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Sample records for oxygen reduction catalyzed

  1. Cathodic oxygen reduction catalyzed by bacteria in microbial fuel cells.

    PubMed

    Rabaey, Korneel; Read, Suzanne T; Clauwaert, Peter; Freguia, Stefano; Bond, Philip L; Blackall, Linda L; Keller, Jurg

    2008-05-01

    Microbial fuel cells (MFCs) have the potential to combine wastewater treatment efficiency with energetic efficiency. One of the major impediments to MFC implementation is the operation of the cathode compartment, as it employs environmentally unfriendly catalysts such as platinum. As recently shown, bacteria can facilitate sustainable and cost-effective cathode catalysis for nitrate and also oxygen. Here we describe a carbon cathode open to the air, on which attached bacteria catalyzed oxygen reduction. The bacteria present were able to reduce oxygen as the ultimate electron acceptor using electrons provided by the solid-phase cathode. Current densities of up to 2.2 A m(-2) cathode projected surface were obtained (0.303+/-0.017 W m(-2), 15 W m(-3) total reactor volume). The cathodic microbial community was dominated by Sphingobacterium, Acinetobacter and Acidovorax sp., according to 16S rRNA gene clone library analysis. Isolates of Sphingobacterium sp. and Acinetobacter sp. were obtained using H(2)/O(2) mixtures. Some of the pure culture isolates obtained from the cathode showed an increase in the power output of up to three-fold compared to a non-inoculated control, that is, from 0.015+/-0.001 to 0.049+/-0.025 W m(-2) cathode projected surface. The strong decrease in activation losses indicates that bacteria function as true catalysts for oxygen reduction. Owing to the high overpotential for non-catalyzed reduction, oxygen is only to a limited extent competitive toward the electron donor, that is, the cathode. Further research to refine the operational parameters and increase the current density by modifying the electrode surface and elucidating the bacterial metabolism is warranted. PMID:18288216

  2. Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets

    NASA Astrophysics Data System (ADS)

    Wang, Qiannan; Wang, Likai; Tang, Zhenghua; Wang, Fucai; Yan, Wei; Yang, Hongyu; Zhou, Weijia; Li, Ligui; Kang, Xiongwu; Chen, Shaowei

    2016-03-01

    Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-visible absorption spectroscopy, thermogravimetric analysis and BET nitrogen adsorption/desorption. Electrochemical studies showed that the composites demonstrated apparent ORR activity in alkaline media, and the sample with a 30% Au mass loading was identified as the best catalyst among the series, with a performance comparable to that of commercial Pt/C, but superior to those of Au102 nanoclusters and carbon nanosheets alone, within the context of onset potential, kinetic current density, and durability. The results suggest an effective approach to the preparation of high-performance ORR catalysts based on gold nanoclusters supported on carbon nanosheets.Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as

  3. Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets.

    PubMed

    Wang, Qiannan; Wang, Likai; Tang, Zhenghua; Wang, Fucai; Yan, Wei; Yang, Hongyu; Zhou, Weijia; Li, Ligui; Kang, Xiongwu; Chen, Shaowei

    2016-03-28

    Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-visible absorption spectroscopy, thermogravimetric analysis and BET nitrogen adsorption/desorption. Electrochemical studies showed that the composites demonstrated apparent ORR activity in alkaline media, and the sample with a 30% Au mass loading was identified as the best catalyst among the series, with a performance comparable to that of commercial Pt/C, but superior to those of Au102 nanoclusters and carbon nanosheets alone, within the context of onset potential, kinetic current density, and durability. The results suggest an effective approach to the preparation of high-performance ORR catalysts based on gold nanoclusters supported on carbon nanosheets. PMID:26940367

  4. Studies on the electrochemical reduction of oxygen catalyzed by reduced graphene sheets in neutral media

    NASA Astrophysics Data System (ADS)

    Wu, Jiajia; Wang, Yi; Zhang, Dun; Hou, Baorong

    Reduced graphene sheets (RGSs) were prepared via chemical reduction of graphite oxide and their morphology was characterized by atomic force microscopy. The electrochemical reduction of oxygen (O 2) with RGSs was studied by cyclic, rotating disk electrode, and rotating ring-disk electrode voltammetry using the RGSs-modified glassy carbon (RGSs/GC) electrode in 3.5% NaCl solution. The results show that O 2 reduction undergoes three steps at the RGSs/GC electrode: electrochemical reduction of O 2 to H 2O 2 mediated by quinone-like groups on the RGSs surface, a direct 2-electron reduction of O 2, and reduction of the H 2O 2 produced to H 2O. The modification of RGSs results in an obvious positive shift of the peak potential and a larger current density. The kinetics study shows that the number of electrons transferred for O 2 reduction can reach to 3.0 at potentials of the first reduction step, indicating RGSs can effectively catalyze the disproportionation of H 2O 2. Such catalytic activity of RGSs enables a 4-electron reduction of O 2 at a relatively low overpotential in neutral media. RGSs are a potential electrode material for microbial fuel cells.

  5. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles

    PubMed Central

    Dumitrescu, Ioana; Crooks, Richard M.

    2012-01-01

    Here we report on the effect of the mass transfer rate (kt) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt147 and Pt55). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high kt conditions with simultaneous detection of H2O2. At low kt (0.02 to 0.12 cm s-1) the effective number of electrons involved in ORR, neff, is 3.7 for Pt147 and 3.4 for Pt55. As kt is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H2O2 detected remains constant, such that neff barely changes over the entire kt range explored (0.02 cm s-1). This suggests that mass transfer does not affect neff, which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in neff for the two sizes of Pt DENs (neff = 3.7 and 3.5 for Pt147 and Pt55, respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  6. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    PubMed

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  7. Inhibitory effect of water on the oxygen reduction catalyzed by cobalt(II) tetraphenylporphyrin.

    PubMed

    Trojánek, Antonín; Langmaier, Jan; Kvapilová, Hana; Záliš, Stanislav; Samec, Zdeněk

    2014-03-20

    Stopped-flow kinetic measurements, UV-vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O2 to H2O2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(pentafluorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21H,23H-porphine]cobalt(II) (Co(II)TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O2 molecule coordinated to the metal center producing the O2H(•) radical. This rate-determining step is common to both the O2 reduction by Fc catalyzed by Co(II)TPP and the O2 reduction by Co(II)TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2TPP), though its rate is lower by 2 orders of magnitude. PMID:24564521

  8. An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

    PubMed Central

    Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

    2008-01-01

    Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

  9. A lithium-air fuel cell using copper to catalyze oxygen-reduction based on copper-corrosion mechanism.

    PubMed

    Wang, Yonggang; Zhou, Haoshen

    2010-09-14

    The copper-catalyzed O(2) reduction in aqueous electrolyte and the Li-anode in organic electrolyte were united together by a ceramic Li-ions exchange film to form a lithium-air fuel cell. The achieved results demonstrate the cycle between Cu and Cu(2)O can be used to catalyze O(2) electrochemical reduction based on the copper-corrosion mechanism. PMID:20668776

  10. Reduction of the explosive 2,4,6-trinitrophenylmethylnitramine (tetryl) catalyzed by oxygen sensitive nitro reductase enzymes

    SciTech Connect

    Shah, M.M.; Spain, J.C.

    1995-12-01

    Reduction of nitroaromatic compounds by nitroreductase enzymes generally leads to the formation of the corresponding amines. However, we recently found that the incubation of the explosive 2,4,6-trinitrophenylmethylnitramine (tetryl) with ferredoxin-NADP oxidoreductase, an oxygen sensitive nitroreductase from spinach in the presence of NADPH led to the elimination of the nitramine nitro group from tetryl and the formation of N-methylpicramide (NMP). Other oxygen sensitive nitroreductase enzymes including glutathione reductase, xanthine oxidase, and cytochrome c reductase were also able to release nitrite from tetryl. Nitrite was not eliminated from tetryl by an oxygen insensitive nitrobenzene reductase. For every mole of tetryl reduced, one mole each of nitrite and NMP were produced. The rate of nitrite elimination was inhibited under aerobic conditions. Subsequent oxygen uptake studies suggested that under aerobic conditions, molecular oxygen was reduced by FNR and tetryl served as the redox mediator. Our results suggest that under aerobic conditions; tetryl is reduced to the nitroanion radical by the enzyme and this radical is involved in the reduction of molecular oxygen.

  11. Oxygen reduction reaction catalyzed by platinum nanonetwork prepared by template free one step synthesis for polymer electrolyte membrane fuel cells

    SciTech Connect

    Narayanamoorthy, B.; Kumar, B.V.V.S. Pavan; Eswaramoorthy, M.; Balaji, S.

    2014-07-01

    Highlights: • Supportless Pt nanonetwork (Pt NN) synthesized by novel template free one step method as per our earlier reported procedure. • Electrocatalytic activity of Pt NN studied taking oxygen reduction reaction in acid medium. • Kinetic and thermodynamic parameters were deduced under hydrodynamic conditions. • ORR mechanistic pathway was proposed based on kinetic rate constants. • ADT analysis found enhanced stability (5000 cycles) for Pt NN than Pt NN/VC and reported Pt/C. - Abstract: The reduction reaction of molecular oxygen (ORR) was investigated using supportless Pt nanonetwork (Pt NN) electrocatalyst in sulfuric acid medium. Pt NN was prepared by template free borohydride reduction. The transmission electron microscope images revealed a network like nano-architecture having an average cluster size of 30 nm. The electrochemical characterization of supportless and Vulcan carbon supported Pt NN (Pt NN/VC) was carried out using rotating disc and ring disc electrodes at various temperatures. Kinetic and thermodynamic parameters were estimated under hydrodynamic conditions and compared with Pt NN/VC and reported Pt/C catalysts. The accelerated durability test revealed that supportless Pt NN is quite stable for 5000 potential cycles with 22% reduction in electrochemical surface area (ECSA). While the initial limiting current density has in fact increased by 11.6%, whereas Pt NN/VC suffered nearly 55% loss in ECSA and 13% loss in limiting current density confirming an enhanced stability of supportless Pt NN morphology for ORR compared to conventional Pt/C ORR catalysts in acid medium.

  12. Nickel-Catalyzed Reductive Couplings.

    PubMed

    Wang, Xuan; Dai, Yijing; Gong, Hegui

    2016-08-01

    The Ni-catalyzed reductive coupling of alkyl/aryl with other electrophiles has evolved to be an important protocol for the construction of C-C bonds. This chapter first emphasizes the recent progress on the Ni-catalyzed alkylation, arylation/vinylation, and acylation of alkyl electrophiles. A brief overview of CO2 fixation is also addressed. The chemoselectivity between the electrophiles and the reactivity of the alkyl substrates will be detailed on the basis of different Ni-catalyzed conditions and mechanistic perspective. The asymmetric formation of C(sp(3))-C(sp(2)) bonds arising from activated alkyl halides is next depicted followed by allylic carbonylation. Finally, the coupling of aryl halides with other C(sp(2))-electrophiles is detailed at the end of this chapter. PMID:27573395

  13. Electrochemiluminescent quenching of quantum dots for ultrasensitive immunoassay through oxygen reduction catalyzed by nitrogen-doped graphene-supported hemin.

    PubMed

    Deng, Shengyuan; Lei, Jianping; Huang, Yin; Cheng, Yan; Ju, Huangxian

    2013-06-01

    A hemin functionalized graphene sheet was prepared via the noncovalent assembly of hemin on nitrogen-doped graphene. The graphene sheet could act as an oxygen reduction catalyst to produce sensitive electrochemiluminescent (ECL) quenching of quantum dots (QDs) due to the annihilation of dissolved oxygen, the ECL coreactant, by its electrocatalytic reduction. With the use of the catalyst with high loading of hemin as a signal tag of the secondary antibody, a novel ultrasensitive immunoassay method for biomarker detection was proposed. In an air-saturated pH 8.0 buffer, the immunosensor constructed by a stepwise immobilization of bidentate-chelated CdTe QDs and capture antibody showed an intensive cathodic ECL irradiation, which could be scavenged upon the formation of the catalyst-bound sandwich immunocomplex. With the use of the carcinoembryonic antigen as a model analyte, the immunoassay method showed a linear range from 0.1 pg mL(-1) to 10 ng mL(-1) and a detection limit of 24 fg mL(-1). The immunosensor exhibited good stability, acceptable fabrication reproducibility, and practicability. The electrocatalytic reduction-based ECL quenching strategy provided a powerful avenue for the design of the ultrasensitive detection method, showing great promise for clinical application. PMID:23659573

  14. Mechanisms of bacterially catalyzed reductive dehalogenation

    SciTech Connect

    Picardal, F.W.

    1992-12-31

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using {sup 14}C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  15. Palladium Catalyzed Reduction of Nitrobenzene.

    ERIC Educational Resources Information Center

    Mangravite, John A.

    1983-01-01

    Compares two palladium (Pd/C) reducing systems to iron/tin-hydrochloric acid (Fe/HCl and Sn/HCl) reductions and suggests an efficient, clean, and inexpensive procedures for the conversion of nitrobenzene to aniline. Includes laboratory procedures used and discussion of typical results obtained. (JN)

  16. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry

    NASA Astrophysics Data System (ADS)

    Wang, Jiong; Wang, Huai-Song; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-10-01

    In recent years, doped carbonaceous materials as alternative catalysts for oxygen reduction reaction (ORR) have received considerable attention due to the low cost and high CO tolerance capability. Different theoretical studies have suggested that oxygen is reduced in a rapid sequence intermediated by diverse oxygen-containing reactive intermediates (ORI). However, due to the short lifetimes of the possible ORI, direct experimental evidence is very difficult to be obtained. Here, we report the synthesis of an ultralight and porous nitrogen-doped graphene (NG) by annealing graphite oxide (GO)-melamine scaffold shaped in ice template. The resultant NG exhibits excellent electrocatalytic activity toward 4e-reduction of oxygen with the onset potential as low as -0.05 V vs. Ag/AgCl in alkaline media. Using this material as model study, sensitive in situ fluorescence spectroelectrochemistry is applied to demonstrate the presence the reactive ORI. The global ORR pathway is unraveled as stepwise electron transfer involving hydroxyl radical as the important intermediate via both inner- and outer-sphere process. This result would likely provide a new insight into the further understanding of ORR mechanism on those intrinsic carbonaceous materials.

  17. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry

    PubMed Central

    Wang, Jiong; Wang, Huai-Song; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-01-01

    In recent years, doped carbonaceous materials as alternative catalysts for oxygen reduction reaction (ORR) have received considerable attention due to the low cost and high CO tolerance capability. Different theoretical studies have suggested that oxygen is reduced in a rapid sequence intermediated by diverse oxygen-containing reactive intermediates (ORI). However, due to the short lifetimes of the possible ORI, direct experimental evidence is very difficult to be obtained. Here, we report the synthesis of an ultralight and porous nitrogen-doped graphene (NG) by annealing graphite oxide (GO)-melamine scaffold shaped in ice template. The resultant NG exhibits excellent electrocatalytic activity toward 4e-reduction of oxygen with the onset potential as low as −0.05 V vs. Ag/AgCl in alkaline media. Using this material as model study, sensitive in situ fluorescence spectroelectrochemistry is applied to demonstrate the presence the reactive ORI. The global ORR pathway is unraveled as stepwise electron transfer involving hydroxyl radical as the important intermediate via both inner- and outer-sphere process. This result would likely provide a new insight into the further understanding of ORR mechanism on those intrinsic carbonaceous materials. PMID:25335571

  18. O2 and H2O2 transformation steps for the oxygen reduction reaction catalyzed by graphitic nitrogen-doped carbon nanotubes in acidic electrolyte from first principles calculations.

    PubMed

    Li, Yuhang; Zhong, Guoyu; Yu, Hao; Wang, Hongjuan; Peng, Feng

    2015-09-14

    It is highly challenging but extremely desirable to develop carbon catalysts with high oxygen reduction reaction (ORR) activity and stability in acidic medium for commercial application. In this paper, based on density functional theory (DFT) calculations with long range interaction correction and solvation effects, the elementary transformations of all the probable intermediates in the ORR and the hydrogen peroxide reduction reaction (HPRR) over graphitic nitrogen-doped carbon nanotubes (NCNTs) in acidic medium were evaluated, and it was found that all the rate determining steps are related to the bonding hydroxyl group because of the strong interaction between the hydroxyl group and carbon. Thus, it is hard for the direct four-electron ORR and the two-electron HPRR to proceed. Together with hydrogen peroxide disproportionation (HPD), a mixed mechanism for the ORR in acidic electrolyte was proposed, where the two-electron and three-electron ORRs and HPD dominate the electrode reaction. The experimental result for the ORR catalyzed by NCNTs in acidic electrolyte also well illustrated the rationality of the theoretical calculations. This study not only gives new insights into the effect of graphitic nitrogen doping on the ORR catalyzed by carbon, but also provides a guide to design carbon catalysts with high ORR activity in acidic electrolyte. PMID:26234475

  19. Electrochemical reduction of oxygen and hydrogen peroxide catalyzed by a surface copper(II)-2,4,6-tris(2-piridil)-1,3,5-triazine complex adsorbed on a graphite electrode

    NASA Astrophysics Data System (ADS)

    Dias, Vera L. N.; Fernandes, Elizabeth N.; da Silva, Leila M. S.; Marques, Edmar P.; Zhang, Jiujun; Marques, Aldaléa L. Brandes

    A graphite electrode irreversibly adsorbed by 2,4,6-tris(2-piridil)-1,3,5-triazine (abbreviated as TPT) was examined by cyclic voltammetry. The adsorbed TPT exhibited two irreversible reduction waves in the potential range of -0.7 and -1.0 V (versus SCE). Upon strong adsorption, TPT can serve as a coordination ligand for copper ions to form a surface complex. Its three adjacent nitrogen positions provide strong affinity to the metal ions and bond copper(II) to an electrode surface. A 1:1 coordination between Cu(II) or Cu(I) and the TPT ligand to form [Cu(II)(TPT)] 2+ or [Cu(I)(TPT)] + is the predominant process, evidenced by spectrophotometry, surface cyclic voltammetry, and coordinated structural feasibility of Cu(II)/Cu(I)-TPT complexes. The predominant copper(II)-TPT surface complex shows a reversible redox wave, which is identified as one-electron process of [Cu(II)(TPT)] 2+ ↔ [Cu(I)(TPT)] +. The electrode adsorbed by [Cu(II)(TPT)] 2+ complex showed electrocatalytic activity towards oxygen and/or hydrogen peroxide reductions. The catalyzed reduction of oxygen and hydrogen peroxide were identified as four-electron and two-electron process to form water. It is suggested that the possible electrocatalytic reductions were due to an inner-sphere mechanism, which involved a coordination between substrate (O 2 or H 2O 2) and [Cu(I)(TPT)] +. The reduction kinetics were also investigated by a rotating disk electrode method.

  20. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    DOE PAGESBeta

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 Vmore » (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.« less

  1. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    SciTech Connect

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 V (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.

  2. High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

    2016-09-01

    Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

  3. Titanium Catalyzed Perchlorate Reduction and Applications

    SciTech Connect

    Gu, Baohua; Bonnesen, Peter V; Sloop Jr, Frederick {Fred} V; Brown, Gilbert M

    2006-01-01

    This work provides a proof-of-principle demonstration that Ti(III)-catalyzed electrochemical techniques could potentially be used for reduction of ClO{sub 4}{sup -} in small waste streams, such as the regeneration of selective anion-exchange resins that are loaded with ClO{sub 4}{sup -}. The technique may not be directly applied for the treatment of large volumes of ClO{sub 4}{sup -}-contaminated water at relatively low concentrations because of its slow reaction kinetics and the use of chemical reagents. Further studies are needed to optimize the reaction conditions in order to achieve a complete reduction of ClO{sub 4}{sup -} and the regeneration of spent resin beds. Alternative complexing and reducing agents may be used to enhance the reaction completeness of sorbed ClO{sub 4}{sup -} in the resin and to overcome potential clogging of micropores within the resin beads resulting from the precipitation of TiO{sub 2}.

  4. Electrocatalyst for oxygen reduction

    NASA Technical Reports Server (NTRS)

    Swette, L. L. (Inventor)

    1971-01-01

    The performance and costs of an electrochemical catalyst as compared to a pure platinum catalyst is evaluated. The catalysts are used to reduce oxygen in low temperature alkaline fuel cells. The electrochemical catalyst is composed of silver and platinum and is dispersed in a resinous inert binder to provide a cell electrode. The results indicate the electrochemical catalyst is superior structurally to the platinum one for high current density operation, and is at least as active as the platinum catalyst in other operations.

  5. Catalyzed reduction of nitrate in aqueous solutions

    SciTech Connect

    Haas, P.A.

    1994-08-01

    Sodium nitrate and other nitrate salts in wastes is a major source of difficulty for permanent disposal. Reduction of nitrate using aluminum metal has been demonstrated, but NH{sub 3}, hydrazine, or organic compounds containing oxygen would be advantageous for reduction of nitrate in sodium nitrate solutions. Objective of this seed money study was to determine minimum conditions for reduction. Proposed procedure was batchwise heating of aqueous solutions in closed vessels with monitoring of temperatures and pressures. A simple, convenient apparatus and procedure were demonstrated for observing formation of gaseous products and collecting samples for analyses. The test conditions were 250{degree}C and 1000 psi max. Any useful reduction of sodium nitrate to sodium hydroxide as the primary product was not found. The nitrate present at pHs < 4 as HNO{sub 3} or NH{sub 4}NO{sub 3} is easily decomposed, and the effect of nitromethane at these low pHs was confirmed. When acetic acid or formic acid was added, 21 to 56% of the nitrate in sodium nitrate solutions was reduced by methanol or formaldehyde. With hydrazine and acetic acid, 73 % of the nitrate was decomposed to convert NaNO{sub 3} to sodium acetate. With hydrazine and formic acid, 36% of the nitrate was decomposed. If these products are more acceptable for final disposal than sodium nitrate, the reagents are cheap and the conversion conditions would be practical for easy use. Ammonium acetate or formate salts did not significantly reduce nitrate in sodium nitrate solutions.

  6. Nanoparticulate-catalyzed oxygen transfer processes

    DOEpatents

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

    Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

  7. Cu(II) - Catalyzed Hydrazine Reduction of Ferrous Nitrate

    SciTech Connect

    Karraker, D.G.

    2001-10-15

    This report discusses the results of a study of catalyzed hydrazine reduction of ferrous nitrate. It is apparent that there is a substantial reaction between hydrazine and nitrate ion (or nitric acid) to produce HN3 during both the reduction of Fe(III) and during storage at room temperature.

  8. Oxo-rhenium catalyzed reductive coupling and deoxygenation of alcohols.

    PubMed

    Kasner, Gabrielle R; Boucher-Jacobs, Camille; Michael McClain, J; Nicholas, Kenneth M

    2016-06-01

    Representative benzylic, allylic and α-keto alcohols are deoxygenated to alkanes and/or reductively coupled to alkane dimers by reaction with PPh3 catalyzed by (PPh3)2ReIO2 (1). The newly discovered catalytic reductive coupling reaction is a rare C-C bond-forming transformation of alcohols. PMID:27174412

  9. Nickel-Catalyzed Reductive Amidation of Unactivated Alkyl Bromides.

    PubMed

    Serrano, Eloisa; Martin, Ruben

    2016-09-01

    A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. PMID:27357076

  10. Iridium-Catalyzed Reductive Nitro-Mannich Cyclization

    PubMed Central

    Gregory, Alex W; Chambers, Alan; Hawkins, Alison; Jakubec, Pavol; Dixon, Darren J

    2015-01-01

    A new chemoselective reductive nitro-Mannich cyclization reaction sequence of nitroalkyl-tethered lactams has been developed. Relying on the rapid and chemoselective iridium(I)-catalyzed reduction of lactams to the corresponding enamine, subsequent nitro-Mannich cyclization of tethered nitroalkyl functionality provides direct access to important alkaloid natural-product-like structures in yields up to 81 % and in diastereoselectivities that are typically good to excellent. An in-depth understanding of the reaction mechanism has been gained through NMR studies and characterization of reaction intermediates. The new methodology has been applied to the total synthesis of (±)-epi-epiquinamide in four steps. PMID:25399919

  11. Trypsin-catalyzed oxygen-18 labeling for quantitative proteomics

    SciTech Connect

    Qian, Weijun; Petritis, Brianne O.; Nicora, Carrie D.; Smith, Richard D.

    2011-07-01

    Stable isotope labeling based on relative peptide/protein abundance measurements is commonly applied for quantitative proteomics. Recently, trypsin-catalyzed oxygen-18 labeling has grown in popularity due to its simplicity, cost-effectiveness, and its ability to universally label peptides with high sample recovery. In (18)O labeling, both C-terminal carboxyl group atoms of tryptic peptides can be enzymatically exchanged with (18)O, thus providing the labeled peptide with a 4 Da mass shift from the (16)O-labeled sample. Peptide (18)O labeling is ideally suited for generating a labeled "universal" reference sample used for obtaining accurate and reproducible quantitative measurements across large number of samples in quantitative discovery proteomics.

  12. Monooxygenase Substrates Mimic Flavin to Catalyze Cofactorless Oxygenations.

    PubMed

    Machovina, Melodie M; Usselman, Robert J; DuBois, Jennifer L

    2016-08-19

    Members of the antibiotic biosynthesis monooxygenase family catalyze O2-dependent oxidations and oxygenations in the absence of any metallo- or organic cofactor. How these enzymes surmount the kinetic barrier to reactions between singlet substrates and triplet O2 is unclear, but the reactions have been proposed to occur via a flavin-like mechanism, where the substrate acts in lieu of a flavin cofactor. To test this model, we monitored the uncatalyzed and enzymatic reactions of dithranol, a substrate for the nogalamycin monooxygenase (NMO) from Streptomyces nogalater As with flavin, dithranol oxidation was faster at a higher pH, although the reaction did not appear to be base-catalyzed. Rather, conserved asparagines contributed to suppression of the substrate pKa The same residues were critical for enzymatic catalysis that, consistent with the flavoenzyme model, occurred via an O2-dependent slow step. Evidence for a superoxide/substrate radical pair intermediate came from detection of enzyme-bound superoxide during turnover. Small molecule and enzymatic superoxide traps suppressed formation of the oxygenation product under uncatalyzed conditions, whereas only the small molecule trap had an effect in the presence of NMO. This suggested that NMO both accelerated the formation and directed the recombination of a superoxide/dithranyl radical pair. These catalytic strategies are in some ways flavin-like and stand in contrast to the mechanisms of urate oxidase and (1H)-3-hydroxy-4-oxoquinaldine 2,4-dioxygenase, both cofactor-independent enzymes that surmount the barriers to direct substrate/O2 reactivity via markedly different means. PMID:27307041

  13. CO2 reduction catalyzed by mercaptopteridine on glassy carbon.

    PubMed

    Xiang, Dongmei; Magana, Donny; Dyer, R Brian

    2014-10-01

    The catalytic reduction of CO2 is of great current interest because of its role in climate change and the energy cycle. We report a pterin electrocatalyst, 6,7-dimethyl-4-hydroxy-2-mercaptopteridine (PTE), that catalyzes the reduction of CO2 and formic acid on a glassy carbon electrode. Pterins are natural cofactors for a wide range of enzymes, functioning as redox mediators and C1 carriers, but they have not been exploited as electrocatalysts. Bulk electrolysis of a saturated CO2 solution in the presence of the PTE catalyst produces methanol, as confirmed by gas chromatography and (13)C NMR spectroscopy, with a Faradaic efficiency of 10-23%. FTIR spectroelectrochemistry detected a progression of two-electron reduction products during bulk electrolysis, including formate, aqueous formaldehyde, and methanol. A transient intermediate was also detected by FTIR and tentatively assigned as a PTE carbamate. The results demonstrate that PTE catalyzes the reduction of CO2 at low overpotential and without the involvement of any metal. PMID:25259884

  14. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

    PubMed

    Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

    2015-12-25

    We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance. PMID:26488114

  15. Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes

    NASA Astrophysics Data System (ADS)

    Hintermann, Lukas

    Progress in the field of metal-catalyzed redox-neutral additions of oxygen nucleophiles (water, alcohols, carboxylic acids, and others) to alkenes, alkynes, and allenes between 2001 and 2009 is critically reviewed. Major advances in reaction chemistry include development of chiral Lewis acid catalyzed asymmetric oxa-Michael additions and Lewis-acid catalyzed hydro-alkoxylations of nonactivated olefins, as well as further development of Markovnikov-selective cationic gold complex-catalyzed additions of alcohols or water to alkynes and allenes.

  16. Oxygen reduction reaction: A framework for success

    DOE PAGESBeta

    Allendorf, Mark D.

    2016-05-06

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  17. Oxygen reduction reaction: A framework for success

    NASA Astrophysics Data System (ADS)

    Allendorf, Mark D.

    2016-05-01

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Now, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  18. Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Alkyl Bromides: Et3N as the Terminal Reductant.

    PubMed

    Duan, Zhengli; Li, Wu; Lei, Aiwen

    2016-08-19

    Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants. PMID:27472556

  19. Highly Efficient Oxygen Reduction Electrocatalysts based on Winged Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Cheng, Yingwen; Zhang, Hongbo; Varanasi, Chakrapani V.; Liu, Jie

    2013-11-01

    Developing electrocatalysts with both high selectivity and efficiency for the oxygen reduction reaction (ORR) is critical for several applications including fuel cells and metal-air batteries. In this work we developed high performance electrocatalysts based on unique winged carbon nanotubes. We found that the outer-walls of a special type of carbon nanotubes/nanofibers, when selectively oxidized, unzipped and exfoliated, form graphene wings strongly attached to the inner tubes. After doping with nitrogen, the winged nanotubes exhibited outstanding activity toward catalyzing the ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance. While the doped graphene wings with high active site density bring remarkable catalytic activity, the inner tubes remain intact and conductive to facilitate electron transport during electrocatalysis.

  20. Highly Efficient Oxygen Reduction Electrocatalysts based on Winged Carbon Nanotubes

    PubMed Central

    Cheng, Yingwen; Zhang, Hongbo; Varanasi, Chakrapani V.; Liu, Jie

    2013-01-01

    Developing electrocatalysts with both high selectivity and efficiency for the oxygen reduction reaction (ORR) is critical for several applications including fuel cells and metal-air batteries. In this work we developed high performance electrocatalysts based on unique winged carbon nanotubes. We found that the outer-walls of a special type of carbon nanotubes/nanofibers, when selectively oxidized, unzipped and exfoliated, form graphene wings strongly attached to the inner tubes. After doping with nitrogen, the winged nanotubes exhibited outstanding activity toward catalyzing the ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance. While the doped graphene wings with high active site density bring remarkable catalytic activity, the inner tubes remain intact and conductive to facilitate electron transport during electrocatalysis. PMID:24217312

  1. Highly efficient oxygen reduction electrocatalysts based on winged carbon nanotubes.

    PubMed

    Cheng, Yingwen; Zhang, Hongbo; Varanasi, Chakrapani V; Liu, Jie

    2013-01-01

    Developing electrocatalysts with both high selectivity and efficiency for the oxygen reduction reaction (ORR) is critical for several applications including fuel cells and metal-air batteries. In this work we developed high performance electrocatalysts based on unique winged carbon nanotubes. We found that the outer-walls of a special type of carbon nanotubes/nanofibers, when selectively oxidized, unzipped and exfoliated, form graphene wings strongly attached to the inner tubes. After doping with nitrogen, the winged nanotubes exhibited outstanding activity toward catalyzing the ORR through the four-electron pathway with excellent stability and methanol/carbon monoxide tolerance. While the doped graphene wings with high active site density bring remarkable catalytic activity, the inner tubes remain intact and conductive to facilitate electron transport during electrocatalysis. PMID:24217312

  2. Oxygen reduction on a graphite paste and a catalyst loaded graphite paste electrode

    SciTech Connect

    DiMarco, D.M.

    1980-03-01

    Oxygen reduction was studied in basic solution at a graphite paste electrode (GPE). The GPE was used as the disk of a rotating ring disk electrode (RRDE) and experiments were done using the voltage scan technique. The enhancements afforded by catalysts applied to the GPE were also studied. Oxygen reduction on a GPE was shown to be a two-electron process resulting in the formation of peroxide. The Tafel slope (plotted as potential versus log(i/sub l/ x i/(i/sub l/ - i))) was 180 mV. The presence of gold, silver, or platinum on the GPE shifted the oxygen reduction wave approximately 800 mV in the anodic direction. Comparison of the data on a metal catalyzed GPE to the solid metal electrode showed that the former electrode produced a greater fraction of peroxide as product than did the latter. Silver and gold catalyzed GPEs gave Tagel slopes of about 120 mV. The intermediate catalysis of iron and cobalt porphyrin was also examined. While the cobalt porphyrin catalyzed oxygen reduction at a more anodic potential than the iron porphyrin, the latter appeared more active in reacting the peroxide formed as the product of the disk reaction.

  3. Copper-Catalyzed Homo-Dimerization of Nitronates and Enolates under Oxygen Atmosphere

    PubMed Central

    Do, Hien-Quang; Tran-Vu, Hung

    2012-01-01

    A method for copper-catalyzed oxidative dimerization of nitronates and enolates using oxygen as terminal oxidant has been developed. Cyclization through oxidative intramolecular coupling is also feasible for both nitronates and enolates. The mild reaction conditions lead to good functional group tolerance. PMID:23413317

  4. Oxyl and hydroxyl radical transfer in mitochondrial amidoxime reducing component-catalyzed nitrite reduction.

    PubMed

    Yang, Jing; Giles, Logan J; Ruppelt, Christian; Mendel, Ralf R; Bittner, Florian; Kirk, Martin L

    2015-04-29

    A combination of electron paramagnetic resonance (EPR) spectroscopy and computational approaches has provided insight into the nature of the reaction coordinate for the one-electron reduction of nitrite by the mitochondrial amidoxime reducing component (mARC) enzyme. The results show that a paramagnetic Mo(V) species is generated when reduced enzyme is exposed to nitrite, and an analysis of the resulting EPR hyperfine parameters confirms that mARC is remarkably similar to the low-pH form of sulfite oxidase. Two mechanisms for nitrite reduction have been considered. The first shows a modest reaction barrier of 14 kcal/mol for the formation of ·NO from unprotonated nitrite substrate. In marked contrast, protonation of the substrate oxygen proximal to Mo in the Mo(IV)-O-N-O substrate-bound species results in barrierless conversion to products. A fragment orbital analysis reveals a high degree of Mo-O(H)-N-O covalency that provides a π-orbital pathway for one-electron transfer to the substrate and defines orbital constraints on the Mo-substrate geometry for productive catalysis in mARC and other pyranopterin molybdenum enzymes that catalyze this one-electron transformation. PMID:25897643

  5. A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

    PubMed

    Qi, Xinxin; Li, Chong-Liang; Wu, Xiao-Feng

    2016-04-18

    Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. PMID:26934464

  6. Earth-Abundant Nanomaterials for Oxygen Reduction.

    PubMed

    Xia, Wei; Mahmood, Asif; Liang, Zibin; Zou, Ruqiang; Guo, Shaojun

    2016-02-18

    Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR. PMID:26663778

  7. Bioinspired copper catalyst effective for both reduction and evolution of oxygen.

    PubMed

    Wang, Jiong; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-01-01

    In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water. PMID:25335848

  8. Bioinspired copper catalyst effective for both reduction and evolution of oxygen

    NASA Astrophysics Data System (ADS)

    Wang, Jiong; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-10-01

    In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water.

  9. Regeneration of anion exchange resins by catalyzed electrochemical reduction

    DOEpatents

    Gu, Baohua; Brown, Gilbert M.

    2002-01-01

    Anion exchange resins sorbed with perchlorate may be regenerated by a combination of chemical reduction of perchlorate to chloride using a reducing agent and an electrochemical reduction of the oxidized reducing agent. Transitional metals including Ti, Re, and V are preferred chemical reagents for the reduction of perchlorate to chloride. Complexing agents such as oxalate are used to prevent the precipitation of the oxidized Ti(IV) species, and ethyl alcohol may be added to accelerate the reduction kinetics of perchlorate. The regeneration may be performed by continuously recycling the regenerating solution through the resin bed and an electrochemical cell so that the secondary waste generation is minimized.

  10. Oxygen reduction in fuel cell electrolytes

    SciTech Connect

    Striebel, K.A.

    1987-01-01

    Voltage losses in the O{sub 2} cathode represent the major inefficiency in aqueous fuel cells for transportation or stationary applications. Experimental and theoretical studies of oxygen reduction (OR) in novel acid and alkaline electrolytes on smooth and supported Pt have been carried out. Similar kinetically limited rates for OR were measured in the super-acid electrolytes trifluoromethane sulfonic acid (TFMSA) and tetrafluoroethane-1,2-disulfonic acid (TFEDSA), with the rotating disk electrode (RDE) technique at 23 C and pH = 1. The mechanism for OR on Pt in alkaline electrolytes is complicated by the concurrent oxidation and reduction of Pt. Rotating ring-disk electrode (RRDE) studies carried out with anodic and cathodic potential sweeps in 0.1 to 6.9 M KOH and 0.1 to 4.0 M K{sub 2}CO{sub 3} revealed similar currents when corrected for O{sub 2} solubility differences. Porous gas diffusion electrodes (GDE) with supported Pt catalyst were studied in a special cell with low uncompensated solution resistance. Cyclic voltammograms yielded measurements of the wetted areas of carbon and Pt and the local electrolyte composition. Models for the steady-state operation of porous GDE's were developed. These models account for the diffusion and reaction of O{sub 2} and ionic transport in KOH and K{sub 2}CO{sub 3}. The results suggest that modifications of the GDE structure will be necessary to obtain good performance with aqueous carbonate electrolytes.

  11. The Role of Oxygen in the Copper-Catalyzed Decomposition of Phenylborates in Aqueous Alkaline Solutions

    SciTech Connect

    Hyder, M.L.

    1997-03-17

    The effect of oxygen on the copper-catalyzed hydrolysis of phenyl borates containing from one to four phenyl groups was studied in 1 M aqueous sodium hydroxide solution at 59 degrees C. The results are tentatively explained if the effective catalyst for each of the reactions is either cupric or cuprous ion, with the latter being present in significant concentration only in the absence of air.

  12. Copper-Catalyzed Amino Lactonization and Amino Oxygenation of Alkenes Using O-Benzoylhydroxylamines.

    PubMed

    Hemric, Brett N; Shen, Kun; Wang, Qiu

    2016-05-11

    A copper-catalyzed amino lactonization of unsaturated carboxylic acids has been achieved as well as the analogous intermolecular three-component amino oxygenation of olefins. The transformation features mild conditions and a remarkably broad substrate scope, offering a novel and efficient approach to construct a wide range of amino lactones as well as 1,2-amino alcohol derivatives. Mechanistic studies suggest that the reaction proceeds via a distinctive O-benzoylhydroxylamine-promoted electrophilic amination of alkenes. PMID:27114046

  13. Nickel(0)-catalyzed intramolecular reductive coupling of alkenes and aldehydes or ketones with hydrosilanes.

    PubMed

    Hayashi, Yukari; Hoshimoto, Yoichi; Kumar, Ravindra; Ohashi, Masato; Ogoshi, Sensuke

    2016-05-01

    A nickel(0)-catalyzed reductive coupling of aldehydes and simple alkenes with hydrosilanes has been developed. A variety of silyl-protected 1-indanol derivatives were prepared in a highly diastereoselective manner (up to >99 : 1 dr) by employing a combination of nickel(0)/N-heterocyclic carbene and triethylsilane. The present system was also applied to a reductive coupling with ketones. Preliminary results of a nickel(0)-catalyzed asymmetric three-component coupling reaction of an aldehyde, an alkene, and triethylsilane are also shown. PMID:27077829

  14. Durability Improvement of Pt/RGO Catalysts for PEMFC by Low-Temperature Self-Catalyzed Reduction.

    PubMed

    Sun, Kang Gyu; Chung, Jin Suk; Hur, Seung Hyun

    2015-12-01

    Pt/C catalyst used for polymer electrolyte membrane fuel cells (PEMFCs) displays excellent initial performance, but it does not last long because of the lack of durability. In this study, a Pt/reduced graphene oxide (RGO) catalyst was synthesized by the polyol method using ethylene glycol (EG) as the reducing agent, and then low-temperature hydrogen bubbling (LTHB) treatment was introduced to enhance the durability of the Pt/RGO catalyst. The cyclic voltammetry (CV), oxygen reduction reaction (ORR) analysis, and transmittance electron microscopy (TEM) results suggested that the loss of the oxygen functional groups, because of the hydrogen spillover and self-catalyzed dehydration reaction during LTHB, reduced the carbon corrosion and Pt agglomeration and thus enhanced the durability of the electrocatalyst. PMID:26061443

  15. Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

    PubMed Central

    Yang, Zhi-Yong; Moure, Vivian R.; Dean, Dennis R.; Seefeldt, Lance C.

    2012-01-01

    A doubly substituted form of the nitrogenase MoFe protein (α-70Val→Ala, α-195His→Gln) has the capacity to catalyze the reduction of carbon dioxide (CO2) to yield methane (CH4). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH4 within 20 min. The catalytic rate depends on the partial pressure of CO2 (or concentration of HCO3−) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H2C = CH-CH3) through the reductive coupling of CO2 and acetylene (HC≡CH). In light of these observations, we suggest that an emerging understanding of the mechanistic features of nitrogenase could be relevant to the design of synthetic catalysts for CO2 sequestration and formation of olefins. PMID:23150564

  16. Humic substances as a mediator for microbially catalyzed metal reduction

    USGS Publications Warehouse

    Lovley, D.R.; Fraga, J.L.; Blunt-Harris, E. L.; Hayes, L.A.; Phillips, E.J.P.; Coates, J.D.

    1998-01-01

    The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 ??M of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.

  17. Design Principles for Oxygen Reduction and Evolution on Oxide Catalysts

    NASA Astrophysics Data System (ADS)

    Shao-Horn, Yang

    2012-02-01

    catalytic activities. Using the established molecular principle, we further demonstrate that an alkaline earth cobalt oxide with a chemical formula of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than the state-of-the-art iridium oxide catalyst in basic solutions. [4pt] [1] J. Suntivich, H.A. Gasteiger, N. Yabuuchi, H. Nakanishi, J. B. Goodenough and Y. Shao-Horn, Design Principles for Oxygen Reduction Activity on Perovskite Oxide Catalysts for Fuel Cells and Metal-Air Batteries, Nature Chemistry, 3, 546--550 (2011).[0pt] [2] Jin Suntivich, Kevin J. May, Hubert A. Gasteiger, John B. Goodenough and Yang Shao-Horn, A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles, ScienceExpress, Science DOI: 10.1126/science.1212858, (2011).

  18. Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

    PubMed Central

    Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

    2011-01-01

    The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

  19. Influence of water on the reaction path of the oxygen reduction reaction in fuel cells

    NASA Astrophysics Data System (ADS)

    Malardier-Jugroot, Cecile; Groves, Michael; Jugroot, Manish

    2015-04-01

    The development of fuel cell technology has been limited in part due to the cost of the catalyst used in the cell and the rate limiting oxygen reduction reaction. We will present a molecular modelling study focus toward the prediction of improved durability and catalytic efficiency of the Platinum catalyst using doped graphene and doped single walled carbon nanotube surface. The most promising carbon supports - active centre systems were then studied in the gas phase and with explicit water molecules to model the oxygen reduction reaction and tailor the catalytic centres to improve the efficiency of this reaction while reducing the probability of occurrence of side reactions. Two major conclusions have been drawn from this analysis of the oxygen reduction reaction with and without water present. The doping of the carbon surface leads to a stronger platinum-surface interaction and does help the breaking of the oxygen-oxygen bond. These two are interrelated since the stronger surface-platinum bond allows for the same orbitals to interact with the oxygen-oxygen orbital. In addition, the dopants could make the surfaces more polar thus retaining water which might help catalyze the reaction, this property could be very promising to increase the effectiveness of fuel cell cathodes.

  20. Oxygen reduction in fuel cell electrolytes

    SciTech Connect

    Striebel, K.A.; McLarnon, F.R.; Cairns, E.J.

    1987-12-01

    Experimental and theoretical studies of oxygen reduction (OR) in novel acid and alkaline electrolytes on smooth and supported Pt have been carried out. Similar kinetically limited rates for OR were measured in the /open quotes/super-acid/close quotes/ electrolytes trifluoromethane sulfonic acid (TFMSA) and tetrafluoroethane-1,2-disulfonic acid (TFEDSA), with the rotating disk electrode (RDE) technique at 23/degree/C and pH = 1. A first-order dependence on O/sub 2/ pressure was measured. The mechanism for OR on Pt in alkaline electrolytes is complicated by the concurrent oxidation and reduction of Pt. Rotating ring-disk electrode (RRDE) studies carried out with anodic and cathodic potential sweeps in 0.1 to 6.9 M KOH and 0.1 to 4.0 M K/sub 2/CO/sub 3/ revealed similar currents when corrected for O/sub 2/ solubility differences. In dilute electrolytes, OR proceeds primarily through the 4-electron pathway to water, independent of pH. In KOH, the mechanism for Pt oxidation changes and the fraction of current yielding a peroxide product increases at 2 to 3 M. These changes were not observed in K/sub 2/CO/sub 3/. Porous gas diffusion electrodes (GDE) with supported Pt catalyst were studied in a special cell with low uncompensated solution resistance. Cyclic voltammograms yielded measurements of the wetted areas of carbon and Pt and the local electrolyte composition. GDE galvanostatic steady-state performance with 100% O/sub 2/ was measured in 2 to 11 M KOH and 2 to 5.5 M K/sub 2/CO/sub 3/. Results suggest that OR on carbon contributes to the high currents in 6.9 M KOH at high overpotentials. In K/sub 2/CO/sub 3/, lower wetted areas and slow OH/sup /minus// ion transport are responsible for the poor performance when compared with KOH. Models for the steady-state operation of porous GDE's were developed. These models account for the diffusion and reaction of O/sub 2/ and ionic transport in KOH and K/sub 2/CO/sub 3/. 120 refs., 71 figs., 11 tabs.

  1. Platinum-based oxygen reduction electrocatalysts.

    PubMed

    Wu, Jianbo; Yang, Hong

    2013-08-20

    An efficient oxygen reduction reaction (ORR) offers the potential for clean energy generation in low-temperature, proton-exchange membrane fuel cells running on hydrogen fuel and air. In the past several years, researchers have developed high-performance electrocatalysts for the ORR to address the obstacles of high cost of the Pt catalyst per kilowatt of output power and of declining catalyst activity over time. Current efforts are focused on new catalyst structures that add a secondary metal to change the d-band center and the surface atomic arrangement of the catalyst, altering the chemisorption of those oxygencontaining species that have the largest impact on the ORR kinetics and improving the catalyst activity and cost effectiveness. This Account reviews recent progress in the design of Pt-based ORR electrocatalysts, including improved understanding of the reaction mechanisms and the development of synthetic methods for producing catalysts with high activity and stability. Researchers have made several types of highly active catalysts, including an extended single crystal surface of Pt and its alloy, bimetallic nanoparticles, and self-supported, low-dimensional nanostructures. We focus on the design and synthetic strategies for ORR catalysts including controlling the shape (or facet) and size of Pt and its bimetallic alloys, and controlling the surface composition and structure of core-shell, monolayer, and hollow porous structures. The strong dependence of ORR performance on facet and size suggests that synthesizing nanocrystals with large, highly reactive {111} facets could be as important, if not more important, to increasing their activity as simply making smaller nanoparticles. A newly developed carbon-monoxide (CO)-assisted reduction method produces Pt bimetallic nanoparticles with controlled facets. This CO-based approach works well to control shapes because of the selective CO binding on different, low-indexed metal surfaces. Post-treatment under

  2. Reduction of Dissolved Oxygen at a Copper Rotating Disc Electrode

    ERIC Educational Resources Information Center

    Kear, Gareth; Albarran, Carlos Ponce-de-Leon; Walsh, Frank C.

    2005-01-01

    Undergraduates from chemical engineering, applied chemistry, and environmental science courses, together with first-year postgraduate research students in electrochemical technology, are provided with an experiment that demonstrates the reduction of dissolved oxygen in aerated seawater at 25°C. Oxygen reduction is examined using linear sweep…

  3. Glutathione-supported arsenate reduction coupled to arsenolysis catalyzed by ornithine carbamoyl transferase

    SciTech Connect

    Nemeti, Balazs; Gregus, Zoltan

    2009-09-01

    Three cytosolic phosphorolytic/arsenolytic enzymes, (purine nucleoside phosphorylase [PNP], glycogen phosphorylase, glyceraldehyde-3-phosphate dehydrogenase) have been shown to mediate reduction of arsenate (AsV) to the more toxic arsenite (AsIII) in a thiol-dependent manner. With unknown mechanism, hepatic mitochondria also reduce AsV. Mitochondria possess ornithine carbamoyl transferase (OCT), which catalyzes phosphorolytic or arsenolytic citrulline cleavage; therefore, we examined if mitochondrial OCT facilitated AsV reduction in presence of glutathione. Isolated rat liver mitochondria were incubated with AsV, and AsIII formed was quantified. Glutathione-supplemented permeabilized or solubilized mitochondria reduced AsV. Citrulline (substrate for OCT-catalyzed arsenolysis) increased AsV reduction. The citrulline-stimulated AsV reduction was abolished by ornithine (OCT substrate inhibiting citrulline cleavage), phosphate (OCT substrate competing with AsV), and the OCT inhibitor norvaline or PALO, indicating that AsV reduction is coupled to OCT-catalyzed arsenolysis of citrulline. Corroborating this conclusion, purified bacterial OCT mediated AsV reduction in presence of citrulline and glutathione with similar responsiveness to these agents. In contrast, AsIII formation by intact mitochondria was unaffected by PALO and slightly stimulated by citrulline, ornithine, and norvaline, suggesting minimal role for OCT in AsV reduction in intact mitochondria. In addition to OCT, mitochondrial PNP can also mediate AsIII formation; however, its role in AsV reduction appears severely limited by purine nucleoside supply. Collectively, mitochondrial and bacterial OCT promote glutathione-dependent AsV reduction with coupled arsenolysis of citrulline, supporting the hypothesis that AsV reduction is mediated by phosphorolytic/arsenolytic enzymes. Nevertheless, because citrulline cleavage is disfavored physiologically, OCT may have little role in AsV reduction in vivo.

  4. Oxygen Isotope Evidence for Mn(II)-Catalyzed Recrystallization of Manganite (γ-MnOOH).

    PubMed

    Frierdich, Andrew J; Spicuzza, Michael J; Scherer, Michelle M

    2016-06-21

    Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid. PMID:27249316

  5. Palladium-Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions.

    PubMed

    Long, Ran; Huang, Hao; Li, Yaping; Song, Li; Xiong, Yujie

    2015-11-25

    Oxidation reactions by molecular oxygen (O2 ) over palladium (Pd)-based nanomaterials are a series of processes crucial to the synthesis of fine chemicals. In the past decades, investigations of related catalytic materials have mainly been focused on the synthesis of Pd-based nanomaterials from the angle of tailoring their surface structures, compositions and supporting materials, in efforts to improve their activities in organic reactions. From the perspective of rational materials design, it is imperative to address the fundamental issues associated with catalyst performance, one of which should be oxygen activation by Pd-based nanomaterials. Here, the fundamentals that account for the transformation from O2 to reactive oxygen species over Pd, with a focus on singlet O2 and its analogue, are introduced. Methods for detecting and differentiating species are also presented to facilitate future fundamental research. Key factors for tuning the oxygen activation efficiencies of catalytic materials are then outlined, and recent developments in Pd-catalyzed oxygen-related organic reactions are summarized in alignment with each key factor. To close, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields. PMID:26422795

  6. Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

    PubMed

    Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

    2011-04-01

    Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited. PMID:21526439

  7. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  8. N-Doped graphene frameworks with superhigh surface area: excellent electrocatalytic performance for oxygen reduction.

    PubMed

    Cui, H J; Yu, H M; Zheng, J F; Wang, Z J; Zhu, Y Y; Jia, S P; Jia, J; Zhu, Z P

    2016-02-01

    N-Doped carbon materials are promising candidates as alternative catalysts to noble metals in promoting the oxygen reduction reaction (ORR) in fuel cells. However, methods to further reduce the ORR overpotential and improve related kinetics remain to be developed. This study reports that N-doped graphene frameworks (NGFs) synthesized from the rapid pyrolysis of solid glycine particles in the presence of sodium carbonate, display an extremely large specific surface area (1760 m(2) g(-1)) and a graphitic-N-dominant C-N configuration. The NGFs can efficiently catalyze the electrochemical reduction of molecular oxygen into water following a 4e pathway, with a low overpotential (0.98 V of onset potential vs. RHE), very high kinetic limiting current density (16.06 mA cm(-2)), and turnover frequency (121 s(-1)), much better than the commercial Pt/C catalyst. PMID:26763656

  9. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments. PMID:26471460

  10. Nickel-Catalyzed Asymmetric Reductive Cross-Coupling Between Vinyl and Benzyl Electrophiles

    PubMed Central

    2015-01-01

    A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and benzyl chlorides has been developed. This method provides direct access to enantioenriched products bearing aryl-substituted tertiary allylic stereogenic centers from simple, stable starting materials. A broad substrate scope is achieved under mild reaction conditions that preclude the pregeneration of organometallic reagents and the regioselectivity issues commonly associated with asymmetric allylic arylation. PMID:25245492

  11. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt.

    PubMed

    Wu, Gang; More, Karren L; Johnston, Christina M; Zelenay, Piotr

    2011-04-22

    The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%). PMID:21512028

  12. N-Doped graphene frameworks with superhigh surface area: excellent electrocatalytic performance for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Cui, H. J.; Yu, H. M.; Zheng, J. F.; Wang, Z. J.; Zhu, Y. Y.; Jia, S. P.; Jia, J.; Zhu, Z. P.

    2016-01-01

    N-Doped carbon materials are promising candidates as alternative catalysts to noble metals in promoting the oxygen reduction reaction (ORR) in fuel cells. However, methods to further reduce the ORR overpotential and improve related kinetics remain to be developed. This study reports that N-doped graphene frameworks (NGFs) synthesized from the rapid pyrolysis of solid glycine particles in the presence of sodium carbonate, display an extremely large specific surface area (1760 m2 g-1) and a graphitic-N-dominant C-N configuration. The NGFs can efficiently catalyze the electrochemical reduction of molecular oxygen into water following a 4e pathway, with a low overpotential (0.98 V of onset potential vs. RHE), very high kinetic limiting current density (16.06 mA cm-2), and turnover frequency (121 s-1), much better than the commercial Pt/C catalyst.N-Doped carbon materials are promising candidates as alternative catalysts to noble metals in promoting the oxygen reduction reaction (ORR) in fuel cells. However, methods to further reduce the ORR overpotential and improve related kinetics remain to be developed. This study reports that N-doped graphene frameworks (NGFs) synthesized from the rapid pyrolysis of solid glycine particles in the presence of sodium carbonate, display an extremely large specific surface area (1760 m2 g-1) and a graphitic-N-dominant C-N configuration. The NGFs can efficiently catalyze the electrochemical reduction of molecular oxygen into water following a 4e pathway, with a low overpotential (0.98 V of onset potential vs. RHE), very high kinetic limiting current density (16.06 mA cm-2), and turnover frequency (121 s-1), much better than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06319a

  13. Several new catalysts for reduction of oxygen in fuel cells

    NASA Technical Reports Server (NTRS)

    Cattabriga, R. A.; Cohn, E. M.; Giner, J. D.; Makrides, A. C.; Swette, L. L.

    1970-01-01

    Test results prove nickel carbide or nitride, nickel-cobalt carbide, titanium carbide or nitride, and intermetallic compounds of the transition or noble metals to be efficient electrocatalysts for oxygen reduction in alkaline electrolytes in low temperature fuel cells.

  14. Redox Reactions of Metalloporphyrins and their Role in Catalyzed Reduction of Carbon Dioxide

    SciTech Connect

    Neta, P.

    2002-09-01

    Pulse radiolysis and laser photolysis are used to study redox processes of metalloporphyrins and related complexes in order to evaluate these light absorbing molecules as sensitizers and intermediates in solar energy conversion schemes. The main thrust of the current studies is to investigate the role of reduced metalloporphyrins as intermediates in the catalyzed reduction of carbon dioxide. Studies involve cobalt and iron porphyrins, phthalocyanines, corroles, and corrins as homogeneous catalysts for reduction of carbon dioxide in solution. The main aim is to understand the mechanisms of these photochemical schemes in order to facilitate their potential utilization.

  15. Copper-Catalyzed Reductive N-Alkylation of Amides with N-Tosylhydrazones Derived from Ketones.

    PubMed

    Xu, Peng; Qi, Fu-Ling; Han, Fu-She; Wang, Yan-Hua

    2016-07-20

    A CuI-catalyzed reductive coupling of ketone-derived N-tosylhydrazones with amides is presented. Under the optimized conditions, an array of N-tosylhydrazones derived from aryl-alkyl and diaryl ketones could couple effectively with a wide variety of (hetero)aryl as well as aliphatic amides to afford the N-alkylated amides in high yields. The method represents the very few examples for reliably accessing secondary and tertiary amides through a reductive N-alkylation protocol. PMID:27346856

  16. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    PubMed

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-01

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel. PMID:26566189

  17. Azotobacter vinelandii vanadium nitrogenase: formaldehyde is a product of catalyzed HCN reduction, and excess ammonia arises directly from catalyzed azide reduction.

    PubMed

    Fisher, Karl; Dilworth, Michael J; Newton, William E

    2006-04-01

    The Mo-nitrogenase-catalyzed reduction of both cyanide and azide results in the production of excess NH3, which is an amount of NH3 over and above that expected to be formed from the well-recognized reactions. Several suggestions about the possible sources of excess NH3 have been made, but previous attempts to characterize these reactions have met with either limited (or no) success or controversy. Because V-nitrogenase has a propensity to release partially reduced intermediates, e.g., N2H4 during N2 reduction, it was selected to probe the reduction of cyanide and azide. Sensitive assay procedures were developed and employed to monitor the production of either HCHO or CH3OH (its further two-electron-reduced product) from HCN. Like Mo-nitrogenase, V-nitrogenase suffered electron-flux inhibition by CN- (but was much less sensitive than Mo-nitrogenase), but unlike the case for Mo-nitrogenase, MgATP hydrolysis was also inhibited by CN-. V-Nitrogenase also released more of the four-electron-reduced intermediate, CH3NH2, than did Mo-nitrogenase. At high NaCN concentrations, V-nitrogenase directed a significant percentage of electron flux into excess NH3, and under these conditions, substantial amounts of HCHO, but no CH3OH, were detected for the first time. With azide, in contrast to the case for Mo-nitrogenase, both total electron flux and MgATP hydrolysis with V-nitrogenase were inhibited. V-Nitrogenase, unlike Mo-nitrogenase, showed no preference between the two-electron reduction to N2-plus-NH3 and the six-electron reduction to N2H4-plus-NH3. V-Nitrogenase formed more excess NH3, but reduction of the N2 produced by the two-electron reduction of N3(-) was not its source. Rather, it was formed directly by the eight-electron reduction of N3(-). Unlike Mo-nitrogenase, CO could not completely eliminate either cyanide or azide reduction by V-nitrogenase. CO did, however, eliminate the inhibition of both electron flux and MgATP hydrolysis by CN-, but not that caused by

  18. Oxygen Reduction Catalysis at a Dicobalt Center: The Relationship of Faradaic Efficiency to Overpotential.

    PubMed

    Passard, Guillaume; Ullman, Andrew M; Brodsky, Casey N; Nocera, Daniel G

    2016-03-01

    The selective four electron, four proton, electrochemical reduction of O2 to H2O in the presence of a strong acid (TFA) is catalyzed at a dicobalt center. The faradaic efficiency of the oxygen reduction reaction (ORR) is furnished from a systematic electrochemical study by using rotating ring disk electrode (RRDE) methods over a wide potential range. We derive a thermodynamic cycle that gives access to the standard potential of O2 reduction to H2O in organic solvents, taking into account the presence of an exogenous proton donor. The difference in ORR selectivity for H2O vs H2O2 depends on the thermodynamic standard potential as dictated by the pKa of the proton donor. The model is general and rationalizes the faradaic efficiencies reported for many ORR catalytic systems. PMID:26876226

  19. Lunar oxygen - The reduction of glass by hydrogen

    NASA Technical Reports Server (NTRS)

    Allen, Carlton C.; Mckay, David S.; Morris, Richard V.

    1992-01-01

    The direct reduction of volcanic glass by hydrogen has been proposed as a method of extracting oxygen from the lunar soil. Experiments using lunar simulant glasses reacted with flowing hydrogen gas have demonstrated reduction at temperatures from 1000 to 1200 C. For melted samples ferrous iron was reduced to the metal, which formed large crystals at the expense of the glass. Samples held below the melting point rapidly devitrified, and iron was formed from submicrometer crystals of ilmenite and pyroxene. Weight losses of 3.6 - 4.5 percent, depending on glass composition, were achieved in 3 hours at 1100 C. A lunar oxygen plant operating at this efficiency and utilizing Apollo 17 orange glass as a feedstock could produce 50 kg of oxygen per ton of soil. The processes of reduction and sintering of lunar soil are synergistic, and could be combined to produce both oxygen and construction material at a moon base.

  20. Transition Metal Catalyzed Reactions of Carbohydrates: a Nonoxidative Approach to Oxygenated Organics

    SciTech Connect

    Andrews, Mark

    1997-01-08

    There is a critical need for new environmentally friendly processes in the United States chemical industry as legislative and economic pressures push the industry to zero-waste and cradle-to-grave responsibility for the products they produce. Carbohydrates represent a plentiful, renewable resource, which for some processes might economically replace fossil feedstocks. While the conversion of biomass to fuels, is still not generally economical, the selective synthesis of a commodity or fine chemical, however, could compete effectively if appropriate catalytic conversion systems can be found. Oxygenated organics, found in a variety of products such as nylon and polyester, are particularly attractive targets. We believe that with concerted research efforts, homogeneous transition metal catalyzed reactions could play a significant role in bringing about this future green chemistry technology.

  1. Oxygen reduction and oxygen evolution in DMSO based electrolytes: the role of the electrocatalyst.

    PubMed

    Bondue, C J; Reinsberg, P; Abd-El-Latif, A A; Baltruschat, H

    2015-10-14

    In the present paper the role of the electrode material in oxygen reduction in DMSO based electrolytes is elucidated using DEMS. We have found, employing platinum, gold, ruthenium rhodium, selenium decorated rhodium and boron doped diamond (BDD) as electrode materials, that the actual mechanism of oxygen reduction largely depends on the electrode material. At platinum, rhodium and selenium decorated rhodium the final reduction product, peroxide, is formed electrochemically. At gold and at low overpotentials oxygen is reduced to superoxide and peroxide is only formed by disproportionation of the latter. No oxygen reduction takes place at the diamond surface of the BDD-electrode, hence, showing unambiguously that oxygen reduction is an inner sphere reaction. Also, the rate of oxygen evolution varies with the electrode material, although the onset potential of oxygen evolution is not influenced. The amount of peroxide formed is limited to 1-2 monolayers. Contrary to intuition oxygen reduction and oxygen evolution from peroxide, therefore, are heterogeneous, electrocatalytic reactions. The finding of such an electrocatalytic effect is of great importance for the development and optimization of lithium-air batteries. Aside from the electrode material there are also effects of water as well as of the cation used in the electrolyte. This suggests an influence of the double layer at the interface between the electrode and the electrolyte on oxygen reduction in addition to the well-known higher stability of Na2O2 and K2O2. Electrospray ionization (ESI) results show that any effect of water in the Li(+) containing electrolyte is not due to an altered solvation of the cation. PMID:26371703

  2. Template-free synthesis of porous graphitic carbon nitride/carbon composite spheres for electrocatalytic oxygen reduction reaction.

    PubMed

    Fu, Xiaorui; Hu, Xiaofei; Yan, Zhenhua; Lei, Kaixiang; Li, Fujun; Cheng, Fangyi; Chen, Jun

    2016-01-28

    Porous graphitic carbon nitride/carbon composite spheres were synthesized using melamine and cyanuric acid, and glucose as the carbon nitride and carbon precursor, respectively. The 3D hierarchical composites efficiently catalyzed the oxygen reduction reaction with an onset potential of 0.90 V and a kinetic current density of 23.92 mA cm(-2). These merit their promising applications in fuel cells and metal-air batteries. PMID:26666314

  3. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    PubMed

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media. PMID:25825826

  4. Kinetics of tetrachloroethylene-reductive dechlorination catalyzed by vitamin B{sub 12}

    SciTech Connect

    Burris, D.R.; Deng, B.; Buck, L.E.; Hatfield, K.

    1998-09-01

    Reductive dechlorination kinetics of tetrachloroethylene (PCE) to ethylene catalyzed by vitamin B{sub 12} using Ti[III] citrate as the bulk reductant was examined in a vapor-water batch system. A kinetic model incorporating substrate-B{sub 12} electron-transfer complex formation and subsequent product release was developed. The model also accounted for the primary reductive dechlorination pathways (hydrogenolysis and reductive {beta} elimination) and vapor/water-phase partitioning. Reaction rate constants were sequentially determined by fitting the model to experimental kinetic data while moving upward through consecutive reaction pathways. The release of product from the complex was found to be second order with respect to substrate concentration for both PCE and acetylene; all other substrates appeared to release by first order. Reductive {beta} elimination was found to be a significant reaction pathway for trichloroethylene (TCE), and chloroacetylene was observed as a reactive intermediate. Acetylene production appears to be primarily due to the reduction of chloroacetylene derived from TCE. The reduction of cis-dichloroethylene (cis-DCE), the primary DCE isomer formed, was extremely slow, leading to a significant buildup of cis-DCE. The kinetics of acetylene and vinyl chloride reduction appeared to be limited by the formation of relatively stable substrate-B{sub 12} complexes. The relatively simple model examined appears to adequately represent the main features of the experimental data.

  5. Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

    PubMed

    Lu, Yi-Chun; Gasteiger, Hubert A; Shao-Horn, Yang

    2011-11-30

    We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications. PMID:22044022

  6. Cytochromes P450 Catalyze the Reduction of α,β-Unsaturated Aldehydes

    PubMed Central

    Amunom, Immaculate; Dieter, Laura J.; Tamasi, Viola; Cai, Jan; Conklin, Daniel J.; Srivastava, Sanjay; Martin, Martha V.; Guengerich, F. Peter; Prough, Russell A.

    2011-01-01

    The metabolism of α,β-unsaturated aldehydes, e.g. 4-hydroxynonenal, involves oxidation to carboxylic acids, reduction to alcohols, and glutathionylation to eventually form mercapturide conjugates. Recently we demonstrated that P450s can oxidize aldehydes to carboxylic acids, a reaction previously thought to involve aldehyde dehydrogenase. When recombinant cytochrome P450 3A4 was incubated with 4-hydroxynonenal, O2, and NADPH, several products were produced, including 1,4-dihydroxynonene (DHN), 4-hydroxy-2-nonenoic acid (HNA), and an unknown metabolite. Several P450s catalyzed the reduction reaction in the order (human) P450 2B6 ≅ P450 3A4 > P450 1A2 > P450 2J2 > (mouse) P450 2c29. Other P450s did not catalyze the reduction reaction (human P450 2E1 & rabbit P450 2B4). Metabolism by isolated rat hepatocytes showed that HNA formation was inhibited by cyanamide, while DHN formation was not affected. Troleandomycin increased HNA production 1.6-fold while inhibiting DHN formation, suggesting that P450 3A11 is a major enzyme involved in rat hepatic clearance of 4-HNE. A fluorescent assay was developed using 9-anthracenealdehyde to measure both reactions. Feeding mice diet containing t-butylated hydroxyanisole increased the level of both activities with hepatic microsomal fractions, but not proportionally. Miconazole (0.5 mM) was a potent inhibitor of these microsomal reduction reactions, while phenytoin and α-naphthoflavone (both at 0.5 mM) were partial inhibitors, suggesting the role of multiple P450 enzymes. The oxidative metabolism of these aldehydes was inhibited >90% in an Ar or CO atmosphere, while the reductive reactions were not greatly affected. These results suggest that P450s are significant catalysts of reduction of α,β-unsaturated aldehydes in liver. PMID:21766881

  7. Simultaneous reduction of particulate matter and NO(x) emissions using 4-way catalyzed filtration systems.

    PubMed

    Swanson, Jacob J; Watts, Winthrop F; Newman, Robert A; Ziebarth, Robin R; Kittelson, David B

    2013-05-01

    The next generation of diesel emission control devices includes 4-way catalyzed filtration systems (4WCFS) consisting of both NOx and diesel particulate matter (DPM) control. A methodology was developed to simultaneously evaluate the NOx and DPM control performance of miniature 4WCFS made from acicular mullite, an advanced ceramic material (ACM), that were challenged with diesel exhaust. The impact of catalyst loading and substrate porosity on catalytic performance of the NOx trap was evaluated. Simultaneously with NOx measurements, the real-time solid particle filtration performance of catalyst-coated standard and high porosity filters was determined for steady-state and regenerative conditions. The use of high porosity ACM 4-way catalyzed filtration systems reduced NOx by 99% and solid and total particulate matter by 95% when averaged over 10 regeneration cycles. A "regeneration cycle" refers to an oxidizing ("lean") exhaust condition followed by a reducing ("rich") exhaust condition resulting in NOx storage and NOx reduction (i.e., trap "regeneration"), respectively. Standard porosity ACM 4-way catalyzed filtration systems reduced NOx by 60-75% and exhibited 99.9% filtration efficiency. The rich/lean cycling used to regenerate the filter had almost no impact on solid particle filtration efficiency but impacted NOx control. Cycling resulted in the formation of very low concentrations of semivolatile nucleation mode particles for some 4WCFS formulations. Overall, 4WCFS show promise for significantly reducing diesel emissions into the atmosphere in a single control device. PMID:23550802

  8. Simple and Efficient Ruthenium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen.

    PubMed

    Ray, Ritwika; Chandra, Shubhadeep; Maiti, Debabrata; Lahiri, Goutam Kumar

    2016-06-20

    Oxidative transformations utilizing molecular oxygen (O2 ) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O2 are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O2 as the "primary" oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium-catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen- or electron-transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including (18) O labeling established the in situ formation of an oxo-ruthenium intermediate as the active catalytic species in the cycle and involvement of a two-electron hydride transfer in the rate-limiting step. PMID:27257955

  9. Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

    PubMed

    Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

    2015-08-26

    In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst. PMID:26280984

  10. Two dimensional N-containing carbon materials for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Feng, Yexin; Hu, Zhenpeng; Zhang, Lixin

    2013-03-01

    Seeking Pt replacement catalysts for cathode oxygen reduction reaction (ORR) is very important for the application of some new energy technologies like fuel cells and lithium-air batteries. N-doped graphene and carbon nitride sheets are two kinds of promising materials. For the N-doped graphene, it is found that nitrogen clusters other than isolated substitutionals are the active sites for oxygen reduction. Clusters with three or four N atoms are found to be the most active. Codoping boron (or Fe, Co) can effectively stabilize these high energy clusters while keep the cluster's high activity. For the carbon nitride sheets, in the C:N ratio range of 2.0-3.0, they are stable enough and can potentially catalyze the oxygen reduction as efficiently as Pt. It is revealed that the concentration of nitrogen can tune the Fermi level of the material and thus the catalytic property. The catalytic sites are located at those carbon atoms with special configurations rather than the nitrogen atoms. These results are helpful in designing N-containing carbon materials for ORR.

  11. Hydrogen Reduction of Lunar Regolith Simulants for Oxygen Production

    NASA Technical Reports Server (NTRS)

    Hegde, U.; Balasubramaniam, R.; Gokoglu, S. A.; Rogers, K.; Reddington, M.; Oryshchyn, L.

    2011-01-01

    Hydrogen reduction of the lunar regolith simulants JSC-1A and LHT-2M is investigated in this paper. Experiments conducted at NASA Johnson Space Center are described and are analyzed utilizing a previously validated model developed by the authors at NASA Glenn Research Center. The effects of regolith sintering and clumping, likely in actual production operations, on the oxygen production rate are studied. Interpretations of the obtained results on the basis of the validated model are provided and linked to increase in the effective particle size and reduction in the intra-particle species diffusion rates. Initial results on the pressure dependence of the oxygen production rate are also presented and discussed

  12. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

    PubMed Central

    Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A. A. W.; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V.; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero

    2016-01-01

    Abstract Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2 −. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:27478281

  13. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

    PubMed Central

    Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A. A. W.; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V.; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero

    2016-01-01

    Abstract Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2 −. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:26773287

  14. A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water.

    PubMed

    Schöfberger, Wolfgang; Faschinger, Felix; Chattopadhyay, Samir; Bhakta, Snehadri; Mondal, Biswajit; Elemans, Johannes A A W; Müllegger, Stefan; Tebi, Stefano; Koch, Reinhold; Klappenberger, Florian; Paszkiewicz, Mateusz; Barth, Johannes V; Rauls, Eva; Aldahhak, Hazem; Schmidt, Wolf Gero; Dey, Abhishek

    2016-02-12

    Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H(+)/4 e(-) process, while oxygen can be fully reduced to water by a 4 e(-)/4 H(+) process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2(-). We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes. PMID:26773287

  15. Opening gates to oxygen reduction reactions on Cu(111) surface

    NASA Astrophysics Data System (ADS)

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-01

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O-H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O2 are different in cathodic and anodic potentials. The diffusion of O2 is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

  16. Opening gates to oxygen reduction reactions on Cu(111) surface.

    PubMed

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-28

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O-H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O2 are different in cathodic and anodic potentials. The diffusion of O2 is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency. PMID:25833599

  17. Opening gates to oxygen reduction reactions on Cu(111) surface

    SciTech Connect

    Sumer, Aslihan; Chaudhuri, Santanu

    2015-03-28

    Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O–H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O{sub 2} are different in cathodic and anodic potentials. The diffusion of O{sub 2} is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

  18. Source of the oxygen atom in the product of cytochrome P-450-catalyzed N-demethylation reactions.

    PubMed

    Kedderis, G L; Dwyer, L A; Rickert, D E; Hollenberg, P F

    1983-05-01

    The source of the oxygen atom in the product of the cytochrome P-450-catalyzed N-demethylation of N-methylcarbazole was determined by mass spectral analysis of the carbinolamine precursor of formaldehyde formed during incubation in oxygen 18-enriched medium. Initial experiments demonstrated that N-(hydroxymethyl)carbazole, the carbinolamine product of the metabolism of N-methylcarbazole, did not exchange oxygen with solvent water. When N-methylcarbazole was incubated in oxygen 18-enriched medium with purified cytochrome P-450 in the presence of either purified NADPH-cytochrome P-450 reductase and NADPH, cumene hydroperoxide, t-butyl hydroperoxide, or peracetic acid, there was no incorporation of oxygen 18 from the medium into N-(hydroxymethyl)carbazole. These results clearly demonstrate that the oxygen atom inserted into N-methylcarbazole by cytochrome P-450 to yield N-(hydroxymethyl)carbazole does not come from the medium and show that the N-demethylation reactions catalyzed by cytochrome P-450 proceed in a manner similar to hydroxylation reactions, with the oxygen atom in the product being derived from the oxidant. PMID:6408392

  19. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2.

    PubMed

    Miner, Elise M; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

    2016-01-01

    Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications. PMID:26952523

  20. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

    PubMed Central

    Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

    2016-01-01

    Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications. PMID:26952523

  1. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

    DOE PAGESBeta

    Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dinca, Mircea

    2016-03-08

    Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units.more » Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. As a result, such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.« less

  2. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

    NASA Astrophysics Data System (ADS)

    Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

    2016-03-01

    Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.

  3. Iron- and indium-catalyzed reactions toward nitrogen- and oxygen-containing saturated heterocycles.

    PubMed

    Cornil, Johan; Gonnard, Laurine; Bensoussan, Charlélie; Serra-Muns, Anna; Gnamm, Christian; Commandeur, Claude; Commandeur, Malgorzata; Reymond, Sébastien; Guérinot, Amandine; Cossy, Janine

    2015-03-17

    A myriad of natural and/or biologically active products include nitrogen- and oxygen-containing saturated heterocycles, which are thus considered as attractive scaffolds in the drug discovery process. As a consequence, a wide range of reactions has been developed for the construction of these frameworks, much effort being specially devoted to the formation of substituted tetrahydropyrans and piperidines. Among the existing methods to form these heterocycles, the metal-catalyzed heterocyclization of amino- or hydroxy-allylic alcohol derivatives has emerged as a powerful and stereoselective strategy that is particularly interesting in terms of both atom-economy and ecocompatibility. For a long time, palladium catalysts have widely dominated this area either in Tsuji-Trost reactions [Pd(0)] or in an electrophilic activation process [Pd(II)]. More recently, gold-catalyzed formation of saturated N- and O-heterocycles has received growing attention because it generally exhibits high efficiency and diastereoselectivity. Despite their demonstrated utility, Pd- and Au-complexes suffer from high costs, toxicity, and limited natural abundance, which can be barriers to their widespread use in industrial processes. Thus, the replacement of precious metals with less expensive and more environmentally benign catalysts has become a challenging issue for organic chemists. In 2010, our group took advantage of the ability of the low-toxicity and inexpensive FeCl3 in activating allylic or benzylic alcohols to develop iron-catalyzed N- and O-heterocylizations. We first focused on N-heterocycles, and a variety of 2,6-disubstituted piperidines as well as pyrrolidines were synthesized in a highly diastereoselective fashion in favor of the cis-compounds. The reaction was further extended to the construction of substituted tetrahydropyrans. Besides triggering the formation of heterocycles, the iron salts were shown to induce a thermodynamic epimerization, which is the key to reach the high

  4. Electron/proton coupling in bacterial nitric oxide reductase during reduction of oxygen.

    PubMed

    Flock, Ulrika; Watmough, Nicholas J; Adelroth, Pia

    2005-08-01

    The respiratory nitric oxide reductase (NOR) from Paracoccus denitrificans catalyzes the two-electron reduction of NO to N(2)O (2NO + 2H(+) + 2e(-) --> N(2)O + H(2)O), which is an obligatory step in the sequential reduction of nitrate to dinitrogen known as denitrification. NOR has four redox-active cofactors, namely, two low-spin hemes c and b, one high-spin heme b(3), and a non-heme iron Fe(B), and belongs to same superfamily as the oxygen-reducing heme-copper oxidases. NOR can also use oxygen as an electron acceptor; this catalytic activity was investigated in this study. We show that the product in the steady-state reduction of oxygen is water. A single turnover of the fully reduced NOR with oxygen was initiated using the flow-flash technique, and the progress of the reaction monitored by time-resolved optical absorption spectroscopy. Two major phases with time constants of 40 micros and 25 ms (pH 7.5, 1 mM O(2)) were observed. The rate constant for the faster process was dependent on the O(2) concentration and is assigned to O(2) binding to heme b(3) at a bimolecular rate constant of 2 x 10(7) M(-)(1) s(-)(1). The second phase (tau = 25 ms) involves oxidation of the low-spin hemes b and c, and is coupled to the uptake of protons from the bulk solution. The rate constant for this phase shows a pH dependence consistent with rate limitation by proton transfer from an internal group with a pK(a) = 6.6. This group is presumably an amino acid residue that is crucial for proton transfer to the catalytic site also during NO reduction. PMID:16060680

  5. Oxygen reduction in tetrafluoroethane-1,2-disulfonic acid

    SciTech Connect

    Striebel, K.A.; Andricacos, P.C.; Cairns, E.J.; Ross, P.N.; McLarnon, F.R.

    1985-10-01

    The kinetics of oxygen reduction on platinum in tetrafluoroethane-1,2-disulfonic acid (TFEDSA) and trifluoromethane sulfonic acid (TFMSA) have been studied with the rotating disk electrode technique at pH 1. The resulting Tafel plots coincide within the error of the experiment, indicating similar kinetics in the two electrolytes. The reaction order with respect to oxygen concentration was studied by varying the partial pressure of oxygen above the electrolyte. The rotation-independent currents at 0.90V vs. DHE were used to calculate a reaction order equal to one. A first-order analysis of the rotation-dependent currents was then used to extract kinetic currents at lower potentials. These kinetic currents also exhibited first-order dependence on oxygen concentration. 12 references, 7 figures.

  6. Comparison of lignin derivatives as substrates for laccase-catalyzed scavenging of oxygen in coatings and films

    PubMed Central

    2014-01-01

    Background Lignin derivatives are phenylpropanoid biopolymers derived from pulping and biorefinery processes. The possibility to utilize lignin derivatives from different types of processes in advanced enzyme-catalyzed oxygen-scavenging systems intended for active packaging was explored. Laccase-catalyzed oxidation of alkali lignin (LA), hydrolytic lignin (LH), organosolv lignin (LO), and lignosulfonates (LS) was compared using oxygen-scavenging coatings and films in liquid and gas phase systems. Results When coatings containing lignin derivatives and laccase were immersed in a buffered aqueous solution, the oxygen-scavenging capability increased in the order LO < LH < LA < LS. Experiments with coatings containing laccase and LO, LH or LA incubated in oxygen-containing gas in air-tight chambers and at a relative humidity (RH) of 100% showed that paperboard coated with LO and laccase reduced the oxygen content from 1.0% to 0.4% during a four-day period, which was far better than the results obtained with LA or LH. LO-containing coatings incubated at 92% RH also displayed activity, with a decrease in oxygen from 1.0% to 0.7% during a four-day period. The oxygen scavenging was not related to the content of free phenolic hydroxyl groups, which increased in the order LO < LS < LH < LA. LO and LS were selected for further studies and films containing starch, clay, glycerol, laccase and LO or LS were characterized using gel permeation chromatograpy, dynamic mechanical analysis, and wet stability. Conclusions The investigation shows that different lignin derivatives exhibit widely different properties as a part of active coatings and films. Results indicate that LS and LO were most suitable for the application studied and differences between them were attributed to a higher degree of laccase-catalyzed cross-linking of LS than of LO. Inclusion in active-packaging systems offers a new way to utilize some types of lignin derivatives from biorefining

  7. Asymmetric reduction of prochiral ketones to chiral alcohols catalyzed by plants tissue.

    PubMed

    Yang, Zhong-Hua; Zeng, Rong; Yang, Gai; Wang, Yu; Li, Li-Zhen; Lv, Zao-Sheng; Yao, Man; Lai, Bin

    2008-09-01

    As an important organic compound, chiral alcohols are the key chiral building blocks to many single enantiomer pharmaceuticals. Asymmetric reduction of the corresponding prochiral ketones to produce the chiral alcohols by biocatalysis is one of the most promising routes. Asymmetric reduction of different kinds of non-natural prochiral ketones catalyzed by various plants tissue was studied in this work. Acetophenone, 4'-chloroacetophenone and ethyl 4-chloroacetoacetate were chosen as the model substrates for simple ketone, halogen-containing aromatic ketone and beta-ketoesters, respectively. Apple (Malus pumila), carrot (Daucus carota), cucumber (Cucumis sativus), onion (Allium cepa), potato (Soanum tuberosum), radish (Raphanus sativus) and sweet potato (Ipomoea batatas) were chosen as the biocatalysts. It was found that these kinds of prochiral ketoness could be reduced by these plants tissue with high enantioselectivity. Both R- and S-form configuration chiral alcohols could be obtained. The e.e. and chemical yield could reach about 98 and 80% respectively for acetophenone and 4'-chloroacetophenone reduction reaction with favorable plant tissue. And the e.e. and yield for ethyl 4-chloroacetoacetate reduction reaction was about 91 and 45% respectively. PMID:18548304

  8. Oxygen reduction by lithium on model carbon and oxidized carbon structures

    SciTech Connect

    Xu, Ye; Shelton Jr, William Allison

    2011-01-01

    Li-air batteries have attracted substantial interest for their high theoretical specific energies, but the oxygen reduction reaction by Li (Li-ORR) that occurs at the carbon cathode remains poorly understood. Periodic density functional theory calculations have been performed to examine the Li-ORR on several model carbon structures, including the graphite(0001) basal plane, the (8,0) single-wall nanotube, the armchair-type edge, and a di-vacancy in the basal plane. The inertness of the basal plane limits the reversible potential of O{sub 2} reduction to 1.1 V, and slightly higher to 1.2 V on the curved nanotube. The armchair edge and di-vacancy are highly reactive and significantly oxidized at ambient conditions to various CO{sub x} groups, which are reduced by Li via redox mechanisms at 1.2-1.4 V. These CO{sub x} groups can also catalyze O{sub 2} reduction at up to 2.3 V (an overpotential of 0.4 V vs. the calculated equilibrium potential for bulk Li{sub 2}O{sub 2} formation) by chelating and stabilizing the LiO{sub 2} intermediate. The Li-ORR on graphitic carbon, if via concerted Li{sup +}/e{sup -} transfer and involving carbon, lithium, and oxygen only, is therefore expected to initiate with the smallest overpotential at under-coordinated carbon centers that are oxidized at ambient conditions.

  9. Intracellular phosphorous compounds and the reversibility of dissimilatory sulfate reduction: what do we learn from oxygen isotopes?

    NASA Astrophysics Data System (ADS)

    Brunner, B.

    2012-12-01

    Dissimilatory sulfate reduction (DSR) leads to an overprint of the oxygen isotope composition of sulfate by the oxygen isotope composition of water. This overprint is assumed to occur via cell-internally formed sulfuroxy intermediates in the sulfate reduction pathway. Unlike sulfate, the sulfuroxy intermediates can readily exchange oxygen isotopes with water. Subsequent to the oxygen isotope exchange, these intermediates, e.g. sulfite, are re-oxidized by reversible enzymatic reactions to sulfate, incorporating the oxygen used for the re-oxidation of the sulfur intermediates. Consequently, the rate and expression of DSR-mediated oxygen isotope exchange between sulfate and water depends not only on the oxygen isotope exchange between sulfuroxy intermediates and water, but also on cell-internal forward and backward reactions. The latter are the very same processes that control the extent of sulfur isotope fractionation expressed by DSR. In the stepwise reduction of sulfate to sulfide, intracellular phosphorous compounds are pivotal for the conversion of intracellular sulfate to sulfite. Because of thermodynamics, the concentration of thereby produced intracellular phosphorous compounds affects the reversibility of this reduction step and thereby impacts the oxygen isotope composition of sulfate. Consequently, there should be a link between cell-internal management of phosphorous pools and the expression of sulfur and oxygen isotope effects. The measurement of multiple sulfur isotope fractionation has successfully been applied to obtain information on the reversibility of individual enzymatically catalyzed steps in DSR. Similarly, also the oxygen isotope signature of sulfate reveals information on the reversibility of DSR. High reversibility (i.e. large isotope effects) is generally assumed to be tied to low energy availability. This raises the question if and how cell-internal management of phosphorous pools could be tied to survival strategies under energy limitation.

  10. Dimer Involvement and Origin of Crossover in Nickel-Catalyzed Aldehyde–Alkyne Reductive Couplings

    PubMed Central

    2015-01-01

    The mechanism of nickel(0)-catalyzed reductive coupling of aldehydes and alkynes has been studied. Extensive double-labeling crossover studies have been conducted. While previous studies illustrated that phosphine- and N-heterocyclic carbene-derived catalysts exhibited differing behavior, the origin of these effects has now been evaluated in detail. Many variables, including ligand class, sterics of the ligand and alkyne, temperature, and ring size being formed in intramolecular versions, all influence the extent of crossover observed. A computational evaluation of these effects suggests that dimerization of a key metallacyclic intermediate provides the origin of crossover. Protocols that proceed with crossover are typically less efficient than those without crossover given the thermodynamic stability and low reactivity of the dimeric metallacycles involved in crossover pathways. PMID:25401337

  11. Mechanistic implications of variable stoichiometries of oxygen consumption during tyrosinase catalyzed oxidation of monophenols and o-diphenols.

    PubMed

    Peñalver, María José; Hiner, Alexander N P; Rodríguez-López, José Neptuno; García-Cánovas, Francisco; Tudela, José

    2002-05-20

    The stoichiometry of oxygen consumption during tyrosinase-catalyzed oxidation of an o-diphenol (4-tert-butylcatechol, TBC) and a monophenol (4-tert-butylphenol, TBP) has been determined. At high [substrate]/[enzyme] ratios, in the case of o-diphenols, the stoichiometry of the enzyme-catalyzed reaction was always 1 O(2)/2 o-diphenols, although if the o-quinone product was unstable, the apparent stoichiometry could tend to 1 O(2)/1 o-diphenol due to regeneration of an o-diphenol in a side reaction. In the case of monophenols, the stoichiometry could be 1 O(2)/1 monophenol or 1.5 O(2)/1 monophenol depending if the o-quinone product was stable or unstable, respectively. However, at low [substrate]/[enzyme] ratios, the oxygen/substrate stoichiometry could, even in the case where stable products are formed, be lower than 1 O(2)/2 substrates for o-diphenols or higher than 1 O(2)/1 substrate for monophenols. These data supported the mechanism proposed by Rodríguez-López et al. [J. Biol. Chem. 267 (1992) 3801-3810], in which, during hydroxylation of monophenols, tyrosinase first transformed monophenol to o-diphenol and then either catalyzed a further oxidation to form o-quinone or released it into the reaction medium. In this second case, subsequent oxidation of the o-diphenol resulted in additional oxygen consumption. PMID:12009413

  12. Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones: A Detailed Mechanistic Study.

    PubMed

    Raoufmoghaddam, Saeed; Mannathan, Subramaniyan; Minnaard, Adriaan J; de Vries, Johannes G; Reek, Joost N H

    2015-12-14

    We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic analysis have provided a detailed insight into the reaction. Progress kinetic analysis demonstrated that neither catalyst decomposition nor product inhibition occurred during the catalysis. The reaction is first order in the palladium and aryl iodide, and zero order in the activated alkene, N-heterocyclic carbene (NHC) ligand, and DIPEA. The experiments with deuterated solvent ([D7]DMF) and deuterated base ([D15]Et3N) supported the role of the amine as a reductant in the reaction. The palladium complex [Pd(0)(NHC)(1)] has been identified as the resting state. The kinetic experiments by stopped-flow UV/Vis also revealed that the presence of the second substrate, benzylideneacetone 1, slows down the oxidative addition of 4-iodoanisole through its competing coordination to the palladium center. The kinetic and mechanistic studies indicated that the oxidative addition of the aryl iodide is the rate-determining step. Various scenarios for the oxidative addition step have been analyzed by using DFT calculations (bp86/def2-TZVP) that supported the inhibiting effect of substrate 1 by formation of resting state [Pd(0)(NHC)(1)] species at the cost of further increase in the energy barrier of the oxidative addition step. PMID:26561034

  13. Direct Comparison of Electrochemical and Spectrochemical Kinetics for Catalytic Oxygen Reduction

    SciTech Connect

    Wasylenko, Derek J.; Rodriguez, Carlos; Pegis, Michael L.; Mayer, James M.

    2014-09-10

    We describe here a direct comparison of electrochemical and spectrochemical experiments to determine rates and selectivity of oxygen reduction catalyzed by iron 5,10,15,20-meso-tetraphenylporphyrin chloride. Strong agreement was found between the two methods suggesting the same mechanism is occurring under both conditions, with the same overall third order rate constant kcat = (1.1 ± 0.1) × 106 M-2 s-1. This report provides a rare example of characterization of a redox catalytic process by two common but very different methods. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

  14. REDUCTION OF NOx EMISSION FROM COAL COMBUSTION THROUGH OXYGEN ENRICHMENT

    SciTech Connect

    Western Research Institute

    2006-07-01

    BOC Process Gas Solutions and Western Research Institute (WRI) conducted a pilot-scale test program to evaluate the impact of oxygen enrichment on the emissions characteristics of pulverized coal. The combustion test facility (CTF) at WRI was used to assess the viability of the technique and determine the quantities of oxygen required for NOx reduction from coal fired boiler. In addition to the experimental work, a series of Computational Fluid Dynamics (CFD) simulations were made of the CTF under comparable conditions. A series of oxygen enrichment test was performed using the CTF. In these tests, oxygen was injected into one of the following streams: (1) the primary air (PA), (2) the secondary air (SA), and (3) the combined primary and secondary air. Emission data were collected from all tests, and compared with the corresponding data from the baseline cases. A key test parameter was the burner stoichiometry ratio. A series of CFD simulation models were devised to mimic the initial experiments in which secondary air was enriched with oxygen. The results from these models were compared against the experimental data. Experimental evidence indicated that oxygen enrichment does appear to be able to reduce NOx levels from coal combustion, especially when operated at low over fire air (OFA) levels. The reductions observed however are significantly smaller than that reported by others (7-8% vs. 25-50%), questioning the economic viability of the technique. This technique may find favor with fuels that are difficult to burn or stabilize at high OFA and produce excessive LOI. While CFD simulation appears to predict NO amounts in the correct order of magnitude and the correct trend with staging, it is sensitive to thermal conditions and an accurate thermal prediction is essential. Furthermore, without development, Fluent's fuel-NO model cannot account for a solution sensitive fuel-N distribution between volatiles and char and thus cannot predict the trends seen in the

  15. Charge transfer induced activity of graphene for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Shen, Anli; Xia, Weijun; Zhang, Lipeng; Dou, Shuo; Xia, Zhenhai; Wang, Shuangyin

    2016-05-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR.

  16. Practical aspects of the oxygen reduction reaction (ORR)

    SciTech Connect

    Uribe, F.A.; Springer, T.E.; Wilson, M.S.; Zawodzinski, T.A. Jr.; Gottesfeld, S.

    1995-12-31

    The oxygen reduction reaction (ORR) is quite sensitive to the details of the three phase interface at which the reaction occurs. We describe here studies of the ORR at a well-defined recast Nafion/Pt microelectrode interface, emphasizing the effects of temperature and humidification on the reaction rate. We compare our results to those obtained in thin film composite electrodes used in polymer electrolyte fuel cells.

  17. Oxygen Evolution Catalyzed by Nickel-Iron Oxide Nanocrystals with a Nonequilibrium Phase.

    PubMed

    Bau, Jeremy A; Luber, Erik J; Buriak, Jillian M

    2015-09-01

    Mixed nickel-iron oxides are of great interest as electrocatalysts for the oxygen evolution reaction (OER), the kinetically challenging half-reaction required for the generation of hydrogen gas from water via electrolysis. Previously, we had reported the synthesis of single crystal, soluble nickel-iron oxide nanoparticles over a wide range of nickel:iron compositions, with a metastable cubic rock salt phase ([Ni,Fe]O) that can be isolated despite the low solubility of iron in cubic nickel oxide at ambient temperatures. Here, activity for OER was examined, catalyzed by these [Ni,Fe]O nanoparticles integrated with indium tin oxide (ITO) electrodes. Because the as-prepared [Ni,Fe]O nanoparticles are oleate-capped, the surface ligands needed to be removed to induce adherence to the ITO substrate, and to enable charge transfer and contact with water to enable OER catalysis. Two different approaches were taken to reduce or eliminate the coverage of oleate ligands in these films: UV irradiation (254 nm) and air plasma. UV irradiation proved to lead to better results in terms of stable and OER-active films at pH 13. Kinetic analysis revealed that the Tafel slopes of these nanoparticle [Ni,Fe]O OER electrodes were limited by the electrochemical surface area and were found to be within the range of 30 to 50 mV/decade. Across the four compositions of Ni:Fe studied, from 24:76 to 88:12, the observed overpotential at 10 mA/cm2 for the OER in basic conditions decreased from 0.47 to 0.30 V as the proportion of nickel increased from 24% to 88%. PMID:26293239

  18. Melanin accelerates the tyrosinase-catalyzed oxygenation of p-hydroxyanisole (MMEH)

    PubMed

    Menter, J M; Townsel, M E; Moore, C L; Williamson, G D; Soteres, B J; Fisher, M S; Willis, I

    1990-01-01

    Although pigment melanin has long been though of as "inert," recent work has attested to its chemical reactivity. In this communication, we report that either commercial synthetic melanin prepared by persulfate oxidation of tyrosine ("Sigma melanin") or sepia melanin extracted from cuttlefish markedly accelerates the in vitro oxygenation of p-hydroxyanisole (MMEH), catalyzed by mushroom or B-16 melanoma tyrosinase. Kinetics of 4-methoxy-1,2-benzoquinone formation (lambda max = 413 nm) or of molecular O2 uptake were biphasic, with an initial slow rate ("lag time") followed by a fast linear increase. The biphasic response reflects an initial slow hydroxylation followed by a fast dehydrogenation. Added melanin markedly decreased the lag time but had little effect on subsequent dehydrogenation. Similar effects were observed for tyrosine itself. A complex between MMEH and melanin appears to be the "active" species in these reactions. The results indicate that melanin acts as an electron conduit, which accepts electrons from the substrate and transfers them to tyrosinase. The magnitude of the effect depends on the type of melanin as well as on its oxidation state. Kinetic analysis indicates that both melanins are very efficient at transferring electron to tyrosinase, and that Sigma melanin is roughly threefold more efficient than sepia melanin. The qualitative similarity of reaction between the synthetic and "natural" melanins suggests that the former may serve as a first approximation to the in vivo situation. On the other hand, the observed quantitative differences and the sensitivity of these results to the chemical state of melanin suggests that this methodology might eventually be adapted as a non-destructive probe of melanin in situ.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2117269

  19. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    SciTech Connect

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  20. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    DOE PAGESBeta

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently andmore » a new strategy of developing the catalyst for oxygen evolution reaction.« less

  1. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao-Qing; Lee, Hung-Sui; Qu, Deyang

    2015-08-01

    Oxygen reduction and oxygen evolution reactions were studied on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2 /O2 rad - are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B -O2 2 - ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  2. Structural group analysis for soot reduction tendency of oxygenated fuels

    SciTech Connect

    Pepiot-Desjardins, P.; Pitsch, H.; Malhotra, R.; Kirby, S.R.; Boehman, A.L.

    2008-07-15

    Oxygenated additives are known to reduce soot formation in diesel engines. Numerous studies, both experimental and numerical, have reported that the reduction of particulate emissions depends on the molecular structure of the additives. In this paper, a structural group contribution approach is proposed to interpret experimental observations on the effect of oxygenated additives on the sooting propensities of hydrocarbon fuels. The statistically based method makes it possible to distinguish between chemical effects caused by the presence of oxygenated groups in the fuel mixture and mere dilution of the original fuel by the additive. The analysis was carried out on several experimental databases encompassing both premixed and nonpremixed configurations that include a new extensive set of smoke point measurements for mixtures of a given fuel with several oxygenated molecules. The current approach unifies the conclusions on the relative efficiency of the various oxygenated functionalities such as alcohols, esters, ethers, and carbonyl groups and provides a potential explanation for the seemingly contradictory trends exhibited by some raw experimental data. (author)

  3. Practical carbon-carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation.

    PubMed

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  4. Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation

    PubMed Central

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon–carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  5. Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

    SciTech Connect

    Stolbov, Sergey Alcántara Ortigoza, Marisol

    2015-04-21

    In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

  6. Sulfur and oxygen isotope studies of sulfate reduction

    NASA Astrophysics Data System (ADS)

    Farquhar, J.; Canfield, D. E.; Bao, H.; Masterson, A.; Johnston, D. T.; Wing, B. A.

    2007-12-01

    I will discuss insights into sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and specifically insight provided by experiments with natural populations of sulfate-reducing bacteria from Faellestrand, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45 ‰ for 34S/32S), with higher δ18O accompanying higher δ34S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of 17O-labelled water and the 17O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The 17O data provides evidence for recycling of sulfur from metabolic intermediates and for an 18O/16O fractionation of ~25-30 ‰ for dissimilatory sulfate reduction, a magnitude that is consistent with isotopic exchange between a sulfite species and cell water. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96 %), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (~70%) and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ18O, δ34S, 17O labels, and Δ33S.

  7. Reductive metabolism of oxymatrine is catalyzed by microsomal CYP3A4

    PubMed Central

    Liu, Wenqin; Shi, Jian; Zhu, Lijun; Dong, Lingna; Luo, Feifei; Zhao, Min; Wang, Ying; Hu, Ming; Lu, Linlin; Liu, Zhongqiu

    2015-01-01

    Oxymatrine (OMT) is a pharmacologically active primary quinolizidine alkaloid with various beneficial and toxic effects. It is confirmed that, after oral administration, OMT could be transformed to the more toxic metabolite matrine (MT), and this process may be through the reduction reaction, but the study on the characteristics of this transformation is limited. The aim of this study was to investigate the characteristics of this transformation of OMT in the human liver microsomes (HLMs) and human intestinal microsomes (HIMs) and the cytochrome P450 (CYP) isoforms involved in this transformation. The current studies demonstrated that OMT could be metabolized to MT rapidly in HLMs and HIMs and CYP3A4 greatly contributed to this transformation. All HLMs, HIMs, and CYP3A4 isoform mediated reduction reaction followed typical biphasic kinetic model, and Km, Vmax, and CL were significant higher in HLMs than those in HIMs. Importantly, different oxygen contents could significantly affect the metabolism of OMT, and with the oxygen content decreased, the formation of metabolite was increased, suggesting this transformation was very likely a reduction reaction. Results of this in vitro study elucidated the metabolic pathways and characteristics of metabolism of OMT to MT and would provide a theoretical basis and guidance for the safe application of OMT. PMID:26586934

  8. Oxygen reduction by lithiated graphene and graphene-based materials.

    PubMed

    Kataev, Elmar Yu; Itkis, Daniil M; Fedorov, Alexander V; Senkovsky, Boris V; Usachov, Dmitry Yu; Verbitskiy, Nikolay I; Grüneis, Alexander; Barinov, Alexei; Tsukanova, Daria Yu; Volykhov, Andrey A; Mironovich, Kirill V; Krivchenko, Victor A; Rybin, Maksim G; Obraztsova, Elena D; Laubschat, Clemens; Vyalikh, Denis V; Yashina, Lada V

    2015-01-27

    Oxygen reduction reaction (ORR) plays a key role in lithium-air batteries (LABs) that attract great attention thanks to their high theoretical specific energy several times exceeding that of lithium-ion batteries. Because of their high surface area, high electric conductivity, and low specific weight, various carbons are often materials of choice for applications as the LAB cathode. Unfortunately, the possibility of practical application of such batteries is still under question as the sustainable operation of LABs with carbon cathodes is not demonstrated yet and the cyclability is quite poor, which is usually associated with oxygen reduced species side reactions. However, the mechanisms of carbon reactivity toward these species are still unclear. Here, we report a direct in situ X-ray photoelectron spectroscopy study of oxygen reduction by lithiated graphene and graphene-based materials. Although lithium peroxide (Li2O2) and lithium oxide (Li2O) reactions with carbon are thermodynamically favorable, neither of them was found to react even at elevated temperatures. As lithium superoxide is not stable at room temperature, potassium superoxide (KO2) prepared in situ was used instead to test the reactivity of graphene with superoxide species. In contrast to Li2O2 and Li2O, KO2 was demonstrated to be strongly reactive. PMID:25560087

  9. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

    SciTech Connect

    Cao, Ruiguo; Walter, Eric D.; Xu, Wu; Nasybulin, Eduard N.; Bhattacharya, Priyanka; Bowden, Mark E.; Engelhard, Mark H.; Zhang, Jiguang

    2014-09-01

    The oxygen reduction/evolution reaction (ORR/OER) mechanisms in nonaqueous Li-O2 batteries have been investigated by using electron paramagnetic resonance spectroscopy in this work. We identified the superoxide radical anion (O2•-) as an intermediate in the ORR process using 5,5-dimethyl-pyrroline N-oxide as a spin trap, while no O2•- in OER was detected during the charge process. These findings provide insightful understanding on the fundamental oxygen reaction mechanisms in rechargeable nonaqueous Li-O2 batteries.

  10. Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

    USGS Publications Warehouse

    Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Marvin-DiPasquale, Mark C.

    2013-01-01

    Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, rhom = khom [FeOH+] [Hg(OH)2]; khom = 7.19 × 10+3 L (mol min)−1. Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe2O3) increased and γ-alumina (γ-Al2O3) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression rhet = khet [>SOFe(II)] [Hg(OH)2], where >SOFe(II) is the total adsorbed Fe(II) concentration; khet values were 5.36 × 10+3, 4.69 × 10+3, and 1.08 × 10+2 L (mol min)−1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

  11. Computational Characterization of Redox Non-Innocence in Cobalt-Bis(Diaryldithiolene)-Catalyzed Proton Reduction.

    PubMed

    Panetier, Julien A; Letko, Christopher S; Tilley, T Don; Head-Gordon, Martin

    2016-01-12

    Localized orbital bonding analysis (LOBA) was employed to probe the oxidation state in cobalt-bis(diaryldithiolene)-catalyzed proton reduction in nonaqueous media. LOBA calculations provide both the oxidation state and chemically intuitive views of bonding in cobalt-bis(diaryldithiolene) species and therefore allow characterization of the role of the redox non-innocent dithiolene ligand. LOBA results show that the reduction of the monoanion species [1Br](-) is metal-centered and gives a cobalt(II) ion species, [1Br](2-), coordinated to two dianionic ene-1,2-dithiolates. This electronic configuration is in agreement with the solution magnetic moment observed for the analogous salt [1F](2-) (μeff = 2.39 μB). Protonation of [1Br](2-) yields the cobalt(III)-hydride [1Br(CoH)](-) species in which the Co-H bond is computed to be highly covalent (Löwdin populations close to 0.50 on cobalt and hydrogen atoms). Further reduction of [1Br(CoH)](-) forms a more basic cobalt(II)-H intermediate [1Br(CoH)](2-) (S = 0) from which protonation at sulfur gives a S-H bond syn to the Co-H bond. Formation of a cobalt-dihydrogen [1Br(CoH2)](-) intermediate is calculated to occur via a homocoupling (H(•) + H(•) → H2) step with a free energy of activation of 5.9 kcal/mol in solution (via C-PCM approach). PMID:26598074

  12. Unification of reaction pathway and kinetic scheme for N2 reduction catalyzed by nitrogenase

    PubMed Central

    Lukoyanov, Dmitriy; Yang, Zhi-Yong; Barney, Brett M.; Dean, Dennis R.; Seefeldt, Lance C.; Hoffman, Brian M.

    2012-01-01

    Nitrogenase catalyzes the reduction of N2 and protons to yield two NH3 and one H2. Substrate binding occurs at a complex organo-metallocluster called FeMo-cofactor (FeMo-co). Each catalytic cycle involves the sequential delivery of eight electrons/protons to this cluster, and this process has been framed within a kinetic scheme developed by Lowe and Thorneley. Rapid freezing of a modified nitrogenase under turnover conditions using diazene, methyldiazene (HN = N-CH3), or hydrazine as substrate recently was shown to trap a common intermediate, designated I. It was further concluded that the two N-atoms of N2 are hydrogenated alternately (“Alternating” (A) pathway). In the present work, Q-band CW EPR and 95Mo ESEEM spectroscopy reveal such samples also contain a common intermediate with FeMo-co in an integer-spin state having a ground-state “non-Kramers” doublet. This species, designated H, has been characterized by ESEEM spectroscopy using a combination of 14,15N isotopologs plus 1,2H isotopologs of methyldiazene. It is concluded that: H has NH2 bound to FeMo-co and corresponds to the penultimate intermediate of N2 hydrogenation, the state formed after the accumulation of seven electrons/protons and the release of the first NH3; I corresponds to the final intermediate in N2 reduction, the state formed after accumulation of eight electrons/protons, with NH3 still bound to FeMo-co prior to release and regeneration of resting-state FeMo-co. A proposed unification of the Lowe-Thorneley kinetic model with the “prompt” alternating reaction pathway represents a draft mechanism for N2 reduction by nitrogenase. PMID:22460797

  13. Oxygen exchange reactions catalyzed by vacuolar H(+)-translocating pyrophosphatase. Evidence for reversible formation of enzyme-bound pyrophosphate.

    PubMed

    Baykov, A A; Kasho, V N; Bakuleva, N P; Rea, P A

    1994-08-22

    Vacuolar membrane-derived vesicles isolated from Vigna radiata catalyze oxygen exchange between medium phosphate and water. On the basis of the inhibitor sensitivity and cation requirements of the exchange activity, it is almost exclusively attributable to the vacuolar H(+)-pyrophosphatase (V-PPase). The invariance of the partition coefficient and the results of kinetic modeling indicate that exchange proceeds via a single reaction pathway and results from the reversal of enzyme-bound pyrophosphate synthesis. Comparison of the exchange reactions catalyzed by V-PPase and soluble PPases suggests that the two classes of enzyme mediate P(i)-HOH exchange by the same mechanism and that the intrinsic reversibility of the V-PPase is no greater than that of soluble PPases. PMID:8070586

  14. Recent advances in the kinetics of oxygen reduction

    SciTech Connect

    Adzic, R.

    1996-07-01

    Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.

  15. Apparatus for Screening Multiple Oxygen-Reduction Catalysts

    NASA Technical Reports Server (NTRS)

    Whitacre, Jay; Narayanan, Sekharipuram

    2009-01-01

    An apparatus that includes an array of multiple electrodes has been invented as a means of simultaneously testing multiple materials for their utility as oxygen-reduction catalysts in fuel cells. The apparatus ensures comparability of test results by exposing all the catalyst-material specimens to the same electrolytic test solution at the same potential. Heretofore, it has been possible to test only one specimen at a time, using a precise rotating disk electrode that provides a controlled flux of solution to the surface of the specimen.

  16. Nickel-Catalyzed Reductive Conjugate Addition to Enones Via Allylnickel Intermediates

    PubMed Central

    Shrestha, Ruja; Dorn, Stephanie C. M.; Weix, Daniel J.

    2013-01-01

    An alternative method to copper-catalyzed conjugate addition followed by enolate silylation for the synthesis of β-di-substituted silyl enol ether products (R1(R2)HCCH=C(OSiR43)R3) is presented. This method uses haloarenes instead of nucleophilic aryl reagents. Nickel ligated to either neocuproine or bipyridine couples an α,β-unsaturated ketone or aldehyde (R2HC=CHC(O)R3) with an organic halide (R1-X) in the presence of a trialkylchlorosilane reagent (Cl-SiR43). Reactions are assembled on the bench-top and tolerate a variety of functional groups (aldehyde, ketone, nitrile, sulfone, pentafluorosulfur, and N-aryltrifluoroacetamide), electron-rich iodoarenes, and electron-poor haloarenes. Mechanistic studies have confirmed the first example of a catalytic reductive conjugate addition of organic halides that proceeds via an allylnickel intermediate. Selectivity is attributed to: 1) rapid, selective reaction of LNi0 with chlorotriethylsilane and enone in the presence of other organic electrophiles, and 2) minimization of enone dimerization by ligand steric effects. PMID:23270480

  17. The heme-copper oxidases of Thermus thermophilus catalyze the reduction of nitric oxide: Evolutionary implications

    PubMed Central

    Giuffrè, Alessandro; Stubauer, Gottfried; Sarti, Paolo; Brunori, Maurizio; Zumft, Walter G.; Buse, Gerhard; Soulimane, Tewfik

    1999-01-01

    We show that the heme-copper terminal oxidases of Thermus thermophilus (called ba3 and caa3) are able to catalyze the reduction of nitric oxide (NO) to nitrous oxide (N2O) under reducing anaerobic conditions. The rate of NO consumption and N2O production were found to be linearly dependent on enzyme concentration, and activity was abolished by enzyme denaturation. Thus, contrary to the eukaryotic enzyme, both T. thermophilus oxidases display a NO reductase activity (3.0 ± 0.7 mol NO/mol ba3 × min and 32 ± 8 mol NO/mol caa3 × min at [NO] ≈ 50 μM and 20°C) that, though considerably lower than that of bona fide NO reductases (300–4,500 mol NO/mol enzyme × min), is definitely significant. We also show that for ba3 oxidase, NO reduction is associated to oxidation of cytochrome b at a rate compatible with turnover, suggesting a mechanism consistent with the stoichiometry of the overall reaction. We propose that the NO reductase activity of T. thermophilus oxidases may depend on a peculiar CuB+ coordination, which may be revealed by the forthcoming three-dimensional structure. These findings support the hypothesis of a common phylogeny of aerobic respiration and bacterial denitrification, which was proposed on the basis of structural similarities between the Pseudomonas stutzeri NO reductase and the cbb3 terminal oxidases. Our findings represent functional evidence in support of this hypothesis. PMID:10611279

  18. Unusual High Oxygen Reduction Performance in All-Carbon Electrocatalysts

    PubMed Central

    Wei, Wei; Tao, Ying; Lv, Wei; Su, Fang-Yuan; Ke, Lei; Li, Jia; Wang, Da-Wei; Li, Baohua; Kang, Feiyu; Yang, Quan-Hong

    2014-01-01

    Carbon-based electrocatalysts are more durable and cost-effective than noble materials for the oxygen reduction reaction (ORR), which is an important process in energy conversion technologies. Heteroatoms are considered responsible for the excellent ORR performance in many carbon-based electrocatalysts. But whether an all-carbon electrocatalyst can effectively reduce oxygen is unknown. We subtly engineered the interfaces between planar graphene sheets and curved carbon nanotubes (G-CNT) and gained a remarkable activity/selectivity for ORR (larger current, and n = 3.86, ~93% hydroxide + ~7% peroxide). This performance is close to that of Pt; and the durability is much better than Pt. We further demonstrate the application of this G-CNT hybrid as an all-carbon cathode catalyst for lithium oxygen batteries.We speculate that the high ORR activity of this G-CNT hybrid stems from the localized charge separation at the interface of the graphene and carbon nanotube, which results from the tunneling electron transfer due to the Fermi level mismatch on the planar and curved sp2 surfaces. Our result represents a conceptual breakthrough and pioneers the new avenues towards practical all-carbon electrocatalysis. PMID:25189141

  19. Oxygen reduction reaction on stepped platinum surfaces in alkaline media.

    PubMed

    Rizo, Ruben; Herrero, Enrique; Feliu, Juan M

    2013-10-01

    The oxygen reduction reaction (ORR) in 0.1 M NaOH on platinum single crystal electrodes has been studied using hanging meniscus rotating disk electrode configuration. Basal planes and stepped surfaces with (111) and (100) terraces have been employed. The results indicate that the Pt(111) electrode has the highest electrocatalytic activity among all the studied surfaces. The addition of steps on this electrode surface significantly diminishes the reactivity of the surface towards the ORR. In fact, the reactivity of the steps on the surfaces with wide terraces can be considered negligible with respect to that measured for the terrace. On the other hand, Pt(100) and Pt(110) electrodes have much lower activity than the Pt(111) electrode. These results have been compared with those obtained in acid media to understand the effect of the pH and the adsorbed OH on the mechanism. It is proposed that the surface covered by adsorbed OH is active for the reduction of the oxygen molecules. PMID:23936903

  20. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  1. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-04-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.

  2. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction

    PubMed Central

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  3. Cage-bell Pt-Pd nanostructures with enhanced catalytic properties and superior methanol tolerance for oxygen reduction reaction.

    PubMed

    Chen, Dong; Ye, Feng; Liu, Hui; Yang, Jun

    2016-01-01

    Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd(2+) ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction. PMID:27079897

  4. Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings

    PubMed Central

    Jackson, Evan P.; Malik, Hasnain A.; Sormunen, Grant J.; Baxter, Ryan D.; Liu, Peng; Wang, Hengbin; Shareef, Abdur-Rafay; Montgomery, John

    2015-01-01

    CONSPECTUS The control of regiochemistry is a considerable challenge in the development of a wide array of catalytic processes. Simple π-components such as alkenes, alkynes, 1,3-dienes, and allenes are among the many classes of substrates that present complexities in regioselective catalysis. Considering an internal alkyne as a representative example, when steric and electronic differences between the two substituents are minimal, differentiating among the two termini of the alkyne presents a great challenge. In cases where the differences between the alkyne substituents are substantial, overcoming those biases to access the regioisomer opposite that favored by substrate biases often presents an even greater challenge. Nickel-catalyzed reductive couplings of unsymmetrical π-components make up a group of reactions where control of regiochemistry presents a challenging but important objective. In the course of our studies of aldehyde-alkyne reductive couplings, complementary solutions to challenges in regiocontrol have been developed. Through careful selection of the ligand and reductant, as well as the more subtle reaction variables such as temperature and concentration, effective protocols have been established that allow highly selective access to either regiosiomer of the the allylic alcohol products using a wide range of unsymmetrical alkynes. Computational studies and an evaluation of reaction kinetics have provided an understanding of the origin of the regioselectivity control. Throughout the various procedures described, the development of ligand-substrate interactions play a key role, and the overall kinetic descriptions were found to differ between protocols. Rational alteration of the rate-determining step plays a key role in the regiochemistry reversal strategy, and in one instance, the two possible regioisomeric outcomes in a single reaction were found to operate by different kinetic descriptions. With this mechanistic information in hand, the

  5. Regional oxygen reduction and denitrification rates, San Joaquin Valley, USA

    NASA Astrophysics Data System (ADS)

    Green, C. T.; Jurgens, B. C.; Zhang, Y.; Starn, J. J.; Visser, A.; Singleton, M. J.; Esser, B. K.

    2015-12-01

    Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into residence times and rates of O2 reduction and denitrification using a novel approach of multi-model residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwater age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The residence time distribution approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF6, CFCs, 3H, He from 3H, 14C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variance than produced by individual RTD models. The set of multi-model RTDs was used in combination with NO3- and dissolved gas data to estimate zero order and first order rates of O2 reduction and denitrification. Results indicated that these rates followed approximately log-normal distributions. Rates of O2 reduction and denitrification were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O2 reduction rates. Results indicate that the multi-model approach can improve estimation of age distributions, and that, because of the correlations, relatively easily measured O2 rates can provide information about trends in denitrification rates, which are more difficult to measure.

  6. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    SciTech Connect

    Gopalan, Srikanth

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  7. Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.

    PubMed

    Garza, Victoria J; Krische, Michael J

    2016-03-23

    Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition. PMID:26958737

  8. A hybrid DNA-templated gold nanocluster for enhanced enzymatic reduction of oxygen

    DOE PAGESBeta

    Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; Desireddy, Anil; Artyushkova, Kateryna; Boncella, Amy E.; Atanassov, Plamen; Martinez, Jennifer S.

    2015-08-19

    We report the synthesis and characterization of a new DNA-templated gold nanocluster (AuNC) of ~1 nm in diameter and possessing ~7 Au atoms. When integrated with bilirubin oxidase (BOD) and single walled carbon nanotubes (SWNTs), the AuNC acts as an enhancer of electron transfer (ET) and lowers the overpotential of electrocatalytic oxygen reduction reaction (ORR) by ~15 mV as compared to the enzyme alone. In addition, the presence of AuNC causes significant enhancements in the electrocatalytic current densities at the electrode. Control experiments show that such enhancement of ORR by the AuNC is specific to nanoclusters and not to plasmonicmore » gold particles. Rotating ring disk electrode (RRDE) measurements confirm 4e– reduction of O2 to H2O with minimal production of H2O2, suggesting that the presence of AuNC does not perturb the mechanism of ORR catalyzed by the enzyme. This unique role of the AuNC as enhancer of ET at the enzyme-electrode interface makes it a potential candidate for the development of cathodes in enzymatic fuel cells, which often suffer from poor electronic communication between the electrode surface and the enzyme active site. In conclusion, the AuNC displays phosphorescence with large Stokes shift and microsecond lifetime.« less

  9. A hybrid DNA-templated gold nanocluster for enhanced enzymatic reduction of oxygen

    SciTech Connect

    Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; Desireddy, Anil; Artyushkova, Kateryna; Boncella, Amy E.; Atanassov, Plamen; Martinez, Jennifer S.

    2015-08-19

    We report the synthesis and characterization of a new DNA-templated gold nanocluster (AuNC) of ~1 nm in diameter and possessing ~7 Au atoms. When integrated with bilirubin oxidase (BOD) and single walled carbon nanotubes (SWNTs), the AuNC acts as an enhancer of electron transfer (ET) and lowers the overpotential of electrocatalytic oxygen reduction reaction (ORR) by ~15 mV as compared to the enzyme alone. In addition, the presence of AuNC causes significant enhancements in the electrocatalytic current densities at the electrode. Control experiments show that such enhancement of ORR by the AuNC is specific to nanoclusters and not to plasmonic gold particles. Rotating ring disk electrode (RRDE) measurements confirm 4e– reduction of O2 to H2O with minimal production of H2O2, suggesting that the presence of AuNC does not perturb the mechanism of ORR catalyzed by the enzyme. This unique role of the AuNC as enhancer of ET at the enzyme-electrode interface makes it a potential candidate for the development of cathodes in enzymatic fuel cells, which often suffer from poor electronic communication between the electrode surface and the enzyme active site. In conclusion, the AuNC displays phosphorescence with large Stokes shift and microsecond lifetime.

  10. Highly Functional Bioinspired Fe/N/C Oxygen Reduction Reaction Catalysts: Structure-Regulating Oxygen Sorption.

    PubMed

    Yao, Yingfang; You, Yong; Zhang, Gaixia; Liu, Jianguo; Sun, Haoran; Zou, Zhigang; Sun, Shuhui

    2016-03-16

    Tuna is one of the most rapid and distant swimmers. Its unique gill structure with the porous lamellae promotes fast oxygen exchange that guarantees tuna's high metabolic and athletic demands. Inspired by this specific structure, we designed and fabricated microporous graphene nanoplatelets (GNPs)-based Fe/N/C electrocatalysts for oxygen reduction reaction (ORR). Careful control of GNP structure leads to the increment of microporosity, which influences the O2 adsorption positively and desorption oppositely, resulting in enhanced O2 diffusion, while experiencing reduced ORR kinetics. Working in the cathode of proton-exchange membrane fuel cells, the GNP catalysts require a compromise between adsorption/desorption for effective O2 exchange, and as a result, appropriate microporosity is needed. In this work, the highest power density, 521 mW·cm(-2), at zero back pressure is achieved. PMID:26902179

  11. Effects of ionomer morphology on oxygen reduction on Pt

    SciTech Connect

    Chlistunoff, Jerzy; Pivovar, Bryan

    2015-05-21

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared and equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.

  12. Recent Advances in Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol; Chenitz, Regis

    2016-03-23

    The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core-shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided. PMID:26886420

  13. First principles based mean field model for oxygen reduction reaction.

    PubMed

    Jinnouchi, Ryosuke; Kodama, Kensaku; Hatanaka, Tatsuya; Morimoto, Yu

    2011-12-21

    A first principles-based mean field model was developed for the oxygen reduction reaction (ORR) taking account of the coverage- and material-dependent reversible potentials of the elementary steps. This model was applied to the simulation of single crystal surfaces of Pt, Pt alloy and Pt core-shell catalysts under Ar and O(2) atmospheres. The results are consistent with those shown by past experimental and theoretical studies on surface coverages under Ar atmosphere, the shape of the current-voltage curve for the ORR on Pt(111) and the material-dependence of the ORR activity. This model suggests that the oxygen associative pathway including HO(2)(ads) formation is the main pathway on Pt(111), and that the rate determining step (RDS) is the removal step of O(ads) on Pt(111). This RDS is accelerated on several highly active Pt alloys and core-shell surfaces, and this acceleration decreases the reaction intermediate O(ads). The increase in the partial pressure of O(2)(g) increases the surface coverage with O(ads) and OH(ads), and this coverage increase reduces the apparent reaction order with respect to the partial pressure to less than unity. This model shows details on how the reaction pathway, RDS, surface coverages, Tafel slope, reaction order and material-dependent activity are interrelated. PMID:22064886

  14. Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

    SciTech Connect

    Schlautman, Mark A.

    2013-07-14

    Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

  15. Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±)-ezetimibe

    PubMed Central

    Isoda, Motoyuki; Sato, Kazuyuki; Kunugi, Yurika; Tokonishi, Satsuki; Tarui, Atsushi; Minami, Hideki

    2016-01-01

    Summary An effective synthesis for syn-β-lactams was achieved using a Rh-catalyzed reductive Mannich-type reaction. A rhodium–hydride complex (Rh–H) derived from diethylzinc (Et2Zn) and a Rh catalyst was used for the 1,4-reduction of an α,β-unsaturated ester to give a Reformatsky-type reagent, which in turn, reacted with an imine to give the syn-β-lactam. Additionally, the reaction was applied to the synthesis of (±)-ezetimibe, a potent β-lactamic cholesterol absorption inhibitor. PMID:27559413

  16. Carbon-Free Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.

    PubMed

    Yang, Yang; Fei, Huilong; Ruan, Gedeng; Li, Lei; Wang, Gunuk; Kim, Nam Dong; Tour, James M

    2015-09-23

    A nanoporous Ag-embedded SnO2 thin film was fabricated by anodic treatment of electrodeposited Ag-Sn alloy layers. The ordered nanoporous structure formed by anodization played a key role in enhancing the electrocatalytic performance of the Ag-embedded SnO2 layer in several ways: (1) the roughness factor of the thin film is greatly increased from 23 in the compact layer to 145 in the nanoporous layer, creating additional active sites that are involved in oxygen electrochemical reactions; (2) a trace amount of Ag (∼1.7 at %, corresponding to a Ag loading of ∼3.8 μg cm(-2)) embedded in the self-organized SnO2 nanoporous matrix avoids the agglomeration of nanoparticles, which is a common problem leading to the electrocatalyst deactivation; (3) the fabricated nanoporous thin film is active without additional additives or porous carbon that is usually necessary to support and stabilize the electrocatalyst. More importantly, the Ag-embedded SnO2 nanoporous thin film shows outstanding bifunctional oxygen electrochemical performance (oxygen reduction and evolution reactions) that is considered a promising candidate for use in metal-air batteries. The present technique has a wide range of applications for the preparation of other carbon-free electrocatalytic nanoporous films that could be useful for renewable energy production and storage applications. PMID:26320368

  17. Nanocatalyst superior to Pt for oxygen reduction reactions: the case of core/shell Ag(Au)/CuPd nanoparticles.

    PubMed

    Guo, Shaojun; Zhang, Xu; Zhu, Wenlei; He, Kai; Su, Dong; Mendoza-Garcia, Adriana; Ho, Sally Fae; Lu, Gang; Sun, Shouheng

    2014-10-22

    Controlling the electronic structure and surface strain of a nanoparticle catalyst has become an important strategy to tune and to optimize its catalytic efficiency for a chemical reaction. Using density functional theory (DFT) calculations, we predicted that core/shell M/CuPd (M = Ag, Au) NPs with a 0.8 or 1.2 nm CuPd2 shell have similar but optimal surface strain and composition and may surpass Pt in catalyzing oxygen reduction reactions. We synthesized monodisperse M/CuPd NPs by the coreduction of palladium acetylacetonate and copper acetylacetonate in the presence of Ag (or Au) nanoparticles with controlled shell thicknesses of 0.4, 0.75, and 1.1 nm and CuPd compositions and evaluated their catalysis for the oxygen reduction reaction in 0.1 M KOH solution. As predicted, our Ag/Cu37Pd63 and Au/Cu40Pd60 catalysts with 0.75 and 1.1 nm shells were more efficient catalysts than the commercial Pt catalyst (Fuel Cells Store), with their mass activity reaching 0.20 A/mg of noble metal at -0.1 V vs Ag/AgCl (4 M KCl); this was over 3 times higher than that (0.06 A/mg Pt) from the commercial Pt. These Ag(Au)/CuPd nanoparticles are promising non-Pt catalysts for oxygen reduction reactions. PMID:25279704

  18. Synthesis of ethers by GaBr3 -catalyzed reduction of carboxylic acid esters and lactones by siloxanes.

    PubMed

    Biermann, Ursula; Metzger, Jürgen O

    2014-02-01

    Ethers were synthesized by reduction of the respective esters catalyzed by gallium bromide (GaBr3 ) and using siloxanes, preferentially 1,1,3,3-tetramethyldisiloxane, as reductant. Methyl oleate, triglycerides, that is, tributyrine and glyceryl triundec-10-enoate as well as γ- and δ-lactones were converted into the respective ethers in high to moderate yields. γ-Lactones were reduced with high selectivity in the presence of a methyl ester functionality. The reduction has been carried out at room temperature or moderately elevated temperature of up to 60 °C using stoichiometric amounts of the reductant and 0.005-0.01 equiv of GaBr3 as catalyst per ester functionality without any solvent added. After a reaction time of 1-4 h the conversion of the substrate was 100 %. The product was separated from polymeric siloxanes formed as coupled product by simple distillation. PMID:24488681

  19. Defective titanium dioxide single crystals exposed by high-energy {001} facets for efficient oxygen reduction

    NASA Astrophysics Data System (ADS)

    Pei, Dan-Ni; Gong, Li; Zhang, Ai-Yong; Zhang, Xing; Chen, Jie-Jie; Mu, Yang; Yu, Han-Qing

    2015-10-01

    The cathodic material plays an essential role in oxygen reduction reaction for energy conversion and storage systems. Titanium dioxide, as a semiconductor material, is usually not recognized as an efficient oxygen reduction electrocatalyst owning to its low conductivity and poor reactivity. Here we demonstrate that nano-structured titanium dioxide, self-doped by oxygen vacancies and selectively exposed with the high-energy {001} facets, exhibits a surprisingly competitive oxygen reduction activity, excellent durability and superior tolerance to methanol. Combining the electrochemical tests with density-functional calculations, we elucidate the defect-centred oxygen reduction reaction mechanism for the superiority of the reductive {001}-TiO2-x nanocrystals. Our findings may provide an opportunity to develop a simple, efficient, cost-effective and promising catalyst for oxygen reduction reaction in energy conversion and storage technologies.

  20. Defective titanium dioxide single crystals exposed by high-energy {001} facets for efficient oxygen reduction

    PubMed Central

    Pei, Dan-Ni; Gong, Li; Zhang, Ai-Yong; Zhang, Xing; Chen, Jie-Jie; Mu, Yang; Yu, Han-Qing

    2015-01-01

    The cathodic material plays an essential role in oxygen reduction reaction for energy conversion and storage systems. Titanium dioxide, as a semiconductor material, is usually not recognized as an efficient oxygen reduction electrocatalyst owning to its low conductivity and poor reactivity. Here we demonstrate that nano-structured titanium dioxide, self-doped by oxygen vacancies and selectively exposed with the high-energy {001} facets, exhibits a surprisingly competitive oxygen reduction activity, excellent durability and superior tolerance to methanol. Combining the electrochemical tests with density-functional calculations, we elucidate the defect-centred oxygen reduction reaction mechanism for the superiority of the reductive {001}-TiO2−x nanocrystals. Our findings may provide an opportunity to develop a simple, efficient, cost-effective and promising catalyst for oxygen reduction reaction in energy conversion and storage technologies. PMID:26493365

  1. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

    PubMed

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-04-13

    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis. PMID:26984323

  2. Palladium Monolayer and Palladium Alloy Electrocatalysts for Oxygen Reduction

    SciTech Connect

    Shao,M.; Huang, T.; Liu, P.; Zhang, J.; Sasaki, K.; Vukmirovic, M.; Adzic, R.

    2006-01-01

    We investigated the oxygen-reduction reaction (ORR) on Pd monolayers on various surfaces and on Pd alloys to obtain a substitute for Pt and to elucidate the origin of their activity. The activity of Pd monolayers supported on Ru(0001), Rh(111), Ir(111), Pt(111), and Au(111) increased in the following order: Pd/Ru(0001) < Pd/Ir(111) < Pd/Rh(111) < Pd/Au(111) < Pd/Pt(111). Their activity was correlated with their d-band centers, which were calculated using density functional theory (DFT). We found a volcano-type dependence of activity on the energy of the d-band center of Pd monolayers, with Pd/Pt(111) at the top of the curve. The activity of the non-Pt Pd{sub 2}Co/C alloy electrocatalyst nanoparticles that we synthesized was comparable to that of commercial Pt-containing catalysts. The kinetics of the ORR on this electrocatalyst predominantly involves a four-electron step reduction with the first electron transfer being the rate-determining step. The downshift of the d-band center of the Pd 'skin', which constitutes the alloy surface due to the strong surface segregation of Pd at elevated temperatures, determined its high ORR activity. Additionally, it showed very high methanol tolerance, retaining very high catalytic activity for the ORR at high concentrations of methanol. Provided its stability is satisfactory, this catalyst might possibly replace Pt in fuel-cell cathodes, especially those of direct methanol oxidation fuel cells (DMFCs).

  3. The concept of reactive surface area applied to uncatalyzed and catalyzed carbon (char) gasification in carbon dioxide and oxygen

    SciTech Connect

    Lizzio, A.A.

    1990-01-01

    The virtues of, and/or problems with, utilizing the concepts of total and active surface area to explain the reactivity profiles were evaluated and discussed. An alternative approach, involving the concept of reactive surface area (RSA), was introduced and results based on the direct measurement of RSA were presented. Here, reactive surface area is defined as the concentration of carbon atoms on which the carbon-oxygen C(O) surface intermediate forms and subsequently decomposes to give gaseous products. The transient kinetics (TK) approach gave a direct measurement of RSA for chars gasified in CO{sub 2} and O{sub 2}. A temperature-programmed desorption technique was also used to determine the amount of reactive surface intermediate formed on these chars during gasification. A comparison of turnover frequencies for different chars gasified in 1 atm CO{sub 2} suggested that char gasification mat be a structure sensitive reaction. The concept of RSA was also used to achieve a better quantitative understanding of catalyzed char reactivity variations with conversion in CO{sub 2}. For a calcium-exchanged lignite char gasified in 1 atm CO{sub 2}, a poor correlation was found between RSA and reactivity, suggesting that in addition to the direct decomposition of the reactive C(O) intermediate, other processes, e.g., oxygen spillover, contributed to the transient evolution of CO. An extensive study of Saran char loaded with calcium, potassium or nickel by impregnation to incipient wetness (IW) or ion exchange (IE) was undertaken. An excellent correlation was found between reactivity and RSA variations with conversion for both IW and IE K-catalyzed chars, suggesting that TK indeed titrates the reactive K-O-C complexes formed during gasification in CO{sub 2}.

  4. Formation of tungsten carbide nanoparticles on graphitized carbon to facilitate the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; He, Guoqiang; Cai, Mei; Meng, Hui; Shen, Pei Kang

    2013-11-01

    Tungsten carbide nanoparticles with the average size less than 5 nm uniformly dispersed on the graphitized carbon matrix have been successfully synthesized by a one-step ion-exchange method. This route is to locally anchor the interested species based on an ionic level exchange process using ion-exchange resin. The advantage of this method is the size control of targeted nanomaterial as well as the graphitization of resin at low temperatures catalyzed by iron salt. The Pt nanoparticles coupled with tungsten carbide nanoparticles on graphitized carbon nanoarchitecture form a stable electrocatalyst (Pt/WC-GC). The typical Pt/WC-GC electrocatalyst gives a Pt-mass activity of 247.7 mA mgPt-1, which is much higher than that of commercial Pt/C electrocatalyst (107.1 mA mgPt-1) for oxygen reduction reaction due to the synergistic effect between Pt and WC. The presented method is simple and could be readily scaled up for mass production of the nanomaterials.

  5. Oxygen reduction reaction on Cu-doped Ag cluster for fuel-cell cathode.

    PubMed

    Ma, Wenqiang; Chen, Fuyi; Zhang, Nan; Wu, Xiaoqiang

    2014-10-01

    The development of fuel cells as clean-energy technologies is largely limited by the prohibitive cost of the noble-metal catalysts needed for catalyzing the oxygen reduction reaction (ORR) in fuel cells. A fundamental understanding of catalyst design principle that links material structures to the catalytic activity can accelerate the search for highly active and abundant bimetallic catalysts to replace platinum. Here, we present a first-principles study of ORR on Ag12Cu cluster in alkaline environment. The adsorptions of O2, OOH, and OH on Cu-doped Ag13 are stronger than on Ag13. The d-band centers of adsorption sites show the Cu-doping makes d-electrons transferred to higher energy state, and improves O2 dissociation. ORR processes on Ag12Cu and Ag13 indicate Cu-doping can strongly promote ORR, and ORR process can be better preformed on Ag12Cu than on Ag13. For four-electron transfer, the effective reversible potential is 0.401 V/RHE on Ag12Cu in alkaline medium. PMID:25227449

  6. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    PubMed

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts. PMID:25334050

  7. Metallocorroles as Nonprecious-Metal Catalysts for Oxygen Reduction.

    PubMed

    Levy, Naomi; Mahammed, Atif; Kosa, Monica; Major, Dan T; Gross, Zeev; Elbaz, Lior

    2015-11-16

    The future of affordable fuel cells strongly relies on the design of earth-abundant (non-platinum) catalysts for the electrochemical oxygen reduction reaction (ORR). However, the bottleneck in the overall process occurs therein. We have examined herein trivalent Mn, Fe, Co, Ni, and Cu complexes of β-pyrrole-brominated corrole as ORR catalysts. The adsorption of these complexes on a high-surface-area carbon powder (BP2000) created a unique composite material, used for electrochemical measurements in acidic aqueous solutions. These experiments disclosed a clear dependence of the catalytic activity on the metal center of the complexes, in the order of Co>Fe>Ni>Mn>Cu. The best catalytic performance was obtained for the Co(III) corrole, whose onset potential was as positive as 0.81 V versus the reversible hydrogen electrode (RHE). Insight into the properties of these systems was gained by spectroscopic and computational characterization of the reduced and oxidized forms of the metallocorroles. PMID:26429211

  8. Porous platinum-based catalysts for oxygen reduction

    DOEpatents

    Erlebacher, Jonah D; Snyder, Joshua D

    2014-11-25

    A porous metal that comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A fuel cell includes a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte arranged between the first and the second electrodes. At least one of the first and second electrodes is coated with a porous metal catalyst for oxygen reduction, and the porous metal catalyst comprises platinum and has a specific surface area that is greater than 5 m.sup.2/g and less than 75 m.sup.2/g. A method of producing a porous metal according to an embodiment of the current invention includes producing an alloy consisting essentially of platinum and nickel according to the formula Pt.sub.xNi.sub.1-x, where x is at least 0.01 and less than 0.3; and dealloying the alloy in a substantially pH neutral solution to reduce an amount of nickel in the alloy to produce the porous metal.

  9. Effects of ionomer morphology on oxygen reduction on Pt

    DOE PAGESBeta

    Chlistunoff, Jerzy; Pivovar, Bryan

    2015-05-21

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared andmore » equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.« less

  10. Reduction in peak oxygen uptake after prolonged bed rest

    NASA Technical Reports Server (NTRS)

    Greenleaf, J. E.; Kozlowski, S.

    1982-01-01

    The hypothesis that the magnitude of the reduction in peak oxygen uptake (VO2) after bed rest is directly proportional to the level of pre-bed rest peak VO2 is tested. Complete pre and post-bed rest working capacity and body weight data were obtained from studies involving 24 men (19-24 years old) and 8 women (23-34 years old) who underwent bed rest for 14-20 days with no remedial treatments. Results of regression analyses of the present change in post-bed rest peak VO2 on pre-bed rest peak VO2 with 32 subjects show correlation coefficients of -0.03 (NS) for data expressed in 1/min and -0.17 for data expressed in ml/min-kg. In addition, significant correlations are found that support the hypothesis only when peak VO2 data are analyzed separately from studies that utilized the cycle ergometer, particularly with subjects in the supine position, as opposed to data obtained from treadmill peak VO2 tests. It is concluded that orthostatic factors, associated with the upright body position and relatively high levels of physical fitness from endurance training, appear to increase the variability of pre and particularly post-bed rest peak VO2 data, which would lead to rejection of the hypothesis.

  11. Oxygen reduction reaction activity on Pt{111} surface alloys.

    PubMed

    Attard, Gary A; Brew, Ashley; Ye, Jin-Yu; Morgan, David; Sun, Shi-Gang

    2014-07-21

    PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions. PMID:24986646

  12. Laccase-modified gold nanorods for electrocatalytic reduction of oxygen.

    PubMed

    Di Bari, Chiara; Shleev, Sergey; De Lacey, Antonio L; Pita, Marcos

    2016-02-01

    cathodes. Nanostructuring was provided by gold nanorods (AuNRs), which were characterized and covalently attached to electrodes made of low-density graphite. The nanostructured electrode was the scaffold for covalent and oriented attachment of ThLc. The bioelectrocatalytic currents measured for oxygen reduction were as high as 0.5 mA/cm(2 and 0.7 mA/cm(2), which were recorded under direct and mediated electron transfer regimes, respectively. )The experimental data were fitted to mathematical models showing that when the O2 is bioelectroreduced at high rotation speed of the electrode the heterogeneous electron transfer step is the rate-liming stage. The electrochemical measurement hints a wider population of non-optimally wired laccases than previously reported for 5–8 nm size Au nanoparticle-modified electrode, which could be due to a larger size of the AuNRs when compared to the laccases as well as their different crystal facets. PMID:26523503

  13. Combinatorial search for oxygen reduction reaction electrocatalysts: A review

    NASA Astrophysics Data System (ADS)

    Jeon, Min Ku; Lee, Chang Hwa; Park, Geun Il; Kang, Kweon Ho

    2012-10-01

    Oxygen reduction reaction (ORR) is one of the most interesting research issues in the academia and industries due to its importance in polymer electrolyte membrane fuel cells. Development of new ORR catalysts with low cost and high activity is under intensive research, but it is a time-consuming process because of wide range of alloys to be explored. Combinatorial synthesis and high-throughput screening techniques were suggested as new experimental approaches to accelerate the ORR electrocatalyst research. The combinatorial method is focused on the synthesis of concentrated arrays and quick evaluation of the arrays via various screening techniques. In this report, the combinatorial approaches for the ORR catalyst research were reviewed based on the screening methods. Four screening techniques of optical screening, scanning electrochemical microscopy, multielectrode half cell, and multielectrode full cell were introduced as the representative ones. Other approaches were also briefly introduced. Merits and limitations of each method were discussed and representative research results of each method were shown in detail.

  14. Occurrence and Characteristics of a Rapid Exchange of Phosphate Oxygens Catalyzed by Sarcoplasmic Reticulum Vesicles

    DOE R&D Accomplishments Database

    Kanazawa, T.; Boyer, P. D.

    1972-01-01

    Sarcoplasmic reticulum vesicles isolated from skeletal muscle actively take up Ca{sup ++} from the medium in the presence of Mg{sup ++} and ATP. This transport is coupled to ATP hydrolysis catalyzed by membrane-bound Ca{sup++}, Mg{sup ++}-ATPase which is activated by concurrent presence of Ca{sup ++} and Mg{sup ++}. Considerable informations have accumulated that give insight into the ATPase and its coupling to the calcium transport. The hydrolysis of ATP by this enzyme occurs through a phosphorylated intermediate. Formation and decomposition of the intermediate show vectorial requirements for Ca{sup ++} and Mg{sup ++}, suggesting an intimate involvement of the intermediate in the transport process. ATP synthesis from P{sub i} and ADP coupled to outflow of Ca{sup ++} from sarcoplasmic reticulum vesicles has recently been demonstrated. This indicates the reversibility of the entire process of calcium transport in sarcoplasmic reticulum vesicles.

  15. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

    PubMed

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  16. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGESBeta

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM basedmore » systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

  17. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  18. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    PubMed Central

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  19. Palladium-Catalyzed Ullmann Cross-Coupling/Tandem Reductive Cyclization Route to Key Members of the Uleine Alkaloid Family.

    PubMed

    Tang, Fei; Banwell, Martin G; Willis, Anthony C

    2016-04-01

    The trisubstituted cyclohexenone 12, generated through a palladium-catalyzed Ullmann cross-coupling reaction between o-iodonitrobenzene and a 4,5-trans-disubstituted 2-iodo-2-cyclohexen-1-one, engaged in a tandem reductive cyclization process upon exposure to hydrogen gas in the presence of Raney cobalt. As a result, the 1,5-methanoazocino[4,3-b]indole 13 was obtained and this could be readily elaborated to the racemic modifications of the alkaloids uleine, dasycarpidone, noruleine, and nordasycarpidone (1-4, respectively). PMID:26914482

  20. Palladium(II) Catalyzed Cyclization-Carbonylation-Cyclization Coupling Reaction of (ortho-Alkynyl Phenyl) (Methoxymethyl) Sulfides Using Molecular Oxygen as the Terminal Oxidant.

    PubMed

    Shen, Rong; Kusakabe, Taichi; Yatsu, Tomofumi; Kanno, Yuichiro; Takahashi, Keisuke; Nemoto, Kiyomitsu; Kato, Keisuke

    2016-01-01

    An efficient Pd(II)/Pd⁰-p-benzoquinone/hydroquinone-CuCl₂/CuCl catalyst system was developed that uses environmentally friendly molecular oxygen as the terminal oxidant to catalyze the cyclization-carbonylation-cyclization coupling reaction (CCC-coupling reaction) of (o-alkynyl phenyl) (methoxymethyl) sulfides. PMID:27607997

  1. Enantioselective Reduction of Ketones and Imines Catalyzed by (CN-Box)Re(V)-Oxo Complexes

    PubMed Central

    Nolin, Kristine A.; Ahn, Richard W.; Kobayashi, Yusuke; Kennedy-Smith, Joshua J.

    2012-01-01

    The development and application of chiral, non-racemic Re(V)-oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to (1) a tandem Meyer-Schuster rearrangement/reduction to access enantioenriched allylic alcohols and (2) the enantioselective reduction of imines. PMID:20623567

  2. Iron catalyzed reduction of chromate by dissimilatory iron-reducing bacteria.

    SciTech Connect

    Wielinga, B.W.; M.M. Mizuba; C.M. Hansel; S. Fendorf

    2001-02-01

    The toxicity and mobility of chromium can be diminished through its reduction from the hexavalent state to the trivalent form. Here we demonstrate a microbially mediated pathway for chromate reduction. Iron reducing bacteria, ubiquitous organisms within soils and sediments, stimulate chromate reduction by generating ferrous iron--a facile reductant of hexavalent chromium. Subsequent to reduction, Cr(III) then precipitates as a chromium hydroxide.

  3. The 2010 Field Demonstration of the Solar Carbothermal Reduction of Regolith to Produce Oxygen

    NASA Technical Reports Server (NTRS)

    Muscatello, Anthony; Gustafson, Robert (Bob)

    2010-01-01

    This slide presentation reviews a demonstration of the use of solar carbothermal reduction processing of regolith to produce oxygen and silicon from silica. A contractor developed the Carbothermal Regolith Reduction Module to demonstrate the extraction of oxygen from lunar regolith simulant using concentrated solar energy at a site that has similar terrain to the moon and Mars.

  4. Nanoparticle-catalyzed reductive bleaching for fabricating turn-off and enzyme-free amplified colorimetric bioassays.

    PubMed

    Li, Wei; Qiang, Weibing; Li, Jie; Li, Hui; Dong, Yifan; Zhao, Yaju; Xu, Danke

    2014-01-15

    Nanoparticle-catalyzed reductive bleaching reactions of colored substrates are emerging as a class of novel indicator reactions for fabricating enzyme-free amplified colorimetric biosensing (turn-off mode), which are exactly opposite to the commonly used oxidative coloring processes of colorless substrates in traditional enzyme-catalyzed amplified colorimetric bioassays (turn-on mode). In this work, a simple theoretical analysis shows that the sensitivity of this colorimetric bioassay can be improved by increasing the amplification factor (kcatΔt), or enhancing the binding affinity between analyte and receptor (Kd), or selecting the colored substrates with high extinction coefficients (ε). Based on this novel strategy, we have developed a turn-off and cost-effective amplified colorimetric thrombin aptasensor. This aptasensor made full use of sandwich binding of two affinity aptamers for increased specificity, magnetic particles for easy separation and enrichment, and gold nanoparticle (AuNP)-catalyzed reductive bleaching reaction to generate the amplified colorimetric signal. With 4-nitrophenol (4-NP) as the non-dye colored substrate, colorimetric bioassay of thrombin was achieved by the endpoint method with a detection limit of 91pM. In particular, when using methylene blue (MB) as the substrate, for the first time, a more convenient and efficient kinetic-based colorimetric thrombin bioassay was achieved without the steps of acidification termination and magnetic removal of particles, with a low detection limit of 10pM, which was superior to the majority of the existing colorimetric thrombin aptasensors. The proposed colorimetric protocol is expected to hold great promise in field analysis and point-of-care applications. PMID:23962710

  5. Sulfur and oxygen isotope fractionation during sulfate reduction coupled to anaerobic oxidation of methane is dependent on methane concentration

    NASA Astrophysics Data System (ADS)

    Deusner, Christian; Holler, Thomas; Arnold, Gail L.; Bernasconi, Stefano M.; Formolo, Michael J.; Brunner, Benjamin

    2014-08-01

    Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments - thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM up to 58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (εS34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (θO), as well as sulfate reduction rates (SRR). Smallest εS34 (21.9±1.9‰) and θO (0.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest εS34 (67.3±26.1‰) and θO (2.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that εS34, θO and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate-methane transition zones, AOM-SR is likely

  6. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions.

    PubMed

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO₂ and MnO₂) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ∼1,663 m(2) g(-1) and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn(-1) (corresponding to an energy density of 835 Wh kgZn(-1)), a peak power density of 55 mW cm(-2), and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm(-2). We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material. PMID:25849787

  7. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ˜1,663 m2 g-1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn-1 (corresponding to an energy density of 835 Wh kgZn-1), a peak power density of 55 mW cm-2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm-2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

  8. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    DOEpatents

    Adzic, Radoslav; Huang, Tao

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  9. Base metal-catalyzed benzylic oxidation of (aryl)(heteroaryl)methanes with molecular oxygen

    PubMed Central

    Sterckx, Hans; De Houwer, Johan; Mensch, Carl; Herrebout, Wouter; Tehrani, Kourosch Abbaspour

    2016-01-01

    Summary The methylene group of various substituted 2- and 4-benzylpyridines, benzyldiazines and benzyl(iso)quinolines was successfully oxidized to the corresponding benzylic ketones using a copper or iron catalyst and molecular oxygen as the stoichiometric oxidant. Application of the protocol in API synthesis is exemplified by the alternative synthesis of a precursor to the antimalarial drug Mefloquine. The oxidation method can also be used to prepare metabolites of APIs which is illustrated for the natural product papaverine. ICP–MS analysis of the purified reaction products revealed that the base metal impurity was well below the regulatory limit. PMID:26877817

  10. Cu(ii)-catalyzed enantioselective oxygen atom transfer from oxaziridine to oxindole derivatives with chiral phenanthroline.

    PubMed

    Naganawa, Yuki; Aoyama, Tomotaka; Nishiyama, Hisao

    2015-12-21

    In the presence of a Cu(ii) complex of axially chiral, N,N,O-tridentate phenanthroline ligand (S)-2, asymmetric oxygen atom transfer of oxindole derivatives (3) using Davis' oxaziridine (4) occurred to give the corresponding 3-aryl-3-hydroxy-2-oxindole derivatives (1) with excellent enantioselectivity (up to 96% ee). The X-ray crystallographic analysis of the isolated Cu(ii) complex disclosed its N,N,O-tridentate coordination, which is critical to realize effective catalytic activity. PMID:26456035

  11. Borane-Catalyzed Reductive α-Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact.

    PubMed

    Kim, Youngchan; Chang, Sukbok

    2016-01-01

    Described herein is the development of the B(C6F5)3-catalyzed hydrosilylation of α,β-unsaturated esters and amides to afford synthetically valuable α-silyl carbonyl products. The α-silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α-silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4-hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate. PMID:26549843

  12. Nitrogen doped carbon nanotubes with encapsulated ferric carbide as excellent electrocatalyst for oxygen reduction reaction in acid and alkaline media

    NASA Astrophysics Data System (ADS)

    Zhong, Guoyu; Wang, Hongjuan; Yu, Hao; Peng, Feng

    2015-07-01

    Nitrogen doped carbon nanotubes (NCNTs) with encapsulated Fe3C nanoparticles (Fe3C@NCNTs) are synthesized by a simple direct pyrolysis of melamine and ferric chloride. The characterization results reveal that Fe3C is mainly encapsulated in the interior of NCNTs and N species is mainly distributed on the outside surface of NCNTs. Iron and iron carbide catalyze the growth of NCNTs and are wrapped by carbon to form Fe3C@NCNTs. The as-prepared Fe3C@NCNTs catalyst exhibits superior oxygen reduction reaction (ORR) activity, excellent methanol tolerance and long-term stability in both acid and alkaline media. It is proven that the doped N is the main active site for ORR and the inner Fe3C with outside carbon form the synergetic active site to enhance ORR activity. The ORR mechanism of direct four electron transfer pathway is proved in acid and alkaline media.

  13. Linking structure to function: The search for active sites in non-platinum group metal oxygen reduction reaction catalysts

    DOE PAGESBeta

    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 thesemore » materials.« less

  14. Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

    PubMed Central

    Xiao, Junwu; Kuang, Qin; Yang, Shihe; Xiao, Fei; Wang, Shuai; Guo, Lin

    2013-01-01

    Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts. PMID:23892418

  15. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.

    PubMed

    Maiyalagan, Thandavarayan; Jarvis, Karalee A; Therese, Soosairaj; Ferreira, Paulo J; Manthiram, Arumugam

    2014-01-01

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co(3+/4+):3d energy with the top of the O(2-):2p band. PMID:24862287

  16. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj; Ferreira, Paulo J.; Manthiram, Arumugam

    2014-05-01

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co3+/4+:3d energy with the top of the O2-:2p band.

  17. Size-controlled large-diameter and few-walled carbon nanotube catalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Xianliang; Li, Qing; Pan, Hengyu; Lin, Ye; Ke, Yujie; Sheng, Haiyang; Swihart, Mark T.; Wu, Gang

    2015-11-01

    We demonstrate a new strategy for tuning the size of large-diameter and few-walled nitrogen-doped carbon nanotubes (N-CNTs) from 50 to 150 nm by varying the transition metal (TM = Fe, Co, Ni or Mn) used to catalyze graphitization of dicyandiamide. Fe yielded the largest tubes, followed by Co and Ni, while Mn produced a clot-like carbon morphology. We show that morphology is correlated with electrocatalytic activity for the oxygen reduction reaction (ORR). A clear trend of Fe > Co > Ni > Mn for the ORR catalytic activity was observed, in both alkaline media and more demanding acidic media. The Fe-derived N-CNTs exhibited the highest BET (~870 m2 g-1) and electrochemically accessible (~450 m2 g-1) surface areas and, more importantly, the highest concentration of nitrogen incorporated into the carbon planes. Thus, in addition to the intrinsic high activity of Fe-derived catalysts, the high surface area and nitrogen doping contribute to high ORR activity. This work, for the first time, demonstrates size-controlled synthesis of large-diameter N-doped carbon tube electrocatalysts by varying the metal used in N-CNT generation. Electrocatalytic activity of the Fe-derived catalyst is already the best among studied metals, due to the high intrinsic activity of possible Fe-N coordination. This work further provides a promising route to advanced Fe-N-C nonprecious metal catalysts by generating favorable morphology with more active sites and improved mass transfer.We demonstrate a new strategy for tuning the size of large-diameter and few-walled nitrogen-doped carbon nanotubes (N-CNTs) from 50 to 150 nm by varying the transition metal (TM = Fe, Co, Ni or Mn) used to catalyze graphitization of dicyandiamide. Fe yielded the largest tubes, followed by Co and Ni, while Mn produced a clot-like carbon morphology. We show that morphology is correlated with electrocatalytic activity for the oxygen reduction reaction (ORR). A clear trend of Fe > Co > Ni > Mn for the ORR catalytic

  18. Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction.

    PubMed

    Lin, Ziyin; Song, Min-kyu; Ding, Yong; Liu, Yan; Liu, Meilin; Wong, Ching-ping

    2012-03-14

    Nitrogen-doped graphene (nG) is a promising metal-free catalyst for oxygen reduction reaction (ORR) on the cathode of fuel cells. Here we report a facile preparation of nG via pyrolysis of graphene oxide with melamine. The morphology of the nG is revealed using scanning electron microscopy and transmission electron microscopy while the successful N doping is confirmed by electron energy loss spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The resulting nG shows high electrocatalytic activity toward ORR in an alkaline solution with an onset potential of -0.10 V vs. Ag/AgCl reference electrode. The nG catalyzed oxygen reduction exhibits a favorable formation of water via a four-electron pathway. Good stability and anti-crossover property are also observed, which are advantageous over the Pt/C catalyst. Furthermore, the effect of pyrolysis temperature on the structure and activity of nG is systematically studied to gain some insights into the chemical reactions during pyrolysis. PMID:22307527

  19. Platinum particles supported on mesoporous carbons: fabrication and electrocatalytic performance in methanol-tolerant oxygen-reduction reactions

    PubMed Central

    Dong, Cheng-Di; Chen, Chiu-Wen; Chen, Chih-Feng; Hung, Chang-Mao

    2014-01-01

    In this report, we describe the preparation and electrochemical characterization of a Pt electrocatalyst, which was synthesized from hexachloroplatinic acid, using the incipient wetness impregnation method. This carbon mesoporous materials (Pt-CMMs) electrocatalyst was used for catalyzing the oxidation of methanol and its oxygen-reduction reaction. The electrocatalytic oxidation of methanol was studied using linear-sweep voltammograms (LSV), polarization and chronoamperometric measurements. Phase characterizations and morphological analyses were performed using 3D excitation-emission fluorescent matrix (EEFM) spectroscopy, UV-Vis absorption measurements, and X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM) techniques; the ESEM system was equipped with an energy-dispersive spectrometer (EDS). The oxidation capacity measured using a LSV might explain the high activity exhibited by the Pt-CMM electrocatalysts in methanol-tolerant oxygen reduction, and the results demonstrated that the potential and current density of the main reaction peak of the Pt-CMMs electrocatalyst changed during the reaction. Moreover, EEFM spectroscopy and XRD were determined to be appropriate and effective methods for characterizing Pt clusters that enhance their intrinsic emission from Pt-CMMs electrocatalysts in electrocatalytic-treatment systems. Furthermore, the ESEM-EDS results showed that fresh Pt nanoparticles were highly dispersed on CMMs and featured a 20 nm diameter and a narrow particle-size distribution. PMID:25168212

  20. Concise Enantioselective Synthesis of Oxygenated Steroids via Sequential Copper(II)-Catalyzed Michael Addition/Intramolecular Aldol Cyclization Reactions

    PubMed Central

    Cichowicz, Nathan R.; Kaplan, Will; Khomutnyk, Yaroslav; Bhattarai, Bijay; Sun, Zhankui; Nagorny, Pavel

    2015-01-01

    A new scalable enantioselective approach to functionalized oxygenated steroids is described. This strategy is based on chiral bis(oxazoline) copper(II) complex-catalyzed enantioselective and diastereoselective Michael reactions of cyclic ketoesters and enones to install vicinal quaternary and tertiary stereocenters. In addition, the utility of copper(II) salts as highly active catalysts for the Michael reactions of traditionally unreactive ββ′-enones and substituted ββ′-ketoesters that results in unprecedented Michael adducts containing vicinal all-carbon quaternary centers is also demonstrated. The Michael adducts subsequently undergo base-promoted diastereoselective aldol cascade reactions resulting in the natural or unnatural steroid skeletons. The experimental and computational studies suggest that the torsional strain effects arising from the presence of the Δ5-unsaturation are key controling elements for the formation of the natural cardenolide scaffold. The described method enables expedient generation of polycyclic molecules including modified steroidal scaffolds as well as challenging-to-synthesize Hajos-Parrish and Wieland-Miescher ketones. PMID:26491886

  1. Highly enantioselective oxidative couplings of 2-naphthols catalyzed by chiral bimetallic oxovanadium complexes with either oxygen or air as oxidant.

    PubMed

    Guo, Qi-Xiang; Wu, Zhi-Jun; Luo, Zhi-Bin; Liu, Quan-Zhong; Ye, Jian-Liang; Luo, Shi-Wei; Cun, Lin-Feng; Gong, Liu-Zhu

    2007-11-14

    The chiral bimetallic oxovanadium complexes have been designed for the enantioselective oxidative coupling of 2-naphthols bearing various substituents at C6 and/or C7. The chirality transferring from the amino acid to the axis of the biphenyl in oxovanadium complexes 2 was found to occur with the use of UV and CD spectra and DFT calculation. The homo-coupling reaction with oxygen as the oxidant was promoted by 5 mol % of an oxovanadium complex derived from L-isoleucine and achiral biphenol to afford binaphthols in nearly quantitative yields with high enantioselectivities of up to 98% ee. An oxovanadium complex derived from L-isoleucine and H8-binaphthol is highly efficient at catalyzing the air-oxidized coupling of 2-naphthols with excellent enantioselectivities of up to 97% ee. 51V NMR study shows that the oxovanadium complexes have two vanadium(V) species. Kinetic studies, the cross-coupling reaction, and HRMS spectral studies on the reaction have been carried out and illustrate that two vanadium(V) species are both involved in catalysis and that the coupling reaction undergoes a radical-radical mechanism in an intramolecular manner. Quantum mechanical calculations rationalize the importance of the cooperative effects of the axial chirality matching S-amino acids on the stereocontrol of the oxidative coupling reaction. The application of the transformation in the preparation of chiral ligands and conjugated polymers confirms the importance of the current process in organic synthesis. PMID:17956093

  2. Oxygen-Dependent Control of Respiratory Nitrate Reduction in Mycelium of Streptomyces coelicolor A3(2)

    PubMed Central

    Fischer, Marco; Falke, Dörte; Pawlik, Tony

    2014-01-01

    Several members of the obligately aerobic genus Streptomyces are able to reduce nitrate, catalyzed by Nar-type respiratory nitrate reductases. A unique feature of Streptomyces coelicolor A3(2) compared with other streptomycetes is that it synthesizes three nonredundant Nar enzymes. In this study, we show that Nar2 is the main Nar enzyme active in mycelium and could characterize the conditions governing its synthesis. Nar2 was present at low levels in aerobically cultivated mycelium, but synthesis was induced when cultures were grown under oxygen limitation. Growth in the presence of high oxygen concentrations prevented the induction of Nar2 synthesis. Equally, an abrupt shift from aerobiosis to anaerobiosis did not result in the immediate induction of Nar2 synthesis. This suggests that the synthesis of Nar2 is induced during a hypoxic downshift, probably to allow maintenance of a proton gradient during the transition to anaerobiosis. Although no Nar2 could be detected in freshly harvested mature spores, synthesis of the enzyme could be induced after long-term (several days) incubation of these resting spores under anaerobic conditions. Induction of Nar2 synthesis in spores was linked to transcriptional control. Nar2 activity in whole mycelium was strictly dependent on the presence of a putative nitrate transporter, NarK2. The oxygen-dependent inhibition of nitrate reduction by Nar2 was mediated by NarK2-dependent nitrate:nitrite antiport. This antiport mechanism likely prevents the accumulation of toxic nitrite in the cytoplasm. A deletion of the narK2 gene had no effect on Nar1-dependent nitrate reduction in resting spores. Together, our results indicate redox-dependent transcriptional and posttranslational control of nitrate reduction by Nar2. PMID:25225271

  3. Monothiolation and Reduction of Graphene Oxide via One-Pot Synthesis: Hybrid Catalyst for Oxygen Reduction.

    PubMed

    Chua, Chun Kiang; Pumera, Martin

    2015-04-28

    The functionalization of graphene provides diverse possibilities to improve the handling of graphene and enable further chemical transformation on graphene. Graphene functionalized with mainly heteroatom-based functional groups to enhance its chemical and physical properties is intensively pursued but often resulted in grafting of the heteroatoms as various functional groups. Here, we show that graphene oxide can be functionalized with predominantly a single type of sulfur moiety and reduced simultaneously to form monothiol-functionalized graphene. The thiol-functionalized graphene shows a high electrical conductivity and heterogeneous electron transfer rate. Graphene is also embedded with a trace amount of manganese impurities originating from a prior graphite oxidation process, which facilitates the thiol-functionalized graphene to function as a hybrid electrocatalyst for oxygen reduction reactions in alkaline medium with an onset potential lower than for Pt/C. Further characterizations of the graphene are performed with X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, and electrochemical impedance spectroscopy. This material contributes to the class of hybrids that are highly active electrocatalysts. PMID:25816194

  4. Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation.

    PubMed

    Rhee, Jong Uk; Krische, Michael J

    2006-08-23

    Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes. PMID:16910650

  5. Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

    PubMed

    Bandar, Jeffrey S; Ascic, Erhad; Buchwald, Stephen L

    2016-05-11

    A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance. PMID:27121395

  6. Oxygen Reduction on Ag(100) in Alkaline Solutions--A Theoretical Study.

    PubMed

    Goduljan, Aleksej; de Campos Pinto, Leandro Moreira; Juarez, Fernanda; Santos, Elizabeth; Schmickler, Wolfgang

    2016-02-16

    Silver is much more reactive to oxygen than gold; nevertheless, in alkaline solutions, the rates of oxygen reduction on both metals are similar. To explain this phenomenon, the first, rate-determining step of oxygen reduction on Ag(100) is determined by a combination of DFT, molecular dynamics, and electrocatalysis theory. In vacuum, oxygen is adsorbed on Ag(100), but in the electrochemical environment, the adsorption energy is offset by the loss of hydration energy as the molecule approaches the surface. As a result, the first electron transfer should take place in an outer-sphere mode. Previously, the same mechanism for oxygen reduction on Au(100) has been predicted, and these calculations have been repeated by using a more advanced version of the electrocatalysis theory discussed herein to confirm previous conclusions. The theoretical results compare well with experimental data. PMID:26698629

  7. Kinetic modeling of inherent mineral catalyzed NO reduction by biomass char.

    PubMed

    Wu, X Y; Song, Q; Zhao, H B; Zhang, Z H; Yao, Q

    2014-04-01

    The evolution of rice straw char reactivity during reaction with NO was examined in differential reactor at 900 and 1000 °C. Original and acid-washed rice straw chars were used. Surface area and mineral content of char samples with different conversion were analyzed. The reactivity of the acid-washed char increased until conversion Xchar = 20%, remained constant, and then decreased continuously to zero. The reactivity of the original char decreased continuously to zero throughout the reaction, with a faster decrease at 1000 °C. Mineral transformation during original char reaction was obvious. Concentration of acid-soluble K decreased about 56% and 90% at 900 and 1000 °C. Ca and Mg released little to gas phase, but reacted with SiO2 in a small amount. The evolution of the acid-washed char reactivity correlated well with the development of surface area and was well predicted by random pore model. The reactivity of the original char depended not only on the development of surface area, but also on transformation of inherent minerals, mainly K. A two-reaction model was built which well predicted inherent K transformation. A modified random pore model was developed, which successfully simulated inherent mineral catalyzed char-NO reaction. PMID:24588459

  8. Enhanced electrocatalysis of the oxygen reduction reaction based on pattering of platinum surfaces with cyanide.

    SciTech Connect

    Strmcnik, D.; Escudero-Escribano, M.; Kodama, K.; Stamenkovic, V. R.; Cuesta, A.; Markovic, N. M.; Materials Science Division; Inst. de Quimica Fisica; Toyota Central R&D Labs., Inc.

    2010-08-15

    The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.

  9. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide

    SciTech Connect

    Strmcnik, D.; Escudero, M.; Kodama, K.; Stamenkovic, V. R.; Cuesta, A.; Markovic, N. M.

    2010-10-01

    The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.

  10. Studies on the oxygen reduction catalyst for zinc-air battery electrode

    NASA Astrophysics Data System (ADS)

    Wang, Xianyou; Sebastian, P. J.; Smit, Mascha A.; Yang, Hongping; Gamboa, S. A.

    In this paper, perovskite type La 0.6Ca 0.4CoO 3 as a catalyst of oxygen reduction was prepared, and the structure and performance of the catalysts was examined by means of IR, X-ray diffraction (XRD), and thermogravimetric (TG). Mixed catalysts doped, some metal oxides were put also used. The cathodic polarization curves for oxygen reduction on various catalytic electrodes were measured by linear sweep voltammetry (LSV). A Zn-air battery was made with various catalysts for oxygen reduction, and the performance of the battery was measured with a BS-9300SM rechargeable battery charge/discharge device. The results showed that the perovskite type catalyst (La 0.6Ca 0.4CoO 3) doped with metal oxide is an excellent catalyst for the zinc-air battery, and can effectively stimulate the reduction of oxygen and improve the properties of zinc-air batteries, such as discharge capacity, etc.

  11. Method of controlled reduction of nitroaromatics by enzymatic reaction with oxygen sensitive nitroreductase enzymes

    DOEpatents

    Shah, M.M.; Campbell, J.A.

    1998-07-07

    A method is described for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with oxygen sensitive nitroreductase enzymes, such as ferredoxin NADP oxidoreductase. 6 figs.

  12. Method of controlled reduction of nitroaromatics by enzymatic reaction with oxygen sensitive nitroreductase enzymes

    DOEpatents

    Shah, Manish M.; Campbell, James A.

    1998-01-01

    A method for the controlled reduction of nitroaromatic compounds such as nitrobenzene and 2,4,6-trinitrotoluene by enzymatic reaction with oxygen sensitive nitroreductase enzymes, such as ferredoxin NADP oxidoreductase.

  13. Electrochemical reduction of CO2 to formate catalyzed by electroplated tin coating on copper foam

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Zhou, Jing; Lv, Weixin; Fang, Hailin; Wang, Wei

    2016-01-01

    Sn/f-Cu electrode has been prepared by electrodeposition Sn on a Cu foam substrate in aqueous plating solution, which has been used as the cathode for electrochemical reduction of carbon dioxide (CO2) in aqueous KHCO3 solution. Here, we have explored the effects of the deposition time and the electrolysis potential on the Faradaic efficiency for producing formate. The results demonstrate that maximum Faradaic efficiency of 83.5% is obtained at -1.8 V vs. Ag/AgCl when the Sn/f-Cu electrode is prepared by electrodeposition for 35 min. The Sn/f-Cu electrode exhibits excellent catalytic activity for CO2 reduction compared with the Cu foam electrode and the Sn plate electrode. The average current density and the production rate of formate for the Sn/f-Cu electrode are more than twice those for the Sn plate electrode during electrochemical reduction of CO2.

  14. Supported gold nanoparticles catalyzed cis-selective semihydrogenation of alkynes using ammonium formate as the reductant.

    PubMed

    Liang, Shengzong; Hammond, Gerald B; Xu, Bo

    2016-05-21

    TiO2 supported gold nanoparticles with low loading (0.5 mol%) are able to semihydrogenate non-fluorinated and gem-difluorinated alkynes to cis-alkenes with high selectivity, using cost-effective and easy-to-handle ammonium formate as the reductant. No over-reduction was observed. The good recyclability of Au/TiO2 allows for "green" semireduction of alkynes. A difluorinated pyran and α,β-unsaturated δ-lactone were easily prepared from the obtained gem-difluoro alkene building blocks. PMID:27063707

  15. Nickel-Catalyzed Cross-Electrophile Coupling with Organic Reductants in Non-Amide Solvents.

    PubMed

    Anka-Lufford, Lukiana L; Huihui, Kierra M M; Gower, Nicholas J; Ackerman, Laura K G; Weix, Daniel J

    2016-08-01

    Cross-electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non-amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron-poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to 'hold' a reaction without diminishing yield or catalyst activity. PMID:27273457

  16. Ruthenium-catalyzed reductive methylation of imines using carbon dioxide and molecular hydrogen.

    PubMed

    Beydoun, Kassem; Ghattas, Ghazi; Thenert, Katharina; Klankermayer, Jürgen; Leitner, Walter

    2014-10-01

    The use of the well-defined [Ru(triphos)(tmm)] catalyst, CO2 as C1 source, and H2 as reducing agent enabled the reductive methylation of isolated imines, as well as the direct coupling of amines with aldehydes and the subsequent reductive methylation of the in situ formed imines. The method, which afforded the corresponding N-methyl amines in very good to excellent yields, was also used for the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis. PMID:25146346

  17. Platinum-catalyzed reduction of amides with hydrosilanes bearing dual Si-H groups: a theoretical study of the reaction mechanism.

    PubMed

    Nakatani, Naoki; Hasegawa, Jun-ya; Sunada, Yusuke; Nagashima, Hideo

    2015-11-28

    A platinum-catalyzed amide reduction through hydrosilylation with 1,2-bis(dimethylsilyl)benzene (BDSB) was investigated on a theoretical basis. While the platinum-catalyzed hydrosilylation of alkenes is well known, that of carbonyl groups rarely occurs. The only exception involves the use of bifunctional hydrosilanes having dual, closely located Si-H groups, which accelerate the hydrosilylation of carbonyl groups, leading to successful reduction of amides to amines under mild conditions. In the present study, we determined through density functional theory calculations that the platinum-catalyzed hydrosilylation of the C=O bond proceeds via a Pt(IV)-disilyl-dihydride intermediate with an associated activation energy of 29.6 kcal mol(-1). Although it was believed that the hydrosilylation of carbonyl groups does not occur via the classical Chalk-Harrod cycle, the computational results support a mechanism involving the insertion of the amide C=O bond into a Pt-H bond. This insertion readily occurs because a Pt-H bond in the Pt(IV)-disilyl-dihydride intermediate is highly activated due to the strong σ-donating interaction of the silyl groups. The modified Chalk-Harrod mechanism that occurs preferentially in rhodium-catalyzed hydrosilylation as well as the ionic outer sphere mechanism associated with iridium-catalyzed amide reduction were both safely ruled out as mechanisms for this platinum-catalyzed amide reduction, because of the unexpectedly large activation barrier (>40 kcal mol(-1)) for the Si-O bond formation. PMID:26497866

  18. Numerical Study of the Reduction Process in an Oxygen Blast Furnace

    NASA Astrophysics Data System (ADS)

    Zhang, Zongliang; Meng, Jiale; Guo, Lei; Guo, Zhancheng

    2016-02-01

    Based on computational fluid dynamics, chemical reaction kinetics, principles of transfer in metallurgy, and other principles, a multi-fluid model for a traditional blast furnace was established. The furnace conditions were simulated with this multi-fluid mathematical model, and the model was verified with the comparison of calculation and measurement. Then a multi-fluid model for an oxygen blast furnace in the gasifier-full oxygen blast furnace process was established based on this traditional blast furnace model. With the established multi-fluid model for an oxygen blast furnace, the basic characteristics of iron ore reduction process in the oxygen blast furnace were summarized, including the changing process of the iron ore reduction degree and the compositions of the burden, etc. The study found that compared to the traditional blast furnace, the magnetite reserve zone in the furnace shaft under oxygen blast furnace condition was significantly reduced, which is conducive to the efficient operation of blast furnace. In order to optimize the oxygen blast furnace design and operating parameters, the iron ore reduction process in the oxygen blast furnace was researched under different shaft tuyere positions, different recycling gas temperatures, and different allocation ratios of recycling gas between the hearth tuyere and the shaft tuyere. The results indicate that these three factors all have a substantial impact on the ore reduction process in the oxygen blast furnace. Moderate shaft tuyere position, high recycling gas temperature, and high recycling gas allocation ratio between hearth and shaft could significantly promote the reduction of iron ore, reduce the scope of the magnetite reserve zone, and improve the performance of oxygen blast furnace. Based on the above findings, the recommendations for improvement of the oxygen blast furnace design and operation were proposed.

  19. Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; Brüchert, Volker; Lyons, Timothy W.; Engel, Gregory S.; Balci, Nurgul; Schrag, Daniel P.; Brunner, Benjamin

    2010-04-01

    Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ 34S SO4 and δ 18O SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ 18O H2O and initial δ 18O SO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ 18O SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO 32-), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.

  20. Strategic use of nickel(0)-catalyzed enyne-epoxide reductive coupling towards the synthesis of (−)-cyatha-3,12-diene

    PubMed Central

    Sparling, Brian A.; Simpson, Graham L.; Jamison, Timothy F.

    2009-01-01

    Various situations are explored in which the nickel(0)-catalyzed enyne-epoxide reductive coupling was utilized to access key intermediates towards the total synthesis of (−)-cyatha-3,12-diene (1). Enantioenriched 3,5-dien-1-ols with a variety of functionality were obtained in a straightforward manner from easily accessible 1,3-enynes and terminal epoxides. PMID:20161213

  1. Mild and selective Et2Zn-catalyzed reduction of tertiary amides under hydrosilylation conditions.

    PubMed

    Kovalenko, Oleksandr O; Volkov, Alexey; Adolfsson, Hans

    2015-02-01

    Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields. PMID:25587664

  2. Nickel-catalyzed reductive arylation of activated alkynes with aryl iodides

    PubMed Central

    Dorn, Stephanie C. M.; Olsen, Andrew K; Kelemen, Rachel E.; Shrestha, Ruja; Weix, Daniel J.

    2015-01-01

    The direct, regioselective, and stereoselective arylation of activated alkynes with aryl iodides using a nickel catalyst and manganese reductant is described. The reaction conditions are mild (40 °C in MeOH, no acid or base) and an intermediate organomanganese reagent is unlikely. Functional groups tolerated include halides and pseudohalides, free and protected anilines, and a benzyl alcohol. Other activated alkynes including an amide and a ketone also reacted to form arylated products in good yields. PMID:26028781

  3. Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

    PubMed Central

    Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

    2015-01-01

    Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

  4. Gold nanoparticle-catalyzed reduction in a model system: Quantitative determination of reactive heterogeneity of a supported nanoparticle surface

    SciTech Connect

    Nigra, Michael M.; Arslan, Ilke; Katz, Alexander

    2012-11-01

    Kinetic poisoning experiments employing organic ligands were conducted using a gold nanoparticle–catalyzed reaction consisting of the reduction of resazurin to resorufin. The kinetic contributions of three distinct types of sites along with the number density of each of these site types during reaction were determined. The calculated number densities of each of the three types of sites, hypothesized to be corners, edges, and terraces, correlates well with atomic-resolution micrographs of the supported gold nanoparticles, obtained using aberration-corrected transmission electron microscopy and with predictions based on geometric models of idealized gold nanoparticles. The most active sites comprising 1% of the surface atoms exhibit at least 30% of the total activity of the catalyst for resazurin reduction. The selective mechanical blocking of surface sites on nanoparticles, particularly undercoordinated sites, paves the way for novel approaches utilizing organic ligands to quantify the activity of different active sites and control catalysis on metal surfaces. This work was supported in part by the Laboratory Directed Research and Development program at the Pacific Northwest National Laboratory (PNNL). The aberration-corrected electron microscopy was performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a U.S. Department of Energy (DOE) national scientific user facility located at PNNL and funded by BER. PNNL is operated by Battelle for the U.S. DOE under contract DE-AC05-76RL01830.

  5. A General, Practical Triethylborane-Catalyzed Reduction of Carbonyl Functions to Alcohols.

    PubMed

    Peng, Dongjie; Zhang, Mintao; Huang, Zheng

    2015-10-12

    A combination of the abundant and low-cost triethylborane and sodium alkoxide generates a highly efficient catalyst for reduction of esters, as well as ketones and aldehydes, to alcohols using an inexpensive hydrosilane under mild conditions. The catalyst system exhibits excellent chemoselectivity and a high level of functional group tolerance. Mechanistic studies revealed a resting state of sodium triethylalkoxylborate that is the product of the reaction of BEt3 with sodium alkoxide. This borate species reacts with hydrosilane to form NaBEt3 H, which rapidly reduces esters. PMID:26332613

  6. Ruthenium catalyzed C-C bond formation via transfer hydrogenation: branch-selective reductive coupling of allenes to paraformaldehyde and higher aldehydes.

    PubMed

    Ngai, Ming-Yu; Skucas, Eduardas; Krische, Michael J

    2008-07-01

    Under the conditions of ruthenium-catalyzed transfer hydrogenation employing 2-propanol as the terminal reductant, 1,1-disubstituted allenes 1a- h engage in reductive coupling to paraformaldehyde to furnish homoallylic alcohols 2a- h. Under identical transfer hydrogenation conditions, 1,1-disubstituted allenes engage in reductive coupling to aldehydes 3a- f to furnish homoallylic alcohols 4a- n. In all cases, reductive coupling occurs with branched regioselectivity to deliver homoallylic alcohols bearing all-carbon quaternary centers. PMID:18533665

  7. Oxygen Reduction Mechanism of Monometallic Rhodium Hydride Complexes.

    PubMed

    Halbach, Robert L; Teets, Thomas S; Nocera, Daniel G

    2015-08-01

    The reduction of O2 to H2O mediated by a series of electronically varied rhodium hydride complexes of the form cis,trans-Rh(III)Cl2H(CNAd)(P(4-X-C6H4)3)2 (2) (CNAd = 1-adamantylisocyanide; X = F (2a), Cl (2b), Me (2c), OMe (2d)) was examined through synthetic and kinetic studies. Rhodium(III) hydride 2 reacts with O2 to afford H2O with concomitant generation of trans-Rh(III)Cl3(CNAd)(P(4-X-C6H4)3)2 (3). Kinetic studies of the reaction of the hydride complex 2 with O2 in the presence of HCl revealed a two-term rate law consistent with an HX reductive elimination (HXRE) mechanism, where O2 binds to a rhodium(I) metal center and generates an η(2)-peroxo complex intermediate, trans-Rh(III)Cl(CNAd)(η(2)-O2)(P(4-X-C6H4)3)2 (4), and a hydrogen-atom abstraction (HAA) mechanism, which entails the direct reaction of O2 with the hydride. Experimental data reveal that the rate of reduction of O2 to H2O is enhanced by electron-withdrawing phosphine ligands. Complex 4 was independently prepared by the addition of O2 to trans-Rh(I)Cl(CNAd)(P(4-X-C6H4)3)2 (1). The reactivity of 4 toward HCl reveals that such peroxo complexes are plausible intermediates in the reduction of O2 to H2O. These results show that the given series of electronically varied rhodium(III) hydride complexes facilitate the reduction of O2 to H2O according to a two-term rate law comprising HXRE and HAA pathways and that the relative rates of these two pathways, which can occur simultaneously and competitively, can be systematically modulated by variation of the electronic properties of the ancillary ligand set. PMID:26168057

  8. Theoretical insights on the catalytic activity and mechanism for oxygen reduction reaction at Fe and P codoped graphene.

    PubMed

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-05-14

    The non-precious metal graphene catalyst doped with Fe-Px are recently proposed as a promising candidate in substituting Pt for catalyzing oxygen reduction reaction (ORR) in fuel cells. Systematic DFT calculations are performed to investigate the catalytic activity and the ORR mechanism on the Fe-Px (x = 1-4) system in acid medium in this work. Our results indicated that the configuration with one Fe and two P atoms codoped at zigzag edge site (Fe-P2-zig-G) is the most stable, in excellent agreement with the experimental observation that the ratio of Fe and P is nearly 1 : 2. The four-electron reduction mechanism for ORR on the Fe-P2-zig-G is via the competing OOH hydrogenation pathways (to form either OH + OH or O + H2O). The rate determining step is the O2 hydrogenation with an energy barrier of 0.43 eV, much smaller that of calculated 0.80 eV for pure Pt. In addition, the highest energy barrier of the studied ORR mechanism is the O2 dissociation with an energy barrier of 0.70 eV, a value also smaller than that of pure Pt. This demonstrated that the zigzag edge site of the Fe-P2 codoped graphene should be active for the ORR. PMID:27094325

  9. The secondary coordination sphere and axial ligand effects on oxygen reduction reaction by iron porphyrins: a DFT computational study.

    PubMed

    Ohta, Takehiro; Nagaraju, Perumandla; Liu, Jin-Gang; Ogura, Takashi; Naruta, Yoshinori

    2016-09-01

    Oxygen reduction reaction (ORR) catalyzed by a bio-inspired iron porphyrin bearing a hanging carboxylic acid group over the porphyrin ring, and a tethered axial imidazole ligand was studied by DFT calculations. BP86 free energy calculations of the redox potentials and pK a's of reaction components involved in the proton coupled electron transfer (PCET) reactions of the ferric-hydroxo and -superoxo complexes were performed based on Born-Haber thermodynamic cycle in conjunction with a continuum solvation model. The comparison was made with iron porphyrins that lack either in the hanging acid group or axial ligand, suggesting that H-bond interaction between the carboxylic acid and iron-bound hydroxo, aquo, superoxo, and peroxo ligands (de)stabilizes the Fe-O bonding, resulting in the increase in the reduction potential of the ferric complexes. The axial ligand interaction with the imidazole raises the affinity of the iron-bound superoxo and peroxo ligands for proton. In addition, a low-spin end-on ferric-hydroperoxo intermediate, a key precursor for O-O cleavage, can be stabilized in the presence of axial ligation. Thus, selective and efficient ORR of iron porphyrin can be achieved with the aid of the secondary coordination sphere and axial ligand interactions. PMID:27501847

  10. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

    SciTech Connect

    Kasakov, Stanislav; Shi, Hui; Camaioni, Donald M.; Zhao, Chen; Barath, Eszter; Jentys, Andreas; Lercher, Johannes A.

    2015-11-01

    Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  11. Study on kinetics of cathodic reduction of dissolved oxygen in 3.5% sodium chloride solution

    NASA Astrophysics Data System (ADS)

    Li, Yongjuan; Zhang, Dun; Wu, Jiajia

    2010-09-01

    Electrochemical reduction of dissolved oxygen in seawater on metals is of great importance for corrosion studies. The present paper studied cathodic reduction of dissolved oxygen on Q235 carbon steel in 3.5% sodium chloride (NaCl) solutions by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE). The cyclic voltammetric results demonstrated the cathodic process on Q235 carbon steel in O2-saturated 3.5% NaCl solution contains three reactions: dissolved oxygen reduction, iron oxides reduction and hydrogen evolution. The peak potential of oxygen reduction reaction (ORR) is -0.85 V vs Ag/AgCl, 3 molL-1 KCl. The EIS results indicated that the ORR occurring on Q235 carbon steel is a 4-electron process and that no finite diffusion is caused by the intermediate of H2O2 produced by ORR. The RDE and RRDE voltammograms confirmed the EIS results and it was found that the number of transferred electrons for ORR was nearly 4, i.e., dissolved oxygen reduced to water.

  12. Secondary alcohol dehydrogenase catalyzes the reduction of exogenous acetone to 2-propanol in Trichomonas vaginalis.

    PubMed

    Sutak, Robert; Hrdy, Ivan; Dolezal, Pavel; Cabala, Radomir; Sedinová, Miroslava; Lewin, Joern; Harant, Karel; Müller, Miklos; Tachezy, Jan

    2012-08-01

    Secondary alcohols such as 2-propanol are readily produced by various anaerobic bacteria that possess secondary alcohol dehydrogenase (S-ADH), although production of 2-propanol is rare in eukaryotes. Specific bacterial-type S-ADH has been identified in a few unicellular eukaryotes, but its function is not known and the production of secondary alcohols has not been studied. We purified and characterized S-ADH from the human pathogen Trichomonas vaginalis. The kinetic properties and thermostability of T. vaginalis S-ADH were comparable with bacterial orthologues. The substantial activity of S-ADH in the parasite's cytosol was surprising, because only low amounts of ethanol and trace amounts of secondary alcohols were detected as metabolic end products. However, S-ADH provided the parasite with a high capacity to scavenge and reduce external acetone to 2-propanol. To maintain redox balance, the demand for reducing power to metabolize external acetone was compensated for by decreased cytosolic reduction of pyruvate to lactate and by hydrogenosomal metabolism of pyruvate. We speculate that hydrogen might be utilized to maintain cytosolic reducing power. The high activity of Tv-S-ADH together with the ability of T. vaginalis to modulate the metabolic fluxes indicate efficacious metabolic responsiveness that could be advantageous for rapid adaptation of the parasite to changes in the host environment. PMID:22686835

  13. DFT Study of Oxygen Reduction Reaction on N-substituted Carbon Electrodes. Adsorption

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hisayoshi; Tomoya, Nakzono; Miyazaki, Soichi; Miura, Toshiko; Takeuchi, Nobuyuki; Yamabe, Tokio

    2011-05-01

    Carbon alloys attract attention as metal-free cathode catalysts. Mechanisms of oxygen reduction reactions are investigated using the DFT calculations and molecular models such as N-substituted coronene, circum pyrene, and corannulene. The overall oxygen reduction reaction (ORR) is decomposed into five elementary reactions. Adsorption of O2 is important as the first step of reduction, and it depends strongly on the spin density on C atoms, introduced by the N atom. Secondly the peripheral C atoms have an advantage due to the rehybridization freedom to the sp3 configuration. Based on the reversible electrode potential (REP) for each elementary reaction, the overpotential is expected for the first reduction of O2 to OOH and the final reduction of OH to H2O. These features indicate that N-substituted carbon electrode resembles Pt electrode compared to other less active metals, such as Au.

  14. Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Srinivasan, Supramaniam; Appleby, A. J.; Martin, Charles R.

    1992-01-01

    The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

  15. Crystal structure of a blue laccase from Lentinus tigrinus: evidences for intermediates in the molecular oxygen reductive splitting by multicopper oxidases

    PubMed Central

    Ferraroni, Marta; Myasoedova, Nina M; Schmatchenko, Vadim; Leontievsky, Alexey A; Golovleva, Ludmila A; Scozzafava, Andrea; Briganti, Fabrizio

    2007-01-01

    Background Laccases belong to multicopper oxidases, a widespread class of enzymes implicated in many oxidative functions in pathogenesis, immunogenesis and morphogenesis of organisms and in the metabolic turnover of complex organic substances. They catalyze the coupling between the four one-electron oxidations of a broad range of substrates with the four-electron reduction of dioxygen to water. These catalytic processes are made possible by the contemporaneous presence of at least four copper ion sites, classified according to their spectroscopic properties: one type 1 (T1) site where the electrons from the reducing substrates are accepted, one type 2 (T2), and a coupled binuclear type 3 pair (T3) which are assembled in a T2/T3 trinuclear cluster where the electrons are transferred to perform the O2 reduction to H2O. Results The structure of a laccase from the white-rot fungus Lentinus (Panus) tigrinus, a glycoenzyme involved in lignin biodegradation, was solved at 1.5 Å. It reveals a asymmetric unit containing two laccase molecules (A and B). The progressive reduction of the copper ions centers obtained by the long-term exposure of the crystals to the high-intensity X-ray synchrotron beam radiation under aerobic conditions and high pH allowed us to detect two sequential intermediates in the molecular oxygen reduction pathway: the "peroxide" and the "native" intermediates, previously hypothesized through spectroscopic, kinetic and molecular mechanics studies. Specifically the electron-density maps revealed the presence of an end-on bridging, μ-η1:η1 peroxide ion between the two T3 coppers in molecule B, result of a two-electrons reduction, whereas in molecule A an oxo ion bridging the three coppers of the T2/T3 cluster (μ3-oxo bridge) together with an hydroxide ion externally bridging the two T3 copper ions, products of the four-electrons reduction of molecular oxygen, were best modelled. Conclusion This is the first structure of a multicopper oxidase which

  16. Layered perovskite oxide: a reversible air electrode for oxygen evolution/reduction in rechargeable metal-air batteries.

    PubMed

    Takeguchi, Tatsuya; Yamanaka, Toshiro; Takahashi, Hiroki; Watanabe, Hiroshi; Kuroki, Tomohiro; Nakanishi, Haruyuki; Orikasa, Yuki; Uchimoto, Yoshiharu; Takano, Hiroshi; Ohguri, Nobuaki; Matsuda, Motofumi; Murota, Tadatoshi; Uosaki, Kohei; Ueda, Wataru

    2013-07-31

    For the development of a rechargeable metal-air battery, which is expected to become one of the most widely used batteries in the future, slow kinetics of discharging and charging reactions at the air electrode, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively, are the most critical problems. Here we report that Ruddlesden-Popper-type layered perovskite, RP-LaSr3Fe3O10 (n = 3), functions as a reversible air electrode catalyst for both ORR and OER at an equilibrium potential of 1.23 V with almost no overpotentials. The function of RP-LaSr3Fe3O10 as an ORR catalyst was confirmed by using an alkaline fuel cell composed of Pd/LaSr3Fe3O10-2x(OH)2x·H2O/RP-LaSr3Fe3O10 as an open circuit voltage (OCV) of 1.23 V was obtained. RP-LaSr3Fe3O10 also catalyzed OER at an equilibrium potential of 1.23 V with almost no overpotentials. Reversible ORR and OER are achieved because of the easily removable oxygen present in RP-LaSr3Fe3O10. Thus, RP-LaSr3Fe3O10 minimizes efficiency losses caused by reactions during charging and discharging at the air electrode and can be considered to be the ORR/OER electrocatalyst for rechargeable metal-air batteries. PMID:23802735

  17. ANME-2D Archaea Catalyze Methane Oxidation in Deep Subsurface Sediments Independent of Nitrate Reduction

    NASA Astrophysics Data System (ADS)

    Hernsdorf, A. W.; Amano, Y.; Suzuki, Y.; Ise, K.; Thomas, B. C.; Banfield, J. F.

    2015-12-01

    -reducing/oxidizing archaeon Ferroglobus placidus. Thus, we suggest that ANME2-D may couple methane oxidation to reduction of ferric iron minerals in the sediment and may be generally important as a link between the iron and methane cycles in deep subsurface environments. Such information has important implications for modeling the global carbon cycle.

  18. Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

    PubMed

    Gan, Patrick; Foord, John S; Compton, Richard G

    2015-10-01

    Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

  19. Proton switch for modulating oxygen reduction by a copper electrocatalyst embedded in a hybrid bilayer membrane

    NASA Astrophysics Data System (ADS)

    Barile, Christopher J.; Tse, Edmund C. M.; Li, Ying; Sobyra, Thomas B.; Zimmerman, Steven C.; Hosseini, Ali; Gewirth, Andrew A.

    2014-06-01

    Molecular switches gate many fundamental processes in natural and artificial systems. Here, we report the development of an electrochemical platform in which a proton carrier switches the activity of a catalyst. By incorporating an alkyl phosphate in the lipid layer of a hybrid bilayer membrane, we regulate proton transport to a Cu-based molecular oxygen reduction reaction catalyst. To construct this hybrid bilayer membrane system, we prepare an example of a synthetic Cu oxygen reduction reaction catalyst that forms a self-assembled monolayer on Au surfaces. We then embed this Cu catalyst inside a hybrid bilayer membrane by depositing a monolayer of lipid on the self-assembled monolayer. We envisage that this electrochemical system can give a unique mechanistic insight not only into the oxygen reduction reaction, but into proton-coupled electron transfer in general.

  20. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction

    PubMed Central

    Chung, Hoon T.; Won, Jong H.; Zelenay, Piotr

    2013-01-01

    Nanostructured carbon-based materials, such as nitrogen-doped carbon nanotube arrays, Co3O4/nitrogen-doped graphene hybