and alcohols (C{sub 2}-C{sub 5}). Meanwhile, the potassium promoter changes paraffin and olefin distributions. At least for carbon numbers of 25 or less, increasing the K level to 0.9 wt % greatly decreases the amount of n-paraffins and internal olefins (i.e., those with the double bond in other than the terminal positions) and dramatically increases branched paraffins and 1-olefins, but a further increase in the K level shows little additional improvement. The addition of potassium changes the effect of temperature on the selectivity to oxygenates. In the absence of K, oxygenate selectivity decreases with temperature. However, when K is present, the selectivity is almost independent of the temperature. 71 refs., 13 figs., 3 tabs.

  14. Synergistic "ping-pong" energy transfer for efficient light activation in a chromophore-catalyst dyad.

    PubMed

    Quaranta, Annamaria; Charalambidis, Georgios; Herrero, Christian; Margiola, Sofia; Leibl, Winfried; Coutsolelos, Athanassios; Aukauloo, Ally

    2015-10-07

    The synthesis of a porphyrin-Ru(II) polypyridine complex where the porphyrin acts as a photoactive unit and the Ru(II) polypyridine as a catalytic precursor is described. Comparatively, the free base porphyrin was found to outperform the ruthenium based chromophore in the yield of light induced electron transfer. Mechanistic insights indicate the occurrence of a ping-pong energy transfer from the (1)LC excited state of the porphyrin chromophore to the (3)MCLT state of the catalyst and back to the (3)LC excited state of the porphyrin unit. The latter, triplet-triplet energy transfer back to the chromophore, efficiently competes with fast radiationless deactivation of the excited state at the catalyst site. The energy thus recovered by the chromophore allows improved yield of formation of the oxidized form of the chromophore and concomitantly of the oxidation of the catalytic unit by intramolecular charge transfer. The presented results are among the rare examples where a porphyrin chromophore is successfully used to drive an oxidative activation process where reductive processes prevail in the literature.

  15. The Active Sites of a Rod-Shaped Hollandite DeNOx Catalyst.

    PubMed

    Hu, Pingping; Schuster, Manfred Erwin; Huang, Zhiwei; Xu, Fei; Jin, Shifeng; Chen, Yaxin; Hua, Weiming; Su, Dang Sheng; Tang, Xingfu

    2015-06-26

    The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low-temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod-shaped morphology and one-dimensional tunnels. Electron microscopy and synchrotron X-ray diffraction determine the surface and crystal structures of the one-dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X-ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi-tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions.

  16. Active site of bimetallic heterogeneous catalyst by atomic resolution aberration-corrected STEM

    NASA Astrophysics Data System (ADS)

    Hsiao, Chien-Nan; Lin, Chun-Ting

    2015-11-01

    The localized defect of Au-Pd bimetallic heterogeneous nanoparticles catalyst was investigated using HRTEM and aberration-corrected HRSTEM. The phase plates were calculated from the aberration coefficients of the measured probe tableau for various outer tilt angle of the optical axis and the accuracy required for the compensation of the various residual aberration coefficients in order to achieve sub-angstrom resolution with the electron optics system was evaluated up to the fifth order aberrations. It is found that the interplanar spacing of the Au-Pd nanoparticle (1 1 1) planes observed along the [1 1 0] zone axis was approximately 0.24 nm measured by HRTEM. In addition, the HRSTEM HAADF image demonstrated that the twin boundaries on the surfaces of heterogeneous nanoparticles catalysts at atomic scale. These defects might be introduced during the growth to alleviate the internal stress caused by the 4.6% lattice mismatch of Au-Pd bimetallic system. Current research could be applied to the study of active sites in nanocatalysts.

  17. Antifungal activity of heartwood extracts from three Juniperus species

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  18. Deactivation of Oxidation Catalysts

    DTIC Science & Technology

    1991-05-01

    the fresh catalyst . The loss in chromium may be related to the formation of volatile chromium oxychlorde which vaporizes from the catalyst . It is...CeO2 only marginally improved the thtrmal stability. The addition of 2% water vapor inhibited the oxidation of ethanol for all three copper catalysts ...original activity. Field tests of a copper chromite catalyst on process gas containing H2S, methyl mercaptan, n-aldehydes, and furfural showed

  19. A sterically expanded "constrained geometry catalyst" for highly active olefin polymerization and copolymerization: an unyielding comonomer effect.

    PubMed

    Irwin, Levi J; Reibenspies, Joseph H; Miller, Stephen A

    2004-12-29

    The 14 A octamethyloctahydrodibenzofluorene moiety has been incorporated into a sterically expanded constrained geometry catalyst, Me2Si(eta1-C29H36)(eta1-N-tBu)ZrCl2.OEt2 (1). The solid-state structure suggests that the activated olefin polymerization catalyst is quite spatially accessible, rationalizing its extraordinary reactivity toward alpha-olefins. 1/MAO (MAO = methylaluminoxane) can be more reactive toward alpha-olefins than toward ethylene and exhibit activities that are linearly and continuously proportional to 4-methyl-1-pentene or 1-octene concentration in their copolymerizations with ethylene.

  20. Steroid-Derived Naphthoquinoline Asphaltene Model Compounds: Hydriodic Acid Is the Active Catalyst in I2-Promoted Multicomponent Cyclocondensation Reactions.

    PubMed

    Schulze, Matthias; Scott, David E; Scherer, Alexander; Hampel, Frank; Hamilton, Robin J; Gray, Murray R; Tykwinski, Rik R; Stryker, Jeffrey M

    2015-12-04

    A multicomponent cyclocondensation reaction between 2-aminoanthracene, aromatic aldehydes, and 5-α-cholestan-3-one has been used to synthesize model asphaltene compounds. The active catalyst for this reaction has been identified as hydriodic acid, which is formed in situ from the reaction of iodine with water, while iodine is not a catalyst under anhydrous conditions. The products, which contain a tetrahydro[4]helicene moiety, are optically active, and the stereochemical characteristics have been examined by VT-NMR and VT-CD spectroscopies, as well as X-ray crystallography.

  1. Selectivity, activity, and metal-support interactions of Rh bimetallic catalysts. Progress report, 15 November 1981-15 August 1982

    SciTech Connect

    Haller, G L

    1982-08-01

    We report on a detailed investigation of the effect of TiO/sub 2/ support on Rh-Ag interaction as exhibited in catalytic activity. The temporal evolution of activity over Rh-Ag/TiO/sub 2/ for ethane hydrogenolysis and hydrogen chemisorption as a function of temperature, Ag to Rh ratio, the Rh particle size, Rh loading, and ambient gas were studied. Preliminary extended x-ray absorption fine structure (EXAFS) analysis of Rh/TiO/sub 2/ catalysts indicate that 100% exposed (dispersed) catalyst prepared by ion exchange may be atomically dispersed after low temperature reduction. 7 figures, 1 table.

  2. Preliminary results from screening tests of commercial catalysts with potential use in gas turbine combustors. Part 1: Furnace studies of catalyst activity

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1976-01-01

    Thirty commercially produced monolith and pellet catalysts were tested as part of a screening process to select catalysts suitable for use in a gas turbine combustor. The catalysts were contained in a 1.8 centimeter diameter quartz tube and heated to temperatures varying between 300 and 1,200 K while a mixture of propane and air passed through the bed at space velocities of 44,000 to 70,000/hour. The amount of propane oxidized was measured as a function of catalyst temperature. Of the samples tested, the most effective catalysts proved to be noble metal catalysts on monolith substrates.

  3. Activated Carbon Catalysts for the Production of Hydrogen for the Sulfur-Iodine Thermochemical Water Splitting Cycle

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; Harry W. Rollins; Kyle C Burch; Cristina Deiana; Hugo S. Silva; Maria F. Sardella; Dolly Granados

    2009-05-01

    Seven activated carbon catalysts obtained from a variety of raw material sources and preparation methods were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. Within the group of ligno-cellulosic steam-activated carbon catalysts, activity increased with surface area. However, both a mineral-based steam-activated carbon and a ligno-cellulosic chemically-activated carbon displayed activities lower than expected based on their higher surface areas. In general, ash content was detrimental to catalytic activity while total acid sites, as determined by Bohem’s titrations, seemed to favor higher catalytic activity within the group of steam-activated carbons. These results suggest, one more time, that activated carbon raw materials and preparation methods may have played a significant role in the development of surface characteristics that eventually dictated catalyst activity and stability as well.

  4. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste materials in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-10-01

    Recently, carbonaceous materials were proved to be effective catalysts for hazardous waste decomposition in supercritical water. Gasification of the carbonaceous catalyst itself is also expected, however, under supercritical conditions. Thus, it is essential to determine the gasification rate of the carbonaceous materials during this process to determine the active lifetime of the catalysts. For this purpose, the gasification characteristics of granular coconut shell activated carbon in supercritical water alone (600-650{degrees}C, 25.5-34.5 MPa) were investigated. The gasification rate at subatmospheric pressure agreed well with the gasification rate at supercritical conditions, indicating the same reaction mechanism. Methane generation under these conditions is via pyrolysis, and thus is not affected by the water pressure. An iodine number increase of 25% was observed as a result of the supercritical water gasification.

  5. Gasification characteristics of an activated carbon catalyst during the decomposition of hazardous waste material in supercritical water

    SciTech Connect

    Matsumura, Yukihiko; Nuessle, F.W.; Antal, M.J. Jr.

    1996-12-31

    Recently, carbonaceous materials including activated carbon were proven to be effective catalysts for hazardous waste gasification in supercritical water. Using coconut shell activated carbon catalyst, complete decomposition of industrial organic wastes including methanol and acetic acid was achieved. During this process, the total mass of the activated carbon catalyst changes by two competing processes: a decrease in weight via gasification of the carbon by supercritical water, or an increase in weight by deposition of carbonaceous materials generated by incomplete gasification of the biomass feedstocks. The deposition of carbonaceous materials does not occur when complete gasification is realized. Gasification of the activated carbon in supercritical water is often favored, resulting in changes in the quality and quantity of the catalyst. To thoroughly understand the hazardous waste decomposition process, a more complete understanding of the behavior of activated carbon in pure supercritical water is needed. The gasification rate of carbon by water vapor at subcritical pressures was studied in relation to coal gasification and generating activated carbon.

  6. Controlled leaching with prolonged activity for Co-LDH supported catalyst during treatment of organic dyes using bicarbonate activation of hydrogen peroxide.

    PubMed

    Jawad, Ali; Li, Yibing; Lu, Xiaoyan; Chen, Zhuqi; Liu, Weidong; Yin, Guochuan

    2015-05-30

    The effluents from industries are commonly non-biodegradable and produce various hazardous intermediate products by chemical reactions that have direct impact on environment. In the present investigation, a series of Co-Mg/AL ternary LDH catalysts with fixed Mg/Al ratio were prepared by co-precipitation method. The effect of Co on the activity of the catalyst was monitored on the degradation of methylene blue (MB) as model compound at batch level using bicarbonate activation of H2O2 (BAP) system. On bench level, the best CoMgAl-4 catalyst can completely decolorize both methylene blue (MB) and methylene orange (MO) in short time, while in fixed bed, the catalyst was found stable for over 300 h with nearly 100% decolorization and excellent chemical oxygen demand (COD) removal. No leaching of Co was detected for the entire fixed experiment which may be accounted for long life stability and good activity of the catalyst. The ternary LDH catalysts were characterized by AES, XRD, FTIR, BET, and SEM for its compositional, phase structure, optical properties, textural, and surface morphology respectively. The XRD analysis confirmed characteristic pattern of hydrotalcite like structures without impurity phases. The formation of superoxide and hydroxyl radical as ROS was proposed with CoMgAl-4 by radical's scavengers.

  7. Fe3-xCuxO4 as highly active heterogeneous Fenton-like catalysts toward elemental mercury removal.

    PubMed

    Zhou, Changsong; Sun, Lushi; Zhang, Anchao; Wu, Xiaofeng; Ma, Chuan; Su, Sheng; Hu, Song; Xiang, Jun

    2015-04-01

    A series of novel spinel Fe3-xCuxO4 (0active heterogeneous Fenton-like catalysts to remove elemental mercury (Hg0) from the simulated flue gases. Inductively coupled plasma-Atomic emission spectrometry (ICP-AES), X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectrometer (XPS) were used to characterize the catalysts. The catalysts were confirmed the presence of the redox pairs Fesurf2+/Fesurf3+ and Cusurf+/Cusurf2+ on the surface of the cubic structure. The performance of heterogeneous Fenton-like reactions for Hg0 removal was evaluated in a lab-scale bubbling reactor at the solution temperature of 50°C. The systematic studies on the effects of different catalysts, H2O2 concentration and solution pH values on Hg0 removal efficiencies were performed. The recycling of the Fe3-xCuxO4 catalysts in Fenton-like solution is stable and Hg0 removal efficiency remain above 90% after 3 cycles. The active hydroxyl radical (OH) generated during heterogeneous Fenton-like reactions was confirmed through electron spin resonance (ESR) spin-trapping technique. The Hg0 removal mechanism has been discussed based on the experimental and analytical results.

  8. Structural and mechanistic basis for the high activity of Fe–N–C catalysts toward oxygen reduction

    SciTech Connect

    Li, Jingkun; Ghoshal, Shraboni; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Halevi, Barr; McKinney, Samuel; McCool, Geoff; Ma, Chunrong; Yuan, Xianxia; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

    2016-11-11

    The development of efficient non-platinum group metal (non-PGM) catalysts for oxygen reduction reaction (ORR) is of paramount importance for clean and sustainable energy storage and conversion devices. The major bottleneck in developing Fe–N–C materials as the leading non-PGM catalysts lies in the poor understanding of the nature of active sites and reaction mechanisms. Herein, we report a scalable metal organic framework-derived Fe–N–C catalyst with high ORR activity demonstrated in practical H2/air fuel cells, and an unprecedented turnover frequency (TOF) in acid in rotating disk electrode. By characterizing the catalyst under both ex situ and operando conditions using combined microscopic and spectroscopic techniques, we show that the structures of active sites under ex situ and working conditions are drastically different. Resultantly, the active site proposed here, a non-planar ferrous Fe–N4 moiety embedded in distorted carbon matrix characterized by a high Fe2+/3+ redox potential, is in contrast with those proposed hitherto derived from ex situ characterizations. This site reversibly switches to an in-plane ferric Fe–N4 moiety poisoned by oxygen adsorbates during the redox transition, with the population of active sites controlled by the Fe2+/3+ redox potential. The unprecedented TOF of the active site is correlated to its near-optimal Fe2+/3+ redox potential, and essentially originated from its favorable biomimetic dynamic nature that balances the site-blocking effect and O2 dissociation. The porous and disordered carbon matrix of the catalyst plays pivotal roles for its measured high ORR activity by hosting high population of reactant-accessible active sites.

  9. Composition dependence of ternary Pt-Ni-Cr catalyst activity for the methanol electro-oxidation reaction

    NASA Astrophysics Data System (ADS)

    Jeon, Min Ku; McGinn, Paul J.

    Various compositions of binary and ternary Pt-Ni-Cr alloys were investigated as catalysts for the methanol electro-oxidation reaction (MOR). Among the binary (Pt 28Ni 72/C and Pt 28Cr 72/C) and ternary Pt-Ni-Cr catalysts (Pt 28Ni 36Cr 36/C, Pt 22Ni 39Cr 39/C, Pt 33Ni 31Cr 36/C, and Pt 33Ni 36Cr 31/C) examined, the Pt 28Ni 36Cr 36/C composition exhibited the highest MOR mass activity (4.42 A g cat. -1) in the as-prepared version, which was higher than the 3.58 A g cat. -1 value of the PtRu/C catalyst after 60 min of chronoamperometry testing. The order of mass activity for the MOR was Pt 28Ni 36Cr 36/C > Pt 33Ni 36Cr 31/C > Pt 22Ni 39Cr 39/C > Pt 33Ni 31Cr 36/C > Pt 28Cr 72/C > Pt 28Ni 72/C, which was slightly changed to Pt 28Ni 36Cr 36/C > Pt 22Ni 39Cr 39/C > Pt 33Ni 36Cr 31/C > Pt 33Ni 31Cr 36/C > Pt 28Cr 72/C > Pt 28Ni 72/C after a conditioning process. The effect of anodic conditioning was also studied. A combination of X-ray diffraction, cyclic voltammetry, and chronoamperometry experiments revealed that the conditioning process caused dissolution and an oxidation state change of metallic Ni and Cr 2O 3 in the binary catalysts. The higher MOR mass activities of the ternary catalysts compared to the binary ones is attributed to co-alloying of Ni and Cr, leading to exposure of more Pt on the catalyst surface without reducing specific activities of the catalysts. The results of this study also correlate well with a prior ranking of catalytic activity of the same compositions in the form of thin film catalysts that we processed and evaluated by a high-throughput combinatorial approach [J.S. Cooper, M.K. Jeon, P.J. McGinn, Electrochem. Commun. 10 (2008) 1545-1547].

  10. Reactivity of atomically dispersed Pt(2+) species towards H2: model Pt-CeO2 fuel cell catalyst.

    PubMed

    Lykhach, Yaroslava; Figueroba, Alberto; Camellone, Matteo Farnesi; Neitzel, Armin; Skála, Tomáš; Negreiros, Fabio R; Vorokhta, Mykhailo; Tsud, Nataliya; Prince, Kevin C; Fabris, Stefano; Neyman, Konstantin M; Matolín, Vladimír; Libuda, Jörg

    2016-03-21

    The reactivity of atomically dispersed Pt(2+) species on the surface of nanostructured CeO2 films and the mechanism of H2 activation on these sites have been investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy in combination with density functional calculations. Isolated Pt(2+) sites are found to be inactive towards H2 dissociation due to high activation energy required for H-H bond scission. Trace amounts of metallic Pt are necessary to initiate H2 dissociation on Pt-CeO2 films. H2 dissociation triggers the reduction of Ce(4+) cations which, in turn, is coupled with the reduction of Pt(2+) species. The mechanism of Pt(2+) reduction involves reverse oxygen spillover and formation of oxygen vacancies on Pt-CeO2 films. Our calculations suggest the existence of a threshold concentration of oxygen vacancies associated with the onset of Pt(2+) reduction.

  11. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

    PubMed Central

    Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  12. Waste shells of mollusk and egg as biodiesel production catalysts.

    PubMed

    Viriya-Empikul, N; Krasae, P; Puttasawat, B; Yoosuk, B; Chollacoop, N; Faungnawakij, K

    2010-05-01

    The solid oxide catalysts derived from waste shells of egg, golden apple snail, and meretrix venus were employed to produce biodiesel from transesterification of palm olein oil. The shell materials were calcined in air at 800 degrees C with optimum time of 2-4h to transform calcium species in the shells into active CaO catalysts. All catalysts showed the high biodiesel production activity over 90% fatty acid methyl ester (FAME) in 2h, whilst the eggshell-derived catalyst showed comparable activity to the one derived from commercial CaCO(3). The catalytic activity was in accordance with the surface area of and the Ca content in the catalysts.

  13. Highly Active Nickel Catalysts for C-H Functionalization Identified through Analysis of Off-Cycle Intermediates.

    PubMed

    Nett, Alex J; Zhao, Wanxiang; Zimmerman, Paul M; Montgomery, John

    2015-06-24

    An inhibitory role of 1,5-cyclooctadiene (COD) in nickel-catalyzed C-H functionalization processes was identified and studied. The bound COD participates in C-H activation by capturing the hydride, leading to a stable off-cycle π-allyl complex that greatly diminished overall catalytic efficiency. Computational studies elucidated the origin of the effect and enabled identification of a 1,5-hexadiene-derived pre-catalyst that avoids the off-cycle intermediate and provides catalytic efficiencies that are superior to those of catalysts derived from Ni(COD)2.

  14. Impact of carbon on the surface and activity of silica-carbon supported copper catalysts for reduction of nitrogen oxides

    NASA Astrophysics Data System (ADS)

    Spassova, I.; Stoeva, N.; Nickolov, R.; Atanasova, G.; Khristova, M.

    2016-04-01

    Composite catalysts, prepared by one or more active components supported on a support are of interest because of the possible interaction between the catalytic components and the support materials. The supports of combined hydrophilic-hydrophobic type may influence how these materials maintain an active phase and as a result a possible cooperation between active components and the support material could occur and affects the catalytic behavior. Silica-carbon nanocomposites were prepared by sol-gel, using different in specific surface areas and porous texture carbon materials. Catalysts were obtained after copper deposition on these composites. The nanocomposites and the catalysts were characterized by nitrogen adsorption, TG, XRD, TEM- HRTEM, H2-TPR, and XPS. The nature of the carbon predetermines the composite's texture. The IEPs of carbon materials and silica is a force of composites formation and determines the respective distribution of the silica and carbon components on the surface of the composites. Copper deposition over the investigated silica-carbon composites leads to formation of active phases in which copper is in different oxidation states. The reduction of NO with CO proceeds by different paths on different catalysts due to the textural differences of the composites, maintaining different surface composition and oxidation states of copper.

  15. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    DOE PAGES

    Liu, Wen; Hu, Enyuan; Jiang, Hong; ...

    2016-02-19

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superiormore » activity for hydrogen evolution, achieving current densities of 10 mA cm–2 and 100 mA cm–2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.« less

  16. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    SciTech Connect

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-02-19

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm–2 and 100 mA cm–2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

  17. A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

    PubMed Central

    Liu, Wen; Hu, Enyuan; Jiang, Hong; Xiang, Yingjie; Weng, Zhe; Li, Min; Fan, Qi; Yu, Xiqian; Altman, Eric I.; Wang, Hailiang

    2016-01-01

    Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm−2 and 100 mA cm−2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation. PMID:26892437

  18. Exceptional methanol electro-oxidation activity by bimetallic concave and dendritic Pt-Cu nanocrystals catalysts

    NASA Astrophysics Data System (ADS)

    Wang, Ying-Xia; Zhou, Hui-Jing; Sun, Ping-Chuan; Chen, Tie-Hong

    2014-01-01

    PtCux (x = 1, 2 and 3) bimetallic nanocrystals with concave surface and dendritic morphology were prepared and used as electrocatalysts in methanol oxidation reaction (MOR) for polymer electrolyte membrane fuel cells. The bimetallic nanocrystals were synthesized via one-pot co-reduction of H2PtCl6 and Cu(acac)2 by oleylamine and polyvinyl pyrrolidone (PVP) in an autoclave at 180 °C. The concave dendritic bimetallic nanostructure consisted of a core rich in Cu and nanodendrites rich in Pt, which was formed via galvanic replacement of Cu by Pt. It was found that PVP played an important role in initiating, facilitating, and directing the replacement reaction. The electrochemical properties of the PtCux were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The concave dendritic PtCu2/C nanocrystals exhibited exceptionally high activity and strong poisoning resistance in MOR. At 0.75 V (vs. reversible hydrogen electrode, RHE) the mass activity and specific activity of PtCu2/C were 3.3 and 4.1 times higher than those of the commercial Pt/C catalysts, respectively. The enhanced catalytic activity could be attributed to the unique concave dendritic morphology of the bimetallic nanocrystals.

  19. Origin of highly active metal-organic framework catalysts: defects? Defects!

    PubMed

    Canivet, J; Vandichel, M; Farrusseng, D

    2016-03-14

    This article provides a comprehensive review of the nature of catalytic sites in MOFs. In the last decade, a number of striking studies have reported outstanding catalytic activities of MOFs. In all cases, the authors were intrigued as it was unexpected from the ideal structure. We demonstrate here that (surface) defects are at the origin of the catalytic activities for the reported examples. The vacancy of ligands or linkers systematically generates (surface) terminations which can possibly show Lewis and/or Brønsted acido-basic features. The engineering of catalytic sites at the nodes by the creation of defects (on purpose) appears today as a rational approach for the design of active MOFs. Similarly to zeolite post-treatments, post-modifications of MOFs by linker or metal cation exchange appear to be methods of choice. Despite the mild acidity of defective MOFs, we can account for very active MOFs in a number of catalytic applications which show higher performances than zeolites or benchmark catalysts.

  20. Production of biodiesel fuel from canola oil with dimethyl carbonate using an active sodium methoxide catalyst prepared by crystallization.

    PubMed

    Kai, Takami; Mak, Goon Lum; Wada, Shohei; Nakazato, Tsutomu; Takanashi, Hirokazu; Uemura, Yoshimitsu

    2014-07-01

    In this study, a novel method for the production of biodiesel under mild conditions using fine particles of sodium methoxide formed in dimethyl carbonate (DMC) is proposed. Biodiesel is generally produced from vegetable oils by the transesterification of triglycerides with methanol. However, this reaction produces glycerol as a byproduct, and raw materials are not effectively utilized. Transesterification with DMC has recently been studied because glycerol is not formed in the process. Although solid-state sodium methoxide has been reported to be inactive for this reaction, the catalytic activity dramatically increased with the preparation of fine catalyst powders by crystallization. The transesterification of canola oil with DMC was studied using this catalyst for the preparation of biodiesel. A conversion greater than 96% was obtained at 65°C for 2h with a 3:1M ratio of DMC and oil and 2.0 wt% catalyst.

  1. Effect of a catalyst on the kinetics of reduction of celestite (SrSO{sub 4}) by active charcoal

    SciTech Connect

    Sonawane, R.S.; Kale, B.B.; Apte, S.K.; Dongare, M.K.

    2000-02-01

    Reduction of celestite (SrSO{sub 4}) powder with particles of active charcoal has been studied extensively in the absence and presence of catalysts. The optimum temperature at the charging zone has been optimized to get a maximum water-soluble strontium sulfide value. The strontium value has been analyzed using a chemical method, which was verified by the instrumental method using an inductively coupled plasma-optical emission spectrophotometer (ICP-OES). The conversion-time data have been analyzed by using a modified volume-reaction (MVR) model, and the effect of the catalyst on kinetic parameters has been elucidated. It was found that potassium carbonate, potassium dichromate, sodium carbonate, and sodium dichromate catalysts were found to enhance the reaction rate quite satisfactorily in the reduction of the celestite (SrSO{sub 4}).

  2. The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

    SciTech Connect

    Davidson, Stephen D.; Sun, Junming; Wang, Yong

    2016-07-01

    The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway, evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.

  3. Methane conversion to aromatics on Mo/H-ZSM5: Structure of molybdenum species in working catalysts

    SciTech Connect

    Ding, Weiping; Li, Senzi; Meitzner, George D.; Iglesia, Enrique

    2000-10-27

    The structure and density of Mo species in Mo/H-ZSM5 during catalytic CH4 reactions was investigated using in-situ X-ray absorption spectroscopy (XAS), temperature-programmed oxidation after reaction, and the isotopic exchange of D2 with OH groups in H-ZSM5 before and after CH4 reactions. These methods reveal that CH4 reactions cause exchanged Mo2O52+ dimers, formed from physical mixtures of MoO3 and H-ZSM5, to reduce and carburize to form small (0.6-1 nm) MoCx clusters with the concurrent regeneration of the bridging OH groups that were initially replaced by Mo oxo dimers during exchange. In this manner, catalytically inactive Mo oxo species activate in contact with CH4 to form the two sites required for the conversion of CH4 to aromatics: MoCx for C-H bond activation and initial C-C bond formation and acid sites for oligomerization and cyclization of C2+ hydrocarbons to form stable aromatics. These MoCx clusters resist agglomeration during methane reactions at 950 K for > 10 h. The Bronsted acid sites formed during carburization and oligomerization of MoCx species ultimately become covered with hydrogen-deficient reaction intermediates (H/C{sup X} 0.2) or unreactive deposits. The highly dispersed nature of the MoCx clusters was confirmed by detailed simulations of the XAS radial structure function and by the low temperatures required for the complete oxidation of these MoCx species compared with bulk Mo2C. Initial CH4 reactions with MoOx precursors are stoichiometric and lead first to the removal of oxygen as CO, CO2, and H2O and to the introduction of carbidic carbons into the reduced structures. As carbidic carbon passivates the surface, C-H bond activation reactions become catalytic by the coupling of this activation step with the removal of the resulting CHx species to form C2 hydrocarbons, which desorb to re-form the MoCx sites required for C-H bond activation steps.

  4. Active hydrogen species on TiO2 for photocatalytic H2 production.

    PubMed

    Wu, Zongfang; Zhang, Wenhua; Xiong, Feng; Yuan, Qing; Jin, Yuekang; Yang, Jinlong; Huang, Weixin

    2014-04-21

    Photocatalytic H2 production over TiO2 has attracted tremendous attention and achieved great progress, but the active hydrogen species is still unknown. Employing a rutile TiO2(110) surface as a model catalyst we report here for the first time the direct observation of photocatalytic H2 production under ultrahigh vacuum conditions during UV-light irradiation at 115 K and the identification of negatively-charged hydride-type H-Ti species as the corresponding photoactive surface species by means of thermal desorption spectroscopy, photon-stimulated desorption spectroscopy, X-ray photoelectron spectroscopy and DFT calculations. The formation and stability of H-Ti species are closely related to available surplus electrons on the rutile TiO2(110) surface that can be created by the formation of surface BBO vacancies or by the formation of surface hydroxyls via the adsorption of atomic H or molecular H2 on O sites. The photocatalytic H2 production from H-Ti species is hole-mediated and co-existing water exerts a negative effect on this process.

  5. Ti or Sn doping as a way to increase activity and sulfur tolerance of Mn/CeO2 catalyst for low temperature NH3 selective catalytic reduction of NO

    NASA Astrophysics Data System (ADS)

    Xiong, Yan; Tang, Changjin; Dong, Lin

    2015-04-01

    Mn/CeO2 catalysts modified by doping of Ti or Sn were investigated for low temperature selective catalytic reduction (SCR) of NO by NH3 with the aim of studying the effects of Ti, Sn doping on the catalytic performance. Ceria-based solid solutions (Ce0.8Ti0.2O2 and Ce0.8Sn0.2O2) were synthesized via inverse co-precipitation, and used as supports to prepare MnOx/Ce0.8M0.2O2 (M =Ti4+, Sn4+) catalysts through wetness impregnation method. The results showed that doping of Ti or Sn to the CeO2 support increase the NO removal efficiency. A NO conversion of more than 90 % was obtained over the Mn/CeTi catalyst at the temperature window of 175 ~ 300 °C under a gas hourly space velocity (GHSV) of 60,000 mL•g-1•h-1. Catalysts modified by Ti and Sn were also found to obtain higher SO2 resistance than Mn/CeO2 catalyst. More than 90% NO conversion and 95% N2 selectivity could be provided by Mn/CeTi catalyst in the presence of 100 ppm SO2 at 250 °C for 10 h. A series of characterization techniques, namely XRD, BET, H2-TPR, XPS, NH3-TPD and in situ DRIFTS were used to elucidate the structure and surface properties of the obtained supports and catalysts. The results indicate that doping of Ti or Sn brings about catalysts with favorable properties such as higher BET surface area, better oxygen storage capacity and stronger surface acidity. The relative amount of Mn4+, Ce3+, adsorbed oxygen species and oxygen vacancies on the surface of catalysts are in the order of Mn/CeTi>Mn/CeSn>Mn/CeO2, which is thought to make positive a contribution to the low-temperature SCR activity. The promoted SCR activity is considered as well to be related to the dual redox cycles in Mn/CeTi (Mn4+ + Ce3+ ↔ Mn3+ + Ce4+, Ce4+ + Ti3+ ↔ Ce3+ + Ti4+) and Mn/CeSn (Mn4+ + Ce3+ ↔ Mn3+ + Ce4+, Ce4+ + Sn2+ ↔ Ce3+ + Sn4+ ) catalysts.

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

    PubMed

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

    2014-11-17

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

  7. Does diet influence salivary enzyme activities in elephant species?

    PubMed

    Boehlke, Carolin; Pötschke, Sandra; Behringer, Verena; Hannig, Christian; Zierau, Oliver

    2017-01-01

    Asian elephants (Elephas maximus) and African elephants (Loxodonta africana) are herbivore generalists; however, Asian elephants might ingest a higher proportion of grasses than Africans. Although some studies have investigated nutrition-specific morphological adaptations of the two species, broader studies on salivary enzymes in both elephant species are lacking. This study focuses on the comparison of salivary enzymes activity profiles in the two elephant species; these enzymes are relevant for protective and digestive functions in humans. We aimed to determine whether salivary amylase (sAA), lysozyme (sLYS), and peroxidase (sPOD) activities have changed in a species-specific pattern during evolutionary separation of the elephant genera. Saliva samples of 14 Asian and eight African elephants were collected in three German zoos. Results show that sAA and sLYS are salivary components of both elephant species in an active conformation. In contrast, little to no sPOD activity was determined in any elephant sample. Furthermore, sAA activity was significantly higher in Asian compared with African elephants. sLYS and sPOD showed no species-specific differences. The time of food provision until sample collection affected only sAA activity. In summary, the results suggest several possible factors modulating the activity of the mammal-typical enzymes, such as sAA, sLYS, and sPOD, e.g., nutrition and sampling procedure, which have to be considered when analyzing differences in saliva composition of animal species.

  8. In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts

    PubMed Central

    Malko, Daniel; Kucernak, Anthony; Lopes, Thiago

    2016-01-01

    The economic viability of low temperature fuel cells as clean energy devices is enhanced by the development of inexpensive oxygen reduction reaction catalysts. Heat treated iron and nitrogen containing carbon based materials (Fe–N/C) have shown potential to replace expensive precious metals. Although significant improvements have recently been made, their activity and durability is still unsatisfactory. The further development and a rational design of these materials has stalled due to the lack of an in situ methodology to easily probe and quantify the active site. Here we demonstrate a protocol that allows the quantification of active centres, which operate under acidic conditions, by means of nitrite adsorption followed by reductive stripping, and show direct correlation to the catalytic activity. The method is demonstrated for two differently prepared materials. This approach may allow researchers to easily assess the active site density and turnover frequency of Fe–N/C catalysts. PMID:27796287

  9. In situ electrochemical quantification of active sites in Fe-N/C non-precious metal catalysts

    NASA Astrophysics Data System (ADS)

    Malko, Daniel; Kucernak, Anthony; Lopes, Thiago

    2016-10-01

    The economic viability of low temperature fuel cells as clean energy devices is enhanced by the development of inexpensive oxygen reduction reaction catalysts. Heat treated iron and nitrogen containing carbon based materials (Fe-N/C) have shown potential to replace expensive precious metals. Although significant improvements have recently been made, their activity and durability is still unsatisfactory. The further development and a rational design of these materials has stalled due to the lack of an in situ methodology to easily probe and quantify the active site. Here we demonstrate a protocol that allows the quantification of active centres, which operate under acidic conditions, by means of nitrite adsorption followed by reductive stripping, and show direct correlation to the catalytic activity. The method is demonstrated for two differently prepared materials. This approach may allow researchers to easily assess the active site density and turnover frequency of Fe-N/C catalysts.

  10. PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

    PubMed

    Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

    2011-06-01

    The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance.

  11. CO oxidation activity of Cu-CeO2 nano-composite catalysts prepared by laser vaporization and controlled condensation

    NASA Astrophysics Data System (ADS)

    Sundar, Rangaraj S.; Deevi, Sarojini

    2006-08-01

    Ceria supported copper catalysts were synthesized by laser vaporization and controlled condensation method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and temperature programmed reduction (TPR). The catalytic activity of the nanopowders for CO oxidation reaction was tested in a fixed bed flow tube reactor in Ar-20%O2-4%CO mixture. Irrespective of the copper content, the catalytic activity of the nanopowders is similar in the initial CO test, and the catalytic activity improves (i.e. the light-off temperature decreases) during a subsequent run. The lowest light-off temperature during the second run is recorded in the material with 20% copper. TEM studies on 20%Cu-CeO2 sample in the as-prepared condition and after CO test exhibit two types of ceria particles namely, polygonal particles 3-5 nm in size and spherical particles of 15-20 nm in size. Rapid cooling of the nanoparticles formed during the laser ablation results in incorporation of a large amount of copper within the ceria as solid solution. Presence of solid solution of copper is confirmed by EDAX and electron diffraction analyses. In addition, copper-rich surface layer of Cu2O is found over the spherical particles. The cerium oxide components are essentially identical before and after CO test, except that the polygonal CeO2 particles contain newly formed fine crystals of CuO. TPR results reveal two reduction peaks, which further supports, the presence of two different copper species in the material. The shift in light-off temperature during the second run is attributed to the synergistic interaction between newly formed CuO crystals with the CeO2 matrix.

  12. Enhanced Activity and Durability of Nanosized Pt-SnO2/IrO2/CNTs Catalyst for Methanol Electrooxidation.

    PubMed

    Wang, Hongjuan; Wang, Xiaohui; Zheng, Jiadao; Peng, Feng; Yu, Hao

    2015-05-01

    Pt-SnO2/IrO2/CNTs anode catalyst for direct methanol fuel cell was designed and prepared with IrO2/CNTs as support for the subsequent immobilization of Pt and SnO2 at the same time. The structure of the catalysts and their catalytic performance in methanol electrooxidation were investigated and the roles of IrO2 and SnO2 in methanol electrooxidation were discussed as well. Results show that Pt-SnO2/IrO2/CNTs catalyst exhibits the best activity and durability for methanol electrooxidation when compared with Pt/CNTs, Pt/IrO2/CNTs and Pt-SnO2/CNTs. According to the results of electrochemical tests and physicochemical characterizations, the enhancements of Pt-SnO2/IrO2/CNTs were attributed to the special properties of IrO2 and SnO2, in which IrO2 mainly increases the methanol oxidation activity and SnO2 mainly improves the CO oxidation ability and durability. Therefore, Pt-SnO2/IrO2/CNTs exhibits excellent performance for methanol oxidation with higher electrocatalytic activity (I(f) of 1054 A g(Pt(-1)) and powerful anti-poisoning ability (the onset potential for CO oxidation of 0.3 V) and outstanding durability (the sustained time t in CP of 617 s), revealing a suitable anode catalyst for DMFCs.

  13. Origin of the Electrocatalytic Oxygen Reduction Activity of Graphene-Based Catalysts: A Roadmap to Achieve the Best Performance

    PubMed Central

    2015-01-01

    The mutually corroborated electrochemical measurements and density functional theory (DFT) calculations were used to uncover the origin of electrocatalytic activity of graphene-based electrocatalysts for oxygen reduction reaction (ORR). A series of graphenes doped with nonmetal elements was designed and synthesized, and their ORR performance was evaluated in terms of four electrochemical descriptors: exchange current density, on-set potential, reaction pathway selectivity and kinetic current density. It is shown that these descriptors are in good agreement with DFT calculations, allowing derivation of a volcano plot between the ORR activity and the adsorption free energy of intermediates on metal-free materials, similarly as in the case of metallic catalysts. The molecular orbital concept was used to justify this volcano plot, and to theoretically predict the ORR performance of an ideal graphene-based catalyst, the ORR activity of which is comparable to the state-of-the-art Pt catalyst. Moreover, this study may stimulate the development of metal-free electrocatalysts for other key energy conversion processes including hydrogen evolution and oxygen evolution reactions and largely expand the spectrum of catalysts for energy-related electrocatalysis reactions. PMID:24580116

  14. Prussian blue analogue derived magnetic carbon/cobalt/iron nanocomposite as an efficient and recyclable catalyst for activation of peroxymonosulfate.

    PubMed

    Lin, Kun-Yi Andrew; Chen, Bo-Jau

    2017-01-01

    A Prussian blue analogue, cobalt hexacyanoferrate Co3[Fe(CN)6]2, was used for the first time to prepare a magnetic carbon/cobalt/iron (MCCI) nanocomposite via one-step carbonization of Co3[Fe(CN)6]2. The resulting MCCI consisted of evenly-distributed cobalt and cobalt ferrite in a porous carbonaceous matrix, making it an attractive magnetic heterogeneous catalyst for activating peroxymonosulfate (PMS). As Rhodamine B (RhB) degradation was adopted as a model test for evaluating activation capability of MCCI, factors influencing RhB degradation were thoroughly examined, including MCCI and PMS dosages, temperature, pH, salt and radical scavengers. A higher MCCI dosage noticeably facilitated the degradation kinetics, whereas insufficient PMS dosage led to ineffective degradation. RhB degradation by MCCI-activated PMS was much more favorable at high temperatures and under neutral conditions. The presence of high concentration of salt slightly interfered with RhB degradation by MCCI-activated PMS. Through examining effects of radical scavengers, RhB degradation by MCCI-activated PMS can be primarily attributed to sulfate radicals instead of a combination of sulfate and hydroxyl radicals. Compared to Co3O4, a typical catalyst for PMS activation, MCCI also exhibited a higher catalytic activity for activating PMS. In addition, MCCI was proven as a durable and recyclable catalyst for activating PMS over multiple cycles without efficiency loss and significant changes of chemical characteristics. These features demonstrate that MCCI, simply prepared from a one-step carbonization of Co3[Fe(CN)6]2 is a promising heterogeneous catalyst for activating PMS to degrade organic pollutants.

  15. In-situ activation of CuO/ZnO/Al.sub.2 O.sub.3 catalysts in the liquid phase

    DOEpatents

    Brown, Dennis M.; Hsiung, Thomas H.; Rao, Pradip; Roberts, George W.

    1989-01-01

    The present invention relates to a method of activation of a CuO/ZnO/Al.sub.2 O.sub.3 catalyst slurried in a chemically inert liquid. Successful activation of the catalyst requires the use of a process in which the temperature of the system at any time is not allowed to exceed a certain critical value, which is a function of the specific hydrogen uptake of the catalyst at that same time. This process is especially critical for activating highly concentrated catalyst slurries, typically 25 to 50 wt %. Activation of slurries of CuO/ZnO/Al.sub.2 O.sub.3 catalyst is useful in carrying out the liquid phase methanol or the liquid phase shift reactions.

  16. Microwave enhanced alcoholysis of non-edible (algal, jatropha and pongamia) oils using chemically activated egg shell derived CaO as heterogeneous catalyst.

    PubMed

    Joshi, Girdhar; Rawat, Devendra S; Sharma, Amit Kumar; Pandey, Jitendra K

    2016-11-01

    Microwave enhanced fast and efficient alcoholysis (methanolysis and ethanolysis) of non-edible oils (algal, jatropha and pongamia) is achieved using chemically activated waste egg shell derived CaO (i.e. CaO(cesp)) as heterogeneous catalyst. CaO(cesp) was extracted from waste chicken egg shell and further activated chemically by supporting transition metal oxide. The maximum conversion was achieved using 3wt% catalysts under 700W microwave irradiation and 10:1 alcohol/oil ratio in 6min. Alcoholysis using ZnO activated CaO(cesp) catalyst has shown higher reaction yields in comparison to other modified catalysts. Methanolysis has shown better biodiesel conversion in comparison to ethanolysis. The catalyst has shown longer lifetime and sustained activity after being used for four cycles. Due to more saturated fatty acid content; algal biodiesel has shown improved fuel properties in comparison to other biodiesels.

  17. Amorphous molybdenum sulfides as hydrogen evolution catalysts.

    PubMed

    Morales-Guio, Carlos G; Hu, Xile

    2014-08-19

    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  18. Nature of copper active sites in the carbon monoxide oxidation on CuAl{sub 2}O{sub 4} and CuCr{sub 2}O{sub 4} spinel type catalysts

    SciTech Connect

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

    1998-07-01

    Unsupported copper-aluminum and copper-chromium oxides were prepared by mixing solutions of the nitrates and calcining at 1223 K, followed by treatment with washing solutions of either ammonium carbonate or nitric acid in order to extract uncombined copper oxide. Ammonium carbonate was only effective for removal of dispersed CuO, whereas nitric acid removed both dispersed a/nd crystalline CuO. Catalyst activity for CO oxidation increased with the extraction treatments, particularly with the nitric acid washing solution, indicating that the active sites are copper species derived from CuAl{sub 2}O{sub 4} and CuCr{sub 2}O{sub 4} spinels rather than from CuO. The CuCr{sub 2}O{sub 4} catalyst exhibited higher activity, suggesting that Cu species in tetrahedral coordination lead to higher activity. Also, pre-reduction with H{sub 2} produced higher activity than prereduction with CO, which can be attributed to a higher surface concentration of active species or their precursors after the former treatment. Activity results, together with TPR and XPS characterization point out that both Cu{sup 0} and Cu{sup +} species are involved in the mechanism of CO oxidation.

  19. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  20. Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application.

    PubMed

    Chen, Zhu; Yu, Aiping; Higgins, Drew; Li, Hui; Wang, Haijiang; Chen, Zhongwei

    2012-04-11

    A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries.

  1. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  2. Assessment of the ethanol oxidation activity and durability of Pt catalysts with or without a carbon support using Electrochemical Impedance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Saleh, Farhana S.; Easton, E. Bradley

    2014-01-01

    We compared the stability and performance of 3 commercially available Johnson Matthey catalysts with various Pt loadings (20, 40 and 100%) using two different accelerated durability testing (ADT) protocols. The various Pt-loaded catalysts were tested by means of a series of intermittent life tests (1, 200, 400, 1000, 2000, 3000 and 4000 cycles). The electrochemical surface area (ECSA) loss of electrode was investigated by electrochemical technique (CV). The use of EIS as an accelerated-testing protocol distinctly elucidates the extent of degradation of Johnson Matthey catalysts with various Pt loading. Using EIS, it was possible to show that Pt-black catalyst layers suffer from increased electronic resistance over the course of ADT which is not observed when a corrosion stable carbon support is present. The effect of Pt loading was further elucidated by comparing the electrocatalytic activity of the catalyst layers towards ethanol oxidation reaction (EOR). The catalyst layer with the lowest Pt loading showed the enhanced EOR performance.

  3. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    NASA Astrophysics Data System (ADS)

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-06-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

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

    PubMed

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

    2016-03-01

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

  5. Catalytic hydrothermal treatment of pulping effluent using a mixture of Cu and Mn metals supported on activated carbon as catalyst.

    PubMed

    Yadav, Bholu Ram; Garg, Anurag

    2016-10-01

    The present study was performed to investigate the performance of activated carbon-supported copper and manganese base catalyst for catalytic wet oxidation (CWO) of pulping effluent. CWO reaction was performed in a high pressure reactor (capacity = 0.7 l) at temperatures ranging from 120 to 190 °C and oxygen partial pressures of 0.5 to 0.9 MPa with the catalyst concentration of 3 g/l for 3 h duration. With Cu/Mn/AC catalyst at 190 °C temperature and 0.9 MPa oxygen partial pressures, the maximum chemical oxygen demand (COD), total organic carbon (TOC), lignin, and color removals of 73, 71, 86, and 85 %, respectively, were achieved compared to only 52, 51, 53, and 54 % removals during the non-catalytic process. Biodegradability (in terms of 5-day biochemical oxygen demand (BOD5) to COD ratio) of the pulping effluent was improved to 0.38 from an initial value of 0.16 after the catalytic reaction. The adsorbed carbonaceous fraction on the used catalyst was also determined which contributed meager TOC reduction of 3-4 %. The leaching test showed dissolution of the metals (i.e., Cu and Mn) from the catalysts in the wastewater during CWO reaction at 190 °C temperature and 0.9 MPa oxygen partial pressures. In the future, the investigations should focus on the catalyst reusability.

  6. Effect of impregnation protocol in the metallic sites of Pt-Ag/activated carbon catalysts for water denitration

    NASA Astrophysics Data System (ADS)

    Aristizábal, A.; Contreras, S.; Divins, N. J.; Llorca, J.; Medina, F.

    2014-04-01

    The influence of the Pt precursor and the impregnation protocol in the catalytic behavior of 3%Pt-1.5%Ag supported on activated carbon for water denitration in a continuous reactor was studied. Pt(NH3)4(NO3)2 and H2PtCl6 were selected as Pt precursors. Five protocols were investigated: sequential impregnations (both sequences), co-impregnation, physical mixture of monometallic catalysts, and physical mixture of a bimetallic catalyst with a Pt monometallic catalyst. The samples were characterized by XRD, XPS, TPR, HRTEM and physisorption. It was found that the catalytic activity strongly depends on the synthesis protocol and the Pt precursor, which modify the particle size. Higher nitrate rates are achieved using H2PtCl6 than Pt(NH3)4(NO3)2; this is mainly related to the smaller metal particle size of the former, evidenced by HRTEM. Nitrate consumption rate is directly related with the mean particle size. The physical mixture of monometallic catalysts resulted in the highest nitrogen rate.

  7. Preparation of N-doped ZnO-loaded halloysite nanotubes catalysts with high solar-light photocatalytic activity.

    PubMed

    Cheng, Zhi-Lin; Sun, Wei

    2015-01-01

    N-doped ZnO nanoparticles were successfully assembled into hollow halloysite nanotubes (HNTs) by using the impregnation method. The catalysts based on N-doped ZnO-loaded HNTs nanocomposites (N-doped ZnO/HNTs) were characterized by X-ray diffraction (XRD), transmission electron microscopy-energy dispersive X-ray (TEM-EDX), scanning electron microscopy-energy dispersive X-ray (SEM-EDX), UV-vis and Fourier transform infrared spectroscopy (FT-IR) techniques. The XRD pattern showed ZnO nanoparticles with hexagonal structure loaded on HNTs. The TEM-EDX analysis indicated ZnO particles with the crystal size of ca.10 nm scattered in hollow structure of HNTs, and furthermore the concentration of N atom in nanocomposites was up to 2.31%. The SEM-EDX verified most of N-ZnO nanoparticles existing in hollow nanotubes of HNTs. Besides containing an obvious ultraviolet absorbance band, the UV-vis spectra of the N-doped ZnO/HNTs catalysts showed an available visible absorbance band by comparing to HNTs and non-doped ZnO/HNTs. The photocatalytic activity of the N-doped ZnO/HNTs catalysts was evaluated by the degradation of methyl orange (MO) solution with the concentration of 20 mg/L under the simulated solar-light irradiation. The result showed that the N-doped ZnO/HNTs catalyst exhibited a desirable solar-light photocatalytic activity.

  8. Pt/Mo2C/C-cp as a highly active and stable catalyst for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Lin, Lili; Sheng, Wenchao; Yao, Siyu; Ma, Ding; Chen, Jingguang G.

    2017-03-01

    A Pt/Mo2C/C-cp electrocatalyst with optimized Ptsbnd Mo2C chemical bonding is synthesized and evaluated for the ethanol oxidation reaction (EOR). The chemical bonding of Mo2C to Pt particles renders exceptional EOR activity at low potentials, which is 15 and 2.5 times higher than Pt/C and commercial 40% PtRu/C, respectively, at 0.6 V (vs. RHE). The stability of the Pt/Mo2C/C-cp electrocatalyst is comparable to the commercial 40% PtRu/C catalyst. CO stripping test demonstrates the existence of highly active sites for CO oxidation on the Pt/Mo2C/C-cp catalyst. In-situ infrared spectroscopic studies of EOR reveal that the excellent anti-poisoning ability of the Pt/Mo2C/C-cp catalyst is related to the relatively weak binding of carbonyl intermediates over the Pt/Mo2C/C-cp catalysts.

  9. Boron-doped graphene as promising support for platinum catalyst with superior activity towards the methanol electrooxidation reaction

    NASA Astrophysics Data System (ADS)

    Sun, Yongrong; Du, Chunyu; An, Meichen; Du, Lei; Tan, Qiang; Liu, Chuntao; Gao, Yunzhi; Yin, Geping

    2015-12-01

    We report the synthesis of boron-doped graphene by thermally annealing the mixture of graphene oxide and boric acid, and its usage as the support of Pt catalyst towards the methanol oxidation reaction. The composition, structure and morphology of boron-doped graphene and its supported Pt nanoparticles (Pt/BG) are characterized by transmission electron microscopy, inductively coupled plasma mass spectrometry, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It is revealed that boron atoms are doped into graphene network in the form of BC2O and BCO2 bonds, which lead to the increase in defect sites and facilitate the subsequent deposition of Pt nanoparticles. Therefore, the Pt/BG catalyst presents smaller particle size and narrower size distribution than the graphene supported Pt (Pt/G) catalyst. When evaluated as the electrocatalyst for the methanol oxidation reaction, the Pt/BG catalyst exhibits excellent electrochemical activity and stability demonstrated by cyclic voltammetry and chronoamperometry tests. The enhanced activity is mainly ascribed to the electronic interaction between boron-doped graphene and Pt nanoparticles, which lowers the d-band center of Pt and thus weakens the absorption of the poisoning intermediate CO. Our work provides an alternative approach of improving the reaction kinetics for the oxidation of small organic molecules.

  10. Synthesis, characterization and photocatalytic activities of rare earth-loaded BiVO 4 catalysts

    NASA Astrophysics Data System (ADS)

    Xu, Hui; Wu, Chundu; Li, Huaming; Chu, Jinyu; Sun, Guangsong; Xu, Yuanguo; Yan, Yongsheng

    2009-11-01

    The BiVO 4-based photocatalysts loaded with rare earth (RE=Ho, Sm, Yb, Eu, Gd, Nd, Ce and La) were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), nitrogen adsorption for the BET specific surface area and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by decolorization of methylene blue (MB) under visible light irradiation. The results of XRD, SEM and XPS analysis deduced that the rare earth ions were present as RE 2O 3 in the samples. The DRS analysis showed the shift in the absorbption edge from the UV to the visible range: Ho 3+-BiVO 4 < Sm 3+-BiVO 4 < Yb 3+-BiVO 4 < Eu 3+-BiVO 4 < Gd 3+-BiVO 4 < Nd 3+-BiVO 4 < La 3+-BiVO 4 < Ce 3+-BiVO 4 < BiVO 4. Gd 3+-BiVO 4 had the highest photocatalytic activity among all the RE 3+-BiVO 4 catalysts. The optimal Gd content was 8 at% under visible light irradiation. This beneficial effect was attributed to the specific electron structure characteristics of gadolinium and the increasing in the separation efficiency of the electron-hole pairs. On the contrast, the other rare earth ions had the detrimental effect on the photocatalytic decolorization of MB.

  11. Synergistic activation of the Diels-Alder reaction by an organic catalyst and substituents: a computational study.

    PubMed

    Linder, Mats; Brinck, Tore

    2009-04-07

    Density functional theory (DFT), using the hybrid functionals B3LYP and B2PLYP, has been employed to investigate the activation of the acrolein-butadiene Diels-Alder reaction, mediated by a thiourea catalyst. Effects due to electron-donating groups (EDGs) on the diene, as well as electron-withdrawing groups (EWGs) on the dienophile, have also been studied. Organic catalysts such as thioureas are known to lower the activation energy through hydrogen-bonding to the carbonyl oxygen, in a way that mimics the oxyanion holes of hydrolytic enzymes. EDGs and EWGs were found to further activate the reaction, and the catalyst showed a synergistic behavior towards the EDGs. Polar solvents were found to reduce the overall activation energy, but also the relative catalytic effect of the thiourea, in accordance with experimental studies. The substituent-mediated reactions displayed more asynchronous transition structures with lower activation energy, which led us to investigate the possibility of an alternative two-step, Michael-type route, similar to what has been found in macrophomate synthase. Although the concerted Diels-Alder route was found to be favored over the Michael route, the calculated activation energy difference is less than 1 kcal mol(-1), which suggests that the two mechanisms compete, and could be responsible for the particular stereochemical outcome of an experiment.

  12. Highly active and stable iron Fischer-Tropsch catalyst for synthesis gas conversion to liquid fuels

    SciTech Connect

    Bukur, D.B.; Lang, X.

    1999-09-01

    A precipitated iron Fischer-Tropsch (F-T) catalyst (100 Fe/3 Cu/4 K/16 SiO{sub 2} on mass basis) was tested in a stirred tank slurry reactor under reaction conditions representative of industrial practice using CO-rich synthesis gas (260 C, 1.5--2.2 MPa, H{sub 2}/CO = 2/3). Repeatability of performance and reproducibility of catalyst preparation procedure were successfully demonstrated on a laboratory scale. Catalyst productivity was increased by operating at higher synthesis pressure while maintaining a constant contact time in the reactor and through the use of different catalyst pretreatment procedures. In one of the tests (run SA-2186), the catalyst productivity was 0.86 (g hydrocarbons/g Fe/h) at syngas conversion of 79%, methane selectivity of 3% (weight percent of total hydrocarbons produced), and C{sub 5}+ hydrocarbon selectivity of 83 wt %. This represents a substantial improvement in productivity in comparison to state-of-the-art iron F-T catalysts. This catalyst is ideally suited for production of high-quality diesel fuels and C{sub 2}-c{sub 4} olefins from a coal-derived synthesis gas.

  13. Identification of the haemolytic activity of Malassezia species.

    PubMed

    Juntachai, Weerapong; Kummasook, Aksarakorn; Mekaprateep, Malee; Kajiwara, Susumu

    2014-03-01

    Malassezia species are part of the normal skin flora and are associated with a number of human and animal skin diseases. However, the mechanisms that mediate infection and host-fungal interactions are poorly understood. The haemolytic activity of several microorganisms is considered a factor that contributes to pathogenicity of the organism to humans and animals. This virulence factor was previously identified in several pathogenic fungi that cause systemic mycoses, such as Aspergillus and Candida. In this study, the haemolytic activity of six major Malassezia species, including M. furfur, M. globosa, M. pachydermatis, M. restricta, M. slooffiae and M. sympodialis, was investigated. The haemolytic activity of these species was tested on tryptone soya agar with 5% sheep blood. All the examined Malassezia species produced a halo zone of complete haemolysis. A quantitative analysis of the haemolytic activity was performed by incubating sheep erythrocytes with the extraction from culture of each Malassezia species. Interestingly, M. globosa and M. restricta showed significantly high haemolytic activity compared with the other Malassezia species. In addition, M. globosa also exhibited stable haemolytic activity after treatment at 100 °C and in the presence of some proteases, indicating that this haemolytic factor is different from those of other fungi.

  14. Volatile species in halide-activated-diffusion coating packs

    NASA Technical Reports Server (NTRS)

    Bianco, Robert; Rapp, Robert A.; Jacobson, Nathan S.

    1992-01-01

    An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

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

    DOEpatents

    Angelici, R.J.; Gao, H.

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilication, olefin oxidation, isomerization, hydrocyanidation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical. 2 figs.

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

    DOEpatents

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

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

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers.

  18. Unraveling the role of support surface hydroxyls and its effect on the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion: A theoretical study

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Duan, Tian; Wang, Baojun; Ling, Lixia

    2016-08-01

    The supported Rh-based catalysts exhibit the excellent catalytic performances for syngas conversion to C2 species. In this study, all possible elementary steps leading to C2 species from syngas have been explored to identify the role of support and its surface hydroxyls over Rh/γ-Al2O3 catalyst; Here, the results are obtained using density functional theory (DFT) method. Two models: Rh4 cluster supported on the dry γ-Al2O3(110) surface, D(Rh4), and on the hydroxylated γ-Al2O3(110) surface, H(Rh4), have been used to model Rh/γ-Al2O3 catalyst. Our results show that CO prefers to be hydrogenated to CHO, subsequently, starting from CHO species, CH and CH2 species are the dominate monomers among CHx(x = 1-3) species rather than CH3 and CH3OH on D(Rh4) and H(Rh4) surfaces, suggesting that γ-Al2O3-supported Rh catalyst exhibits the high selectivity towards CHx formation compared to the pure Rh catalyst. On the other hand, D(Rh4) is more favorable for C2 hydrocarbon (C2H2) formation, whereas H(Rh4) surface easily produces C2 hydrocarbon (C2H2) and C2 oxygenates (CHCO,CH2CHO), indicating that the surface hydroxyls of support can affect the selectivity of C2 species over Rh/γ-Al2O3 catalyst in syngas conversion. Moreover, compared to the pure Rh(111) surface, Rh/γ-Al2O3 catalyst can achieve the excellent catalytic performances for syngas conversion to C2 species.

  19. Hydrocracking catalyst

    SciTech Connect

    Arias, B.; Galiasso, R.; Kum, H.

    1985-02-12

    The invention relates to a particular method for the preparation of a hydrocracking catalyst, using a high iron content bauxite as a basis. This bauxite is ground and screened to a specific size and mixed with three types of additives: a promoter additive of the P, Mo, Co, Ni, W type. A hardener additive of the phosphoric acid type, ammonium phosphate. And a lubricant and pore-generating additive of the polyvinyl alcohol, polyethylene-glycol, starch type. The particularity consists in that the three additives are added simultaneously during the extrusion of the sample. That way, a particular surface composition is obtained which allows for the activity of the catalyst. Extruded products are obtained in sizes of 1/8, 1/16, and 1/32'' and submitted to drying and calcination programs for their activation. The obtained catalyst offers a good mechanical strength, a high content in macropores and a high activity, specifically for the hydrocracking of heavy Venezuelan crudes or residues.

  20. CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

    PubMed

    Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

    2014-12-10

    Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

  1. Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

    PubMed

    Li, Jingkun; Alsudairi, Amell; Ma, Zi-Feng; Mukerjee, Sanjeev; Jia, Qingying

    2017-02-01

    Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (Eredox) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the Eredox of active sites; and the intrinsic activity of active sites with low Eredox have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high Eredox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low Eredox side is limited by either the site-blocking effect and/or intrinsic activity depending on the Eredox.

  2. Progress in Synthesis of Highly Active and Stable Nickel-Based Catalysts for Carbon Dioxide Reforming of Methane.

    PubMed

    Kawi, Sibudjing; Kathiraser, Yasotha; Ni, Jun; Oemar, Usman; Li, Ziwei; Saw, Eng Toon

    2015-11-01

    In recent decades, rising anthropogenic greenhouse gas emissions (mainly CO2 and CH4 ) have increased alarm due to escalating effects of global warming. The dry carbon dioxide reforming of methane (DRM) reaction is a sustainable way to utilize these notorious greenhouse gases. This paper presents a review of recent progress in the development of nickel-based catalysts for the DRM reaction. The enviable low cost and wide availability of nickel compared with noble metals is the main reason for persistent research efforts in optimizing the synthesis of nickel-based catalysts. Important catalyst features for the rational design of a coke-resistant nickel-based nanocatalyst for the DRM reaction are also discussed. In addition, several innovative developments based on salient features for the stabilization of nickel nanocatalysts through various means (which include functionalization with precursors, synthesis by plasma treatment, stabilization/confinement on mesoporous/microporous/carbon supports, and the formation of metal oxides) are highlighted. The final part of this review covers major issues and proposed improvement strategies pertaining to the rational design of nickel-based catalysts with high activity and stability for the DRM reaction.

  3. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    SciTech Connect

    Cronauer, D. C.

    2011-04-15

    Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry - specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those expected for complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide surfaces. The first

  4. Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth

    NASA Astrophysics Data System (ADS)

    Li, Ling; Li, Lu Hua; Chen, Ying; Dai, Xiujuan J.; Xing, Tan; Petravic, Mladen; Liu, Xiaowei

    2012-07-01

    Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer.

  5. Mechanically activated catalyst mixing for high-yield boron nitride nanotube growth.

    PubMed

    Li, Ling; Li, Lu Hua; Chen, Ying; Dai, Xiujuan J; Xing, Tan; Petravic, Mladen; Liu, Xiaowei

    2012-07-24

    Boron nitride nanotubes (BNNTs) have many fascinating properties and a wide range of applications. An improved ball milling method has been developed for high-yield BNNT synthesis, in which metal nitrate, such as Fe(NO3)3, and amorphous boron powder are milled together to prepare a more effective precursor. The heating of the precursor in nitrogen-containing gas produces a high density of BNNTs with controlled structures. The chemical bonding and structure of the synthesized BNNTs are precisely probed by near-edge X-ray absorption fine structure spectroscopy. The higher efficiency of the precursor containing milling-activated catalyst is revealed by thermogravimetric analyses. Detailed X-ray diffraction and X-ray photoelectron spectroscopy investigations disclose that during ball milling the Fe(NO3)3 decomposes to Fe which greatly accelerates the nitriding reaction and therefore increases the yield of BNNTs. This improved synthesis method brings the large-scale production and application of BNNTs one step closer.

  6. Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions.

    PubMed

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established.

  7. Characteristics of Polyaniline Cobalt Supported Catalysts for Epoxidation Reactions

    PubMed Central

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established. PMID:24701183

  8. Comparison of catalytic activities for photocatalytic and sonocatalytic degradation of methylene blue in present of anatase TiO2-CNT catalysts.

    PubMed

    Zhang, Kan; Zhang, Feng Jun; Chen, Ming Liang; Oh, Won Chun

    2011-05-01

    Anatase TiO(2)-CNT catalysts with high specific surface areas were prepared by depositing TiO(2) particles on the surface of carbon nanotubes (CNTs) using a modified sol-gel technique. These catalysts prepared with different amounts of CNTs were characterized by nitrogen adsorption, Fourier Transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), Transmission Electron Microscope (TEM), X-ray diffraction (XRD), Raman spectroscopy, energy dispersive X-ray (EDX) and ultraviolet-visible (UV-Vis) spectroscopy. The catalytic activity of the anatase TiO(2)-CNT catalysts was assessed by examining the degradation of methylene blue (MB) from model aqueous solutions as a probe reaction under visible light and ultrasonic irradiation. The synergistic effect of the greater surface area and catalytic activities of the composite catalysts was examined in terms of the strong adsorption ability and interphase interaction by comparing the different amounts and roles of CNTs in the catalysts.

  9. Nanosized IrO(x)-Ir Catalyst with Relevant Activity for Anodes of Proton Exchange Membrane Electrolysis Produced by a Cost-Effective Procedure.

    PubMed

    Lettenmeier, Philipp; Wang, Li; Golla-Schindler, Ute; Gazdzicki, Pawel; Cañas, Natalia A; Handl, Michael; Hiesgen, Renate; Hosseiny, Seyed S; Gago, Aldo S; Friedrich, Kaspar A

    2016-01-11

    We have developed a highly active nanostructured iridium catalyst for anodes of proton exchange membrane (PEM) electrolysis. Clusters of nanosized crystallites are obtained by reducing surfactant-stabilized IrCl3 in water-free conditions. The catalyst shows a five-fold higher activity towards oxygen evolution reaction (OER) than commercial Ir-black. The improved kinetics of the catalyst are reflected in the high performance of the PEM electrolyzer (1 mg(Ir) cm(-2)), showing an unparalleled low overpotential and negligible degradation. Our results demonstrate that this enhancement cannot be only attributed to increased surface area, but rather to the ligand effect and low coordinate sites resulting in a high turnover frequency (TOF). The catalyst developed herein sets a benchmark and a strategy for the development of ultra-low loading catalyst layers for PEM electrolysis.

  10. Environmentally-benign catalysts for the selective catalytic reduction of NO(x) from diesel engines: structure-activity relationship and reaction mechanism aspects.

    PubMed

    Liu, Fudong; Yu, Yunbo; He, Hong

    2014-08-11

    Selective catalytic reduction of NOx using NH3 or hydrocarbons (NH3-SCR or HC-SCR) in oxygen-rich exhaust from diesel engines remains a major challenge in environmental catalysis. The development of highly efficient, stable and environmentally-benign catalysts for SCR processes is very important for practical use. In this feature article, the structure-activity relationship of vanadium-free catalysts in the NH3-SCR reaction is discussed in detail, including Fe-, Ce-based oxide catalysts and Fe-, Cu-based zeolite catalysts, which is beneficial for catalyst redesign and activity improvement. Based on our research, a comprehensive mechanism contributing to the performance of Ag/Al2O3 in HC-SCR is provided, giving a clue to the design of a catalytic system with high efficiency.

  11. Environmentally benign heterogeneous nano-particle catalysts: synthesis, characterization and catalytic activity of 4-nitrophenol.

    PubMed

    Murugan, Eagambaram; Jebaranjitham, J Nimita

    2011-02-01

    Pollution free catalyst is an attractive area of current interest. The p-Aminophenol is one of the most significant catalyst, because it involves the manufacture of various pharmaceuticals. Crosslinked poly(styrene)-co-poly(4-vinylimidazole) (PSPVIM) was prepared by varying the crosslinked monomer ratio as 2% and 10% respectively. The 2 (w%) of DVB, 25 (w%) of N-VIm as functional monomer and 73 (w%) of styrene as support monomer as organic phase and gelatin, boric acid and polyvinyl alcohol as aqueous phase was used to prepare cross-linked poly(styrene)-co-poly(N-vinyl imidazole) (PVIM) beads (Type-I). Similarly, Type II beads were also prepared by fixing the 10% as a cross linking ratio (DVB). The immobilization of Ag NPs onto the PS-VIm polymer matrix was performed using AgNO3 as a metal precursor solution. The k(obs) determined from UV-Vis results, reveals that the degree of reduction of 4-nitrophenol using Type-I catalysts is more effective than Type-II catalyst due to lower immobilization of AgNPs at higher cross-linked bead matrix. It was found that on increasing the amount of catalyst i.e., type-I PS-PVIm-AgNPs, the rate constant also increases. Therefore, PS-PVIm-AgNPs (Type-I) heterogeneous catalyst is superior for the reduction of 4-NP.

  12. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    SciTech Connect

    Peng, X.D.; Toseland, B.A.; Underwood, R.P.

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  13. A novel Pt-Co alloy hydrogen anode catalyst with superlative activity, CO-tolerance and robustness

    NASA Astrophysics Data System (ADS)

    Shi, G. Y.; Yano, H.; Tryk, D. A.; Watanabe, M.; Iiyama, A.; Uchida, H.

    2016-07-01

    PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations.PtCo nanoparticles, having two atomic layers of stabilized Pt skin, supported on carbon black (Pt2AL-PtCo/C), exhibited superlative mass activity for the CO-tolerant hydrogen oxidation reaction (HOR), together with high robustness with respect to air exposure, as a novel anode catalyst in reformate gas-based polymer electrolyte fuel cells. The high area-specific HOR activity and CO tolerance are consistent with DFT calculations. Electronic supplementary information (ESI) available: Experimental details, TEM images and particle size distribution histograms of all catalysts, and details of the DFT calculations. See DOI: 10.1039/c6nr00778c

  14. The effects of cerium doping concentration on the properties and photocatalytic activity of bimetallic Mo/Ce catalyst

    NASA Astrophysics Data System (ADS)

    Allaedini, Ghazaleh; Tasirin, Siti Masrinda; Aminayi, Payam

    2016-10-01

    In this study, the characterization and photocatalytic activity of MoO3 nanoparticles doped with various doping concentrations of cerium have been investigated. The Fourier transform infrared (FT-IR) spectra of the prepared catalysts confirmed that MoO3 particles have been successfully doped by cerium. Field emission scanning electron microscopy (FESEM) was performed to visualize the surface morphology of the obtained catalysts. The XRD patterns suggested that the crystallinity of the sample with the lowest doping concentration of 15 mol % was higher in comparison with samples of higher doping concentrations. The volume-averaged crystal sizes of the obtained catalysts were calculated to be 25, 28, and 32 nm for 15, 35, and 60 mol % samples, respectively. The photocatalytic activity along with the reaction kinetics of Ce-doped MoO3 nanoparticles have also been investigated through the dye degradation of methyl orange. The synthesized Ce-doped MoO3 particles with the lowest dopant concentration of 15 mol % exhibited the highest photocatalytic activity for methyl orange dye degradation. It was observed that photo-degradation activity decreased with an increase in the doping concentration of cerium. The predicted rate constants for samples with 15, 35, and 60 mol % doping concentrations were found to be 0.0432, 0.035, and 0.029 min-1, respectively.

  15. A nickel iron diselenide-derived efficient oxygen-evolution catalyst

    NASA Astrophysics Data System (ADS)

    Xu, Xiang; Song, Fang; Hu, Xile

    2016-08-01

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

  16. The effect of activated carbon support surface modification on characteristics of carbon nanospheres prepared by deposition precipitation of Fe-catalyst

    NASA Astrophysics Data System (ADS)

    Kristianto, H.; Arie, A. A.; Susanti, R. F.; Halim, M.; Lee, J. K.

    2016-11-01

    In this study the effect of activated carbon support modification to synthesis of CNSs was observed. Modification of activated carbon was done by using nitric acid. The effect of modification was analyzed from its FTIR spectra. The Fe catalysts were deposited on to the support by using urea deposition precipitation method at various initial catalysts concentration. CNSs was synthesized by utilizing cooking palm oil as renewable carbon source, and pyrolized at 700°C for 1 hour under nitrogen atmosphere. The products obtained then analyzed using SEM-EDS, TEM, XRD, and Raman spectroscopy. The modification of activated carbon support had increased the oxygen functional group. This increase resulted on increase of metal catalysts deposited on activated carbon surface. Peak of C (100) was observed, while ID/IG of samples were obtained around 0.9, which is commonly obtained for CNSs. High catalysts loading on modified activated carbon support caused decomposition of CNSs and formation carbon onion.

  17. Environmentally friendly one-pot synthesis of alpha-alkylated nitriles using hydrotalcite-supported metal species as multifunctional solid catalysts.

    PubMed

    Motokura, Ken; Fujita, Noriaki; Mori, Kohsuke; Mizugaki, Tomoo; Ebitani, Kohki; Jitsukawa, Koichiro; Kaneda, Kiyotomi

    2006-11-06

    A ruthenium-grafted hydrotalcite (Ru/HT) and hydrotalcite-supported palladium nanoparticles (Pd(nano)/HT) are easily prepared by treating basic layered double hydroxide, hydrotalcite (HT, Mg(6)Al(2)(OH)(16)CO(3)) with aqueous RuCl(3)n H(2)O and K(2)[PdCl(4)] solutions, respectively, using surface impregnation methods. Analysis by means of X-ray diffraction, and energy-dispersive X-ray, electron paramagnetic resonance, and X-ray absorption fine structure spectroscopies proves that a monomeric Ru(IV) species is grafted onto the surface of the HT. Meanwhile, after reduction of a surface-isolated Pd(II) species, highly dispersed Pd nanoclusters with a mean diameter of about 70 A is observed on the Pd(nano)/HT surface by transmission electron microscopy analysis. These hydrotalcite-supported metal catalysts can effectively promote alpha-alkylation reactions of various nitriles with primary alcohols or carbonyl compounds through tandem reactions consisting of metal-catalyzed oxidation and reduction, and an aldol reaction promoted by the base sites of the HT. In these catalytic alpha-alkylations, homogeneous bases are unnecessary and the only by-product is water. Additionally, these catalyst systems are applicable to one-pot syntheses of glutaronitrile derivatives.

  18. Comparison of cytotoxic activities of extracts from Selaginella species

    PubMed Central

    Li, Juan; Lei, Xiang; Chen, Ke-li

    2014-01-01

    Background: Selaginella species are resurrection plants, which are known, possess various molecular bioactivities depending on species, but only a few species have been detailed observe in the advanced research. Objective: The objective of the following study is to compare the chemical profiles of different species of Selaginella and to investigate cytotoxicity and induction of apoptosis activities of some species of Selaginella. Materials and Methods: The high-performance liquid chromatography (HPLC) method was developed for chemical analysis. Ethyl acetate, ethanol and water-soluble extracts from seven Selaginella species were submitted to 3-(4,5-dimenthyl thizol-2-yl)-2,5-diphenyl tetrazolium bromide assay, flow cytometry, deoxyribonucleic acid (DNA) laddering analysis and caspase-3 expression using Bel-7402, HT-29 and HeLa cells. Results: The HPLC analysis revealed two major common peaks, which were identified as amentoflavone and robustaflavone and another three main peaks in their chromatograms. The results showed that S. labordei, Selaginella tamariscina and Selaginella uncinata had relatively stronger activities on Bel-7402 and HeLa cells and Selaginella moellendorfii had moderate antiproliferation activities, but Selaginella remotifolia and Selaginella pulvinata had almost no inhibitory activities. The main active components were in the ethyl acetate extracts which had abundant biflavonoids. The effects of these extracts on cell proliferation and apoptosis in different cells were not the same, they were more apparent on HeLa cells than on HT-29 cells. The assay of DNA laddering analysis and caspase-3 expression further confirmed that inducing cell apoptosis was one of antitumor mechanisms and antitumor activities of Selaginella species were related to apoptosis induced by caspase family. Conclusion: S. labordei, S. tamariscina and S. uncinata would be potential antitumor agents. PMID:25422557

  19. A highly active and coke-resistant steam reforming catalyst comprising uniform nickel-iron alloy nanoparticles.

    PubMed

    Koike, Mitsuru; Li, Dalin; Nakagawa, Yoshinao; Tomishige, Keiichi

    2012-12-01

    Doing fine with Ni-Fe: The calcination and reduction of a hydrotalcite precursor containing Ni and Fe ions gives uniform Ni-Fe alloy nanoparticles mixed with Mg(Ni, Fe, Al)O particles. The uniformity of the Ni-Fe alloy nanoparticles is connected to the catalyst's high activity and resistance to coke formation in toluene and phenol steam reforming reactions.

  20. Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

    PubMed

    Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

    2016-06-25

    Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%.

  1. Dry reforming of methane on a highly-active Ni-CeO2 catalyst: Effects of metal-support interactions on C–H bond breaking

    SciTech Connect

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

    2016-05-04

    Ni-CeO2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO2–x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C1s XPS region. As a result, the reforming of methane proceeds in a clean and efficient way.

  2. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    DOE PAGES

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

    2015-02-02

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation ofmore » CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.« less

  3. Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO2 hydrogenation

    NASA Astrophysics Data System (ADS)

    Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; Illas, Francesc

    2015-10-01

    Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO2 decomposition, thiophene hydrodesulfurization, O2 and H2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water-gas shift (CO2 + H2 → CO + H2O) and CO2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalytic activity of Au/TiC towards the hydrogenation of CO or CO2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO2 involves the hydrogenation of a HOCO-like intermediate. When dealing with mixtures of syngas (CO/CO2/H2/H2O), CO could be transformed into CO2 through the water gas shift reaction with subsequent hydrogenation of CO2 to methanol.

  4. Design and preparation of highly active carbon nanotube-supported sulfated TiO 2 and platinum catalysts for methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Song, Huanqiao; Xiao, Pu; Qiu, Xinping; Zhu, Wentao

    A novel electrocatalyst structure of carbon nanotube-supported sulfated TiO 2 and Pt (Pt-S-TiO 2/CNT) is reported. The Pt-S-TiO 2/CNT catalysts are prepared by a combination of improved sol-gel and ethylene glycol reduction methods. Transmission electron microscopy and X-ray diffraction show that the sulfated TiO 2 is amorphous and is coated uniformly on the surface of the CNTs. Pt nanoparticles of about 3.6 nm in size are homogenously dispersed on the sulfated TiO 2 surface. Fourier transform infrared spectroscopy analysis proves that the CNT surfaces are modified with sulfated TiO 2 and a high concentration of SO x, and adsorbed OH species exist on the surface of the sulfated TiO 2. Electrochemical studies are carried out using chronoamperometry, cyclic voltammetry, CO stripping voltammetry and impedance spectroscopy. The results indicate that Pt-S-TiO 2/CNT catalysts have much higher catalytic activity and CO tolerance for methanol electrooxidation than Pt/TiO 2/CNTs, Pt/CNTs and commercial Pt/C.

  5. The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media.

    PubMed

    Rahul, R; Singh, R K; Bera, B; Devivaraprasad, R; Neergat, M

    2015-06-21

    Oxygen reduction reaction (ORR) is investigated on bulk PdO-based catalysts (oxides of Pd and Pd3Co) in oxygen-saturated 0.1 M HClO4 to establish the role of surface oxides and adsorbed hydrogen in the activity and product selectivity (H2O/H2O2). The initial voltammetric features suggest that the oxides are inactive toward ORR. The evolution of the ORR voltammograms and potential-dependent H2O2 generation features on the PdO catalyst suggest gradual and parallel in situ reduction of the bulk PdO phase below ∼0.4 V in the hydrogen underpotential deposition (Hupd) region; the reduction of the bulk PdO catalyst is confirmed from the X-ray photoelectron spectra (XPS) and X-ray diffraction (XRD) patterns. The potential-dependent H2O2 generation features originate due to the presence of surface oxides and adsorbed hydrogen; this is further confirmed using halide ions (Cl(-) and Br(-)) and peroxide as the external impurities.

  6. Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

    SciTech Connect

    Holby, Edward F.; Zelenay, Piotr

    2016-05-17

    Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by these materials.

  7. Low-temperature conversion of methane to methanol on CeOx/Cu2O catalysts: Water controlled activation of the C–H Bond

    SciTech Connect

    Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.; Liu, Ping; Rodriguez, Jose A.

    2016-10-10

    Here, an inverse CeO2/Cu2O/Cu(111) catalyst is able to activate methane at room temperature producing C, CHx fragments and COx species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CHx fragments. At a temperature of 450 K, in the presence of water, a CH4 → CH3OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CHx fragments, and generating centers on which methane can directly interact to yield methanol.

  8. Correction: Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions

    NASA Astrophysics Data System (ADS)

    Parapat, Riny Y.; Wijaya, Muliany; Schwarze, Michael; Selve, Sören; Willinger, Marc; Schomäcker, Reinhard

    2016-03-01

    Correction for `Particle shape optimization by changing from an isotropic to an anisotropic nanostructure: preparation of highly active and stable supported Pt catalysts in microemulsions' by Riny Y. Parapat et al., Nanoscale, 2013, 5, 796-805.

  9. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    SciTech Connect

    Jackson, N.B.; Kohler, S.; Harrington, M.

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  10. Propene activation by the oxo-iron active species of taurine/alpha-ketoglutarate dioxygenase (TauD) enzyme. How does the catalysis compare to heme-enzymes?

    PubMed

    de Visser, Sam P

    2006-08-02

    Density functional calculations on the oxygenation reaction of propene by a model for taurine/alpha-ketoglutarate dioxygenase (TauD) enzyme are presented. The oxo-iron active species of TauD is shown to be a powerful and aggressive oxidant, which is able to hydroxylate C-H bonds and epoxidize C=C bonds with low barriers. In the case of propene oxygenation, the hydroxylation and epoxidation mechanisms are competitive on a dominant quintet spin state surface. We have compared the mechanism and thermodynamics of TauD with oxo-iron heme catalysts, such as the cytochromes P450, and found some critical differences. The TauD model is found to be much more reactive toward oxygenation of substrates than oxo-iron complexes in a heme environment with much lower reaction barriers. We have analyzed this and assigned this to the strength of the O-H bond formed after hydrogen abstraction from a substrate, which is at least 10 kcal mol(-)(1) stronger in five-coordinated oxo-iron nonheme complexes than in six-coordinated oxo-iron heme complexes. Since, the metal in TauD enzymes is five-coordinated, whereas in heme-enzymes it is six-coordinated there are some critical differences in the valence molecular orbitals. Thus, in oxo-iron heme catalysts one of the antibonding pi orbitals is replaced by a low-lying nonbonding delta orbital resulting in a lower overall spin state. Moreover, heme-enzymes have an extra oxidation equivalent located on the heme, which is missing in non-heme oxo-iron catalysts. As a result, the oxo-iron species of TauD reacts via single-state reactivity on a dominant quintet spin state surface, whereas oxo-iron heme catalysts react via two-state reactivity on competing doublet and quartet spin states.

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

    PubMed

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

    2015-11-13

    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in "clean" conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm(-2) and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm(-2) by day 13, achieving similar values of an activated carbon based cathode. The presence of S(2-) and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

  12. A highly active and magnetically recoverable tris(triazolyl)-Cu(I) catalyst for alkyne-azide cycloaddition reactions.

    PubMed

    Wang, Dong; Etienne, Laetitia; Echeverria, María; Moya, Sergio; Astruc, Didier

    2014-04-01

    Nanoparticle-supported tris(triazolyl)-CuBr, with a diameter of approximately 25 nm measured by TEM spectroscopy, has been easily prepared, and its catalytic activity was evaluated in the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In initial experiments, 0.5 mol % loading successfully promoted the CuAAC reaction between benzyl azide and phenylacetylene, in water at room temperature (25 °C). During this process, the iron oxide nanoparticle-supported tris(triazolyl)-CuBr displayed good monodispersity, excellent recoverability, and outstanding reusability. Indeed, it was simply collected and separated from the reaction medium by using an external magnet, then used for another five catalytic cycles without significant loss of catalytic activity. Inductively coupled plasma (ICP) analysis for the first cycle revealed that the amount of copper leached from the catalyst into the reaction medium is negligible (1.5 ppm). The substrate scope has been examined, and it was found that the procedure can be successfully extended to various organic azides and alkynes and can also be applied to the one-pot synthesis of triazoles, through a cascade reaction involving benzyl bromides, alkynes, and sodium azide. In addition, the catalyst was shown to be an efficient CuAAC catalyst for the synthesis of allyl- and TEG-ended (TEG=triethylene glycol) 27-branch dendrimers.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm-2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm-2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2- and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

  14. Towards highly active Pd/CeO2 for alkene hydrogenation by tuning Pd dispersion and surface properties of the catalysts.

    PubMed

    Zhang, Sai; Li, Jing; Xia, Zhaoming; Wu, Chao; Zhang, Zhiyun; Ma, Yuanyuan; Qu, Yongquan

    2017-03-02

    Extensive applications of noble metals as heterogeneous catalysts are limited by their global reserve scarcity and exorbitant price. Identifying the intrinsic active nature of a catalyst benefits the designing of catalysts with trace amounts of noble metals; these catalysts display better or comparable overall catalytic efficiency than their heavily loaded counterparts. Herein, systematic studies on Pd dispersion and surface properties of a series of Pd/CeO2 catalysts for styrene hydrogenation showed that high Pd dispersion and surface abundant defects of the catalysts are essential to realize superior activity. Highly dispersed subnanometric Pd clusters on porous nanorods of ceria with a large surface Ce(3+) fraction of 27.4%, high Pd dispersion of 73.6%, and low Pd loading of 0.081 wt% delivered a very large turnover frequency of 103 233 h(-1) based on each exposed Pd atom for styrene hydrogenation at 1.0 MPa H2 and 30 °C. Experimental data, kinetic analysis, and density functional theory calculations revealed that the highly dispersed Pd shows a low affinity for styrene and provides more exposed Pd sites for hydrogen activation. The surface abundant defects (oxygen vacancy) of Pd/CeO2 catalysts can enrich the electron density of Pd, improve its capability for H2 dissociation and lower the affinity of styrene for Pd.

  15. Immobilization of a Metal-Nitrogen-Carbon Catalyst on Activated Carbon with Enhanced Cathode Performance in Microbial Fuel Cells.

    PubMed

    Yang, Wulin; Logan, Bruce E

    2016-08-23

    Applications of microbial fuel cells (MFCs) are limited in part by low power densities mainly due to cathode performance. Successful immobilization of an Fe-N-C co-catalyst on activated carbon (Fe-N-C/AC) improved the oxygen reduction reaction to nearly a four-electron transfer, compared to a twoelectron transfer achieved using AC. With acetate as the fuel, the maximum power density was 4.7±0.2 W m(-2) , which is higher than any previous report for an air-cathode MFC. With domestic wastewater as a fuel, MFCs with the Fe-N-C/AC cathode produced up to 0.8±0.03 W m(-2) , which was twice that obtained with a Pt-catalyzed cathode. The use of this Fe-N-C/AC catalyst can therefore substantially increase power production, and enable broader applications of MFCs for renewable electricity generation using waste materials.

  16. Discovery and exploitation of AZADO: the highly active catalyst for alcohol oxidation.

    PubMed

    Iwabuchi, Yoshiharu

    2013-01-01

    The oxidation of primary and secondary alcohols to the corresponding aldehydes (or carboxylic acids) or ketones is a fundamental transformation in organic synthesis. Stable organic nitroxyl radicals as represented by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) (1) have been used extensively to catalyze the oxidation of a number of alcohol substrates employing environmentally benign co-oxidants such as bleach (NaOCl) or PhI(OAc)2. Although TEMPO oxidation is better known as a method for selective oxidation of primary alcohols to the corresponding aldehydes, the TEMPO-based method is not very efficient for the oxidation of structurally hindered secondary alcohols. We designed and synthesized 2-azaadamantane N-oxyl [AZADO (11)] and 1-Me-AZADO (20), a structurally less hindered class of nitroxyl radical. AZADOs were found to exhibit excellent catalytic activity enabling oxidation of a variety of alcohols with which TEMPO exhibits poor reactivity. Based on structure-activity relationships (SAR) employing AZADO (11), 1-Me-AZADO (20), 1,3-dimethyl-AZADO (33), 9-azabicyclo[3.3.1]nonane-N-oxyl [ABNO (34)] and 9-azanoradamantane N-oxyl [Nor-AZADO (37)], we concluded that the α-methyl group flanked nearby the nitroxyl group affects the reactivity for the oxidation of sterically hindered alcohols and the azaadamantane skeleton contributes to the high turnover of the catalyst. The highly active nature of AZADOs spurred us to exploit their further use in alcohol oxidations. A facile, green, one-pot oxidation of primary alcohols to carboxylic acids with broad substrate applicability has been developed by employing an expedient catalytic system consisting of the oxoammonium salt [1-Me-AZADO(+)X(-) (X=Cl, BF4)]/NaClO2. The synthetic use of AZADOs and the related nitroxyl radicals/oxoammonium salts-based methods for alcohol oxidation have been demonstrated in several total syntheses of natural products. We also describe the development of a Nor-AZADO (37)/DIAD/AcOH method that

  17. Hemolytic Activities of the Candida Species in Liquid Medium

    PubMed Central

    Malcok, Hilal Kuzucu; Aktas, Esin; Ayyildiz, Ahmet; Yigit, Nimet; Yazgi, Halil

    2009-01-01

    Objective The aim of this study was to evaluate the in vitro hemolytic activities of 107 Candida strains isolated from different clinical samples in liquid medium, and to examine the impact of glucose on this activity. Materials and Methods A total of 107 Candida isolates representing seven species (C. albicans, n=28; C. glabrata, n=23; C. tropicalis, n=17; C. parapsilosis, n=16; C. kefyr, n=14; C. krusei, n=5; C. guilliermondii, n=4) were included in the study. The hemolytic activities of the strains were tested on two different Sabouraud dextrose liquid media (SDB) containing 7% defibrinated human blood, one of which is supplemented with 3% glucose and the other without glucose. Cultures were evaluated at the end of a 48-hour incubation. The hemolysis in the media was detected spectrophotometrically by measuring the amount of released hemoglobin and compared with a standard hemolysate which was prepared prior to testing. The degree of hemolysis (percentage value) by an individual strain was calculated according to the following formula below: (Absorbance of supernatant media at 540 nm / Absorbance of standard hemolysate at 540 nm X 100). Results In the liquid medium without glucose, strains generally produced hemolysis at low levels. The degree of hemolysis produced by all species increased noticeably in the liquid medium with glucose. Strains of C. albicans and C.kefyr had demonstrated significant hemolytic activity, whereas others had lower activity. C. parapsilosis exerted very little hemolytic activity in the medium with glucose and showed no activity in the medium without glucose. Conclusion The hemolytic activities of most Candida species was found to be higher in the human blood-enriched SDB medium containing 3% additive glucose than in the one free from additives. This result indicates that increased blood glucose concentration may contribute to increased hemolytic activity in Candida species, and it suggests a parallel with possible pathogenesis of

  18. The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H2, CO, and CH4

    NASA Astrophysics Data System (ADS)

    Lesnyak, V. V.; Yatsimirskii, V. K.; Gut, I. N.; Boldyreva, O. Yu.

    2008-09-01

    The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H2, CO, and CH4 was studied. It was found that the composite catalysts containing H x MO3 phases (M = W or Mo), which were formed by the reduction of MoO3 and WO3 oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H2, CO, and CH4) with excess oxygen than the traditional Pd/Al2O3 deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H x MO3 phases was the limiting factor influencing the activity of these composite catalysts.

  19. Removal of aqueous oxalic acid by heterogeneous catalytic ozonation with MnOx/sewage sludge-derived activated carbon as catalysts.

    PubMed

    Huang, Yuanxing; Sun, Yaru; Xu, Zhihua; Luo, Mengyu; Zhu, Chunlei; Li, Liang

    2017-01-01

    MnOx/sewage sludge-derived activated carbon (MnOx/SAC) was prepared as catalysts to improve the performance of aqueous oxalic acid degradation by ozonation. The results indicated that MnOx/SAC had excellent catalytic activity in mineralization of oxalic acid during heterogeneous catalytic ozonation process. MnOx/SAC with a manganese load of 30% exhibited the strongest catalytic activity under the condition of solution pH3.5, which enhanced the oxalic acid removal from 10.3% to 92.2% in 60min compared with that treated by ozone alone. Increase of catalyst dosage and aqueous ozone concentration was advantageous for oxalic acid removal from water. On the basis of catalyst characterization analysis and the observation of inhibitory effect induced by higher pH, less catalyst dosage as well as the presence of hydroxyl radical scavenger, it was deduced that the reaction mechanism involved both hydroxyl radicals attack and surface reactions.

  20. Fischer-Tropsch Catalysts

    NASA Technical Reports Server (NTRS)

    White, James H. (Inventor); Taylor, Jesse W. (Inventor)

    2008-01-01

    Catalyst compositions and methods for F-T synthesis which exhibit high CO conversion with minor levels (preferably less than 35% and more preferably less than 5%) or no measurable carbon dioxide generation. F-T active catalysts are prepared by reduction of certain oxygen deficient mixed metal oxides.

  1. Diversity and Activity of Lysobacter Species from Disease Suppressive Soils

    PubMed Central

    Gómez Expósito, Ruth; Postma, Joeke; Raaijmakers, Jos M.; De Bruijn, Irene

    2015-01-01

    The genus Lysobacter includes several species that produce a range of extracellular enzymes and other metabolites with activity against bacteria, fungi, oomycetes, and nematodes. Lysobacter species were found to be more abundant in soil suppressive against the fungal root pathogen Rhizoctonia solani, but their actual role in disease suppression is still unclear. Here, the antifungal and plant growth-promoting activities of 18 Lysobacter strains, including 11 strains from Rhizoctonia-suppressive soils, were studied both in vitro and in vivo. Based on 16S rRNA sequencing, the Lysobacter strains from the Rhizoctonia-suppressive soil belonged to the four species Lysobacter antibioticus, Lysobacter capsici, Lysobacter enzymogenes, and Lysobacter gummosus. Most strains showed strong in vitro activity against R. solani and several other pathogens, including Pythium ultimum, Aspergillus niger, Fusarium oxysporum, and Xanthomonas campestris. When the Lysobacter strains were introduced into soil, however, no significant and consistent suppression of R. solani damping-off disease of sugar beet and cauliflower was observed. Subsequent bioassays further revealed that none of the Lysobacter strains was able to promote growth of sugar beet, cauliflower, onion, and Arabidopsis thaliana, either directly or via volatile compounds. The lack of in vivo activity is most likely attributed to poor colonization of the rhizosphere by the introduced Lysobacter strains. In conclusion, our results demonstrated that Lysobacter species have strong antagonistic activities against a range of pathogens, making them an important source for putative new enzymes and antimicrobial compounds. However, their potential role in R. solani disease suppressive soil could not be confirmed. In-depth omics'–based analyses will be needed to shed more light on the potential contribution of Lysobacter species to the collective activities of microbial consortia in disease suppressive soils. PMID:26635735

  2. Mössbauer study of the evolution of a laterite iron mineral based catalyst: Effect of the activation treatment

    NASA Astrophysics Data System (ADS)

    Cubeiro, M. L.; Goldwasser, M. R.; Zurita, M. J. Perez; Franco, C.; González-Jiménez, F.; Jaimes, E.

    1994-12-01

    The syngas reaction has been studied using a laterite iron mineral, promoted with K and Mn. In situ activation under syngas, as well as pre-treatment with H2 followed by CO under mild and more severe conditions were tested. These activation procedures led to different iron phase compositions and to different catalytic selectivities. The C2-C4/CH4 ratio was significantly lower for those catalysts which after reaction showed the presence of hexagonal carbide and magnetite compared to the solid, which showed the highest proportion of Hägg carbide.

  3. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    PubMed Central

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity. PMID:23539324

  4. Alkene metathesis: the search for better catalysts.

    PubMed

    Deshmukh, Prashant H; Blechert, Siegfried

    2007-06-28

    Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

  5. Antioxidant, antimicrobial and antiproliferative activities of five lichen species.

    PubMed

    Mitrović, Tatjana; Stamenković, Slaviša; Cvetković, Vladimir; Tošić, Svetlana; Stanković, Milan; Radojević, Ivana; Stefanović, Olgica; Comić, Ljiljana; Dačić, Dragana; Curčić, Milena; Marković, Snežana

    2011-01-01

    The antioxidative, antimicrobial and antiproliferative potentials of the methanol extracts of the lichen species Parmelia sulcata, Flavoparmelia caperata, Evernia prunastri, Hypogymnia physodes and Cladonia foliacea were evaluated. The total phenolic content of the tested extracts varied from 78.12 to 141.59 mg of gallic acid equivalent (GA)/g of extract and the total flavonoid content from 20.14 to 44.43 mg of rutin equivalent (Ru)/g of extract. The antioxidant capacities of the lichen extracts were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals scavenging. Hypogymnia physodes with the highest phenolic content showed the strongest DPPH radical scavenging effect. Further, the antimicrobial potential of the lichen extracts was determined by a microdilution method on 29 microorganisms, including 15 strains of bacteria, 10 species of filamentous fungi and 4 yeast species. A high antimicrobial activity of all the tested extracts was observed with more potent inhibitory effects on the growth of Gram (+) bacteria. The highest antimicrobial activity among lichens was demonstrated by Hypogymnia physodes and Cladonia foliacea. Finally, the antiproliferative activity of the lichen extracts was explored on the colon cancer adenocarcinoma cell line HCT-116 by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) viability assay and acridine orange/ethidium bromide staining. The methanol extracts of Hypogymnia physodes and Cladonia foliacea showed a better cytotoxic activity than the other extracts. All lichen species showed the ability to induce apoptosis of HCT-116 cells.

  6. [L-lysine-alpha-oxidase activity of some Trichoderma species].

    PubMed

    Smirnova, I P; Khaduev, S Kh

    1984-01-01

    Trichoderma cultures were tested for their ability to produce L-lysine-alpha-oxidase. The highest enzyme activity was manifested by T. harzianum (MGU), T. longibrachiatum Rifai VKM F-2025 and T. aureoviride Rifai VKM F-2026. The biosynthesis of the enzyme did not depend on the growth of the cultures and did not vary among the species.

  7. Antioxidant, Antimicrobial and Antiproliferative Activities of Five Lichen Species

    PubMed Central

    Mitrović, Tatjana; Stamenković, Slaviša; Cvetković, Vladimir; Tošić, Svetlana; Stanković, Milan; Radojević, Ivana; Stefanović, Olgica; Čomić, Ljiljana; Đačić, Dragana; Ćurčić, Milena; Marković, Snežana

    2011-01-01

    The antioxidative, antimicrobial and antiproliferative potentials of the methanol extracts of the lichen species Parmelia sulcata, Flavoparmelia caperata, Evernia prunastri, Hypogymnia physodes and Cladonia foliacea were evaluated. The total phenolic content of the tested extracts varied from 78.12 to 141.59 mg of gallic acid equivalent (GA)/g of extract and the total flavonoid content from 20.14 to 44.43 mg of rutin equivalent (Ru)/g of extract. The antioxidant capacities of the lichen extracts were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals scavenging. Hypogymnia physodes with the highest phenolic content showed the strongest DPPH radical scavenging effect. Further, the antimicrobial potential of the lichen extracts was determined by a microdilution method on 29 microorganisms, including 15 strains of bacteria, 10 species of filamentous fungi and 4 yeast species. A high antimicrobial activity of all the tested extracts was observed with more potent inhibitory effects on the growth of Gram (+) bacteria. The highest antimicrobial activity among lichens was demonstrated by Hypogymnia physodes and Cladonia foliacea. Finally, the antiproliferative activity of the lichen extracts was explored on the colon cancer adenocarcinoma cell line HCT-116 by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) viability assay and acridine orange/ethidium bromide staining. The methanol extracts of Hypogymnia physodes and Cladonia foliacea showed a better cytotoxic activity than the other extracts. All lichen species showed the ability to induce apoptosis of HCT-116 cells. PMID:21954369

  8. Metabolomic profiling and antioxidant activity of some Acacia species

    PubMed Central

    Abdel-Farid, I.B.; Sheded, M.G.; Mohamed, E.A.

    2014-01-01

    Metabolomic profiling of different parts (leaves, flowers and pods) of Acacia species (Acacia nilotica, Acacia seyal and Acacia laeta) was evaluated. The multivariate data analyses such as principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA) were used to differentiate the distribution of plant metabolites among different species or different organs of the same species. A.nilotica was characterized with a high content of saponins and A.seyal was characterized with high contents of proteins, phenolics, flavonoids and anthocyanins. A.laeta had a higher content of carbohydrates than A. nilotica and A. seyal. On the basis of these results, total antioxidant capacity, DPPH free radical scavenging activity and reducing power of the methanolic extracts of studied parts were evaluated. A.nilotica and A.seyal extracts showed less inhibitory concentration 50 (IC50) compared to A.laeta extracts which means that these two species have the strongest radical scavenging activity whereas A. laeta extracts have the lowest radical scavenging activity. A positive correlation between saponins and flavonoids with total antioxidant capacity and DPPH radical scavenging activity was observed. Based on these results, the potentiality of these plants as antioxidants was discussed. PMID:25313274

  9. Nickel phosphide nanoparticles-nitrogen-doped graphene hybrid as an efficient catalyst for enhanced hydrogen evolution activity

    NASA Astrophysics Data System (ADS)

    Pan, Yuan; Yang, Na; Chen, Yinjuan; Lin, Yan; Li, Yanpeng; Liu, Yunqi; Liu, Chenguang

    2015-11-01

    Development of hybrid catalysts with high activity, good stability and low cost is extremely desirable for hydrogen production by electrolysis of water. In this work, a hybrid composed of Ni2P nanoparticles (NPs) on N-doped reduced graphene oxide (NRGO) is synthesized via an in situ thermal decomposition approach for the first time and investigated as a catalyst for the hydrogen evolution reaction (HER). The as-synthesized Ni2P/NRGO hybrid exhibits an enhanced catalytic activity with low onset overpotential (37 mV), a small Tafel slope (59 mV dec-1), a much larger exchange current density (4.9 × 10-5 A cm-2), and lower HER activation energy (46.9 kJ mol-1) than Ni2P/RGO hybrid. In addition, the Ni2P/NRGO hybrid maintains its catalytic activity for at least 60‧000 s in acidic media. The enhanced catalytic activity is attributed to the synergistic effect of N-doped RGO and Ni2P NPs, the charged natures of Ni and P, as well as the high electrical conductivity of Ni2P/NRGO hybrid. This study may offer a new strategy for improving the electrocatalytic activity for hydrogen production.

  10. Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction

    SciTech Connect

    Kandel, Kapil; Althaus, Stacey M; Peeraphatdit, Chorthip; Kobayashi, Takeshi; Trewyn, Brian G; Pruski, Marek; Slowing, Igor I

    2013-01-11

    The relative rates of the aldol reaction catalyzed by supported primary and secondary amines can be inverted by 2 orders of magnitude, depending on the use of hexane or water as a solvent. Our analyses suggest that this dramatic shift in the catalytic behavior of the supported amines does not involve differences in reaction mechanism, but is caused by activation of imine to enamine equilibria and stabilization of iminium species. The effects of solvent polarity and acidity were found to be important to the performance of the catalytic reaction. This study highlights the critical role of solvent in multicomponent heterogeneous catalytic processes.

  11. Removal performance and mechanism of ibuprofen from water by catalytic ozonation using sludge-corncob activated carbon as catalyst.

    PubMed

    Wang, Hongjuan; Zhang, Liqiu; Qi, Fei; Wang, Xue; Li, Lu; Feng, Li

    2014-09-01

    To discover the catalytic activity of sludge-corncob activated carbon in catalytic ozonation of Ibuprofen, the performance of sludge-corncob activated carbon and three selected commercial activated carbons as catalysts in catalytic ozonation was investigated. The observation indicates the degradation rate of Ibuprofen increases significantly in the presence of sludge-corncob activated carbon and the catalytic activity of sludge-corncob activated carbon is much higher than that of the other three commercial activated carbons. Ibuprofen's removal rate follows pseudo-first order kinetics model well. It is also found that the adsorption removal of Ibuprofen by sludge-corncob activated carbon is less than 30% after 40 min. And the removal efficiency of Ibuprofen in the hybrid ozone/sludge-corncob activated carbon system is higher than the sum of sludge-corncob activated carbon adsorption and ozonation alone, which is a supportive evidence for catalytic reaction. In addition, the results of radical scavenger experiments demonstrate that catalytic ozonation of Ibuprofen by sludge-corncob activated carbon follows a hydroxyl radical reaction pathway. During ozonation of Ibuprofen in the presence of activated carbon, ozone could be catalytically decomposed to form hydrogen peroxide, which can promote the formation of hydroxyl radical. The maximum amount of hydrogen peroxide occurs in the presence of sludge-corncob activated carbon, which can explain why sludge-corncob activated carbon has the best catalytic activity among four different activated carbons.

  12. Iron(II) Active Species in Iron-Bisphosphine Catalyzed Kumada and Suzuki-Miyaura Cross-Couplings of Phenyl Nucleophiles and Secondary Alkyl Halides.

    PubMed

    Daifuku, Stephanie L; Kneebone, Jared L; Snyder, Benjamin E R; Neidig, Michael L

    2015-09-09

    While previous studies have identified FeMes2(SciOPP) as the active catalyst species in iron-SciOPP catalyzed Kumada cross-coupling of mesitylmagnesium bromide and primary alkyl halides, the active catalyst species in cross-couplings with phenyl nucleophiles, where low valent iron species might be prevalent due to accessible reductive elimination pathways, remains undefined. In the present study, in situ Mössbauer and magnetic circular dichroism spectroscopic studies combined with inorganic syntheses and reaction studies are employed to evaluate the in situ formed iron species and identify the active catalytic species in iron-SciOPP catalyzed Suzuki-Miyaura and Kumada cross-couplings of phenyl nucleophiles and secondary alkyl halides. While reductive elimination to form Fe(η(6)-biphenyl)(SciOPP) occurs upon reaction of FeCl2(SciOPP) with phenyl nucleophiles, this iron(0) species is not found to be kinetically competent for catalysis. Importantly, mono- and bis-phenylated iron(II)-SciOPP species that form prior to reductive elimination are identified, where both species are found to be reactive toward electrophile at catalytically relevant rates. The higher selectivity toward the formation of cross-coupled product observed for the monophenylated species combined with the undertransmetalated nature of the in situ iron species in both Kumada and Suzuki-Miyaura reactions indicates that Fe(Ph)X(SciOPP) (X = Br, Cl) is the predominant reactive species in cross-coupling. Overall, these studies demonstrate that low-valent iron is not required for the generation of highly reactive species for effective aryl-alkyl cross-couplings.

  13. ZSM-5 catalyst developed for toluene disproportionation

    SciTech Connect

    Han, S.; Shihabi, D.S. ); Absil, R.P.L.; Huang, Y.Y.; Leiby, S.M.; Marler, D.O.; McWilliams, J.P. )

    1989-08-21

    Toluene disproportionation over a new ZSM-5 catalyst formulation shows better activity and stability compared to the current Mobil Toluene disproportionation (MTDP) catalyst. Subsequent adiabatic pilot plant operations confirmed the activity and stability of the new catalyst. This process flexibility is expected to translate into considerable economic advantages for the process using the new catalyst formulation.

  14. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    PubMed

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

  15. Optimization of Cu/activated carbon catalyst in low temperature selective catalytic reduction of NO process using response surface methodology.

    PubMed

    Amanpour, Javad; Salari, Dariush; Niaei, Aligholi; Mousavi, Seyed Mahdi; Panahi, Parvaneh Nakhostin

    2013-01-01

    Preparation of Cu/Activated Carbon (Cu/AC) catalyst was optimized for low temperature selective catalytic reduction of NO by using response surface methodology. A central composite design (CCD) was used to investigate the effects of three independent variables, namely pre-oxidization degree (HNO3%), Cu loading (wt.%) and calcination temperature on NO conversion efficiency. The CCD was consisted of 20 different preparation conditions of Cu/AC catalysts. The prepared catalysts were characterized by XRD and SEM techniques. Predicting NO conversion was carried out using a second order model obtained from designed experiments and statistical software Minitab 14. Regression and Pareto graphic analysis showed that all of the chosen parameters and some interactions were effective on the NO conversion. The optimal values were pre-oxidization in 10.2% HNO3, 6.1 wt.% Cu loading and 480°C for calcination temperature. Under the optimum condition, NO conversion (94.3%) was in a good agreement with predicted value (96.12%).

  16. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    DOE PAGES

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

  17. Combination of photocatalysis and HC/SCR for improved activity and durability of DeNOx catalysts.

    PubMed

    Heo, Iljeong; Kim, Mun Kyu; Sung, Samkyung; Nam, In-Sik; Cho, Byong K; Olson, Keith L; Li, Wei

    2013-04-16

    A photocatalytic HC/SCR system has been developed and its high deNOx performance (54.0-98.6% NOx conversion) at low temperatures (150-250 °C) demonstrated by using a representative diesel fuel hydrocarbon (dodecane) as the reductant over a hybrid SCR system of a photocatalytic reactor (PCR) and a dual-bed HC/SCR reactor. The PCR generates highly active oxidants such as O3 and NO2 from O2 and NO in the feed stream, followed by the subsequent formation of highly efficient reductants such as oxygenated hydrocarbon (OHC), NH3, and organo-nitrogen compounds. These reductants are the key components for enhancing the low temperature deNOx performance of the dual-bed HC/SCR system containing Ag/Al2O3 and CuCoY in the front and rear bed of the reactor, respectively. The OHCs are particularly effective for both NOx reduction and NH3 formation over the Ag/Al2O3 catalyst, while NH3 and organo-nitrogen compounds are effective for NOx reduction over the CuCoY catalyst. The hybrid HC/SCR system assisted by photocatalysis has shown an overall deNOx performance comparable to that of the NH3/SCR, demonstrating its potential as a promising alternative to the current urea/SCR and LNT technologies. Superior durability of HC/SCR catalysts against coking by HCs has also been demonstrated by a PCR-assisted regeneration scheme for deactivating catalysts.

  18. Activation mechanism of Gi and Go by reactive oxygen species.

    PubMed

    Nishida, Motohiro; Schey, Kevin L; Takagahara, Shuichi; Kontani, Kenji; Katada, Toshiaki; Urano, Yasuteru; Nagano, Tetsuo; Nagao, Taku; Kurose, Hitoshi

    2002-03-15

    Reactive oxygen species are proposed to work as intracellular mediators. One of their target proteins is the alpha subunit of heterotrimeric GTP-binding proteins (Galpha(i) and Galpha(o)), leading to activation. H(2)O(2) is one of the reactive oxygen species and activates purified Galpha(i2). However, the activation requires the presence of Fe(2+), suggesting that H(2)O(2) is converted to more reactive species such as c*OH. The analysis with mass spectrometry shows that seven cysteine residues (Cys(66), Cys(112), Cys(140), Cys(255), Cys(287), Cys(326), and Cys(352)) of Galpha(i2) are modified by the treatment with *OH. Among these cysteine residues, Cys(66), Cys(112), Cys(140), Cys(255), and Cys(352) are not involved in *OH-induced activation of Galpha(i2). Although the modification of Cys(287) but not Cys(326) is required for subunit dissociation, the modification of both Cys(287) and Cys(326) is necessary for the activation of Galpha(i2) as determined by pertussis toxin-catalyzed ADP-ribosylation, conformation-dependent change of trypsin digestion pattern or guanosine 5'-3-O-(thio)triphosphate binding. Wild type Galpha(i2) but not Cys(287)- or Cys(326)-substituted mutants are activated by UV light, singlet oxygen, superoxide anion, and nitric oxide, indicating that these oxidative stresses activate Galpha(i2) by the mechanism similar to *OH-induced activation. Because Cys(287) exists only in G(i) family, this study explains the selective activation of G(i)/G(o) by oxidative stresses.

  19. In vitro antioxidant and antiproliferative activities of nine Salvia species.

    PubMed

    Loizzo, Monica Rosa; Abouali, Morteza; Salehi, Peyman; Sonboli, Ali; Kanani, Mohammad; Menichini, Francesco; Tundis, Rosa

    2014-01-01

    Supported by a growing increase of scientific research attesting the health properties of salvia species, we have decided to investigate nine Salvia namely Salvia sclarea, Salvia atropatana, Salvia sahendica, Salvia hydrangea, Salvia xanthocheila, Salvia macrosiphon, Salvia glutinosa, Salvia chloroleuca and Salvia ceratophylla species for their antioxidant and antiproliferative activities. In order to correlate the bioactivity with their phytochemical content, the total phenol and total flavonoid contents were also determined. S. ceratophylla exhibited the strongest activity against C32 cells with an IC50 value of 20.8 μg mL(- 1), while S. glutinosa exhibited an IC50 value of 29.5 μg mL(- 1) against ACHN cell line. Interestingly, S. glutinosa displayed also the highest DPPH radical-scavenging activity with an IC50 of 3.2 μg mL(- 1). These species are characterised by the highest total phenol and flavonoid contents. The obtained results suggest that Salvia species are healthy plant foods.

  20. Methyl chloride production from methane over lanthanum-based catalysts.

    PubMed

    Podkolzin, Simon G; Stangland, Eric E; Jones, Mark E; Peringer, Elvira; Lercher, Johannes A

    2007-03-07

    The mechanism of selective production of methyl chloride by a reaction of methane, hydrogen chloride, and oxygen over lanthanum-based catalysts was studied. The results suggest that methane activation proceeds through oxidation-reduction reactions on the surface of catalysts with an irreducible metal-lanthanum, which is significantly different from known mechanisms for oxidative chlorination. Activity and spectroscopic measurements show that lanthanum oxychloride (LaOCl), lanthanum trichloride (LaCl3), and lanthanum phases with an intermediate extent of chlorination are all active for this reaction. The catalyst is stable with no noticeable deactivation after three weeks of testing. Kinetic measurements suggest that methane activation proceeds on the surface of the catalyst. Flow and pulse experiments indicate that the presence of hydrogen chloride is not required for activity, and its role appears to be limited to maintaining the extent of catalyst chlorination. In contrast, the presence of gas-phase oxygen is essential for catalytic activity. Density-functional theory calculations suggest that oxygen can activate surface chlorine species by adsorbing dissociatively and forming OCl surface species, which can serve as an active site for methane activation. The proposed mechanism, thus, involves changing of the formal oxidation state of surface chlorine from -1 to +1 without any changes in the oxidation state of the underlying metal.

  1. Radical scavenging, antioxidant and antimicrobial activities of halophytic species.

    PubMed

    Meot-Duros, Laetitia; Le Floch, Gaëtan; Magné, Christian

    2008-03-05

    For the first time, both antioxidant and antimicrobial activities are simultaneously reported in halophytic plants, particularly on polar fractions. Chloroformic and methanolic extracts of the halophytes Eryngium maritimum L., Crithmum maritimum L. and Cakile maritima Scop. were tested for their antimicrobial activities against 12 bacterial and yeast strains. In addition, radical scavenging and antioxidant activities were assessed, as well as total phenol contents. Only one bacterial strain (Listeria monocytogenes) was not inhibited by plants extracts, and apolar (chloroformic) fractions were generally more active than polar (methanolic) ones. Eryngium maritimum presented the weakest radical scavenging activity (ABTS IC(50)=0.28 mg ml(-1)), as well as the lowest total phenol content (16.4 mg GAE g(-1) DW). However, the three halophytic species had relatively strong total antioxidant activities (from 32.7 to 48.6 mg ascorbate equivalents g (-1) DW). Consequences on the potential use of these plants in food or cosmetic industry are discussed.

  2. Mo-Fe catalysts supported on activated carbon for synthesis of liquid fuels by the Fischer-Tropsch process: effect of Mo addition on reducibility, activity, and hydrocarbon selectivity

    SciTech Connect

    Wenping Ma; Edwin L. Kugler; James Wright; Dady B. Dadyburjor

    2006-12-15

    The effects of Mo loading (0-12 wt %) on the properties of activated-carbon- (AC-) supported Fe-Cu-K catalysts and their performance for Fischer-Tropsch synthesis are studied. Physicochemical properties studied include particle size, reducibility, and dispersion, and catalytic properties include activity, selectivity, and stability. Catalysts were characterized by N{sub 2} adsorption, energy-dispersive spectroscopy, X-ray diffraction (XRD), H{sub 2} temperature-programmed reduction (TPR), and CO chemisorption. Catalyst performance was studied at 310-320{sup o}C, 2.2 MPa, 3 Nl/g-cat/h, and H{sub 2}/CO = 0.9. Reaction results in a fixed-bed reactor show that addition of 6% Mo into the Fe-Cu-K/AC catalyst improves catalyst stability without sacrificing activity, but activity is suppressed dramatically on a 12% Mo-loaded catalyst. Detectable hydrocarbons of C{sub 1} to C{sub 34} are produced on the Fe-Cu-K/AC catalysts with or without Mo. However, the addition of Mo results in the production of more CH{sub 4} and less C{sub 5+} hydrocarbons. The Mo promoter greatly enhances secondary reactions of olefins, leading to a large amount of internal olefins (i.e., other than 1-olefins) in the product. TPR shows that a strong interaction between Fe and Mo oxides is present, and the extent of reduction of Fe is suppressed after addition of Mo to the Fe-Cu-K catalyst. CO-chemisorption and XRD studies show increased iron dispersion and decreased particle size of the iron carbide and iron oxide after the addition of Mo. Segregation of iron active sites, thereby preventing them from agglomerating, and a larger number of active sites on the 6% Mo catalyst are possible reasons for the improved stability and higher activity of Mo-promoted catalysts. 54 refs., 5 figs., 6 tabs.

  3. Process of making supported catalyst

    DOEpatents

    Schwarz, James A.; Subramanian, Somasundaram

    1992-01-01

    Oxide supported metal catalysts have an additional metal present in intimate association with the metal catalyst to enhance catalytic activity. In a preferred mode, iridium or another Group VIII metal catalyst is supported on a titania, alumina, tungsten oxide, silica, or composite oxide support. Aluminum ions are readsorbed onto the support and catalyst, and reduced during calcination. The aluminum can be added as aluminum nitrate to the iridium impregnate solution, e.g. chloroiridic acid.

  4. Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

    NASA Astrophysics Data System (ADS)

    Dade, William N.

    Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

  5. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

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

  6. Crystalline titanate catalyst supports

    DOEpatents

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

    1993-01-05

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

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

    DOEpatents

    Wickham, David; Cook, Ronald

    2008-10-28

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

  8. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCox Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

    PubMed Central

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M.; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E.; Mukerjee, Sanjeev

    2015-01-01

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling. PMID:26413384

  9. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

    PubMed

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E; Mukerjee, Sanjeev

    2015-01-02

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt-Pt and Pt-Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.

  10. Improving Morphological Quality and Uniformity of Hydrothermally Grown ZnO Nanowires by Surface Activation of Catalyst Layer

    NASA Astrophysics Data System (ADS)

    Murillo, Gonzalo; Lozano, Helena; Cases-Utrera, Joana; Lee, Minbaek; Esteve, Jaume

    2017-01-01

    This paper presents a study about the dependence of the hydrothermal growth of ZnO nanowires (NWs) with the passivation level of the active surface of the Au catalyst layer. The hydrothermal method has many potential applications because of its low processing temperature, feasibility, and low cost. However, when a gold thin film is utilized as the seed material, the grown NWs often lack morphological homogeneity; their distribution is not uniform and the reproducibility of the growth is low. We hypothesize that the state or condition of the active surface of the Au catalyst layer has a critical effect on the uniformity of the NWs. Inspired by traditional electrochemistry experiments, in which Au electrodes are typically activated before the measurements, we demonstrate that such activation is a simple way to effectively assist and enhance NW growth. In addition, several cleaning processes are examined to find one that yields NWs with optimal quality, density, and vertical alignment. We find cyclic voltammetry measurements to be a reliable indicator of the seed-layer quality for subsequent NW growth. Therefore, we propose the use of this technique as a standard procedure prior to the hydrothermal synthesis of ZnO NWs to control the growth reproducibility and to allow high-yield wafer-level processing.

  11. Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272.

    PubMed

    Park, Kyung Ho; Mohapatra, Debasish; Nam, Chul-Woo

    2007-09-05

    Spent catalyst generally contains valuable metals like Mo, Co, Ni on a supporting material, such as gamma-A1(2)O(3). In the present study, a two stage alkali/acid leaching process is proposed to selectively target molybdenum and cobalt/nickel separately to facilitate the downstream processing. Prior to the leaching, the spent catalyst was calcined at 500 degrees C to remove C and S; and to convert metal sulphides to metal oxides. 98% Mo, 93% Co and 90% Ni was effectively recovered by this process. The sulphuric acid leaching of spent catalyst, previously treated by alkali solutions to remove Mo, yielded a solution rich in Ni, Co and Al. In order to recover Co and Ni, the Al impurity must be eliminated. The extraction and stripping of Al has been carried out using the organo-phosphinic extractant, Cyanex 272 diluted in carbon tetrachloride. Quantitative Al extraction efficiency was achieved with 1.0M Cyanex 272 in two stages at an aqueous:organic (A:O) phase ratio of 1:1 and equilibrium pH of 3.2. Complete stripping of Al from the loaded organic was carried out using 2M H(2)SO(4) at an A:O phase ratio of 1:1. The extraction reaction proceeded via the cation exchange mechanism and the extracted species was assumed to be AlA(3).3HA. The extraction of Al was carried out in the pr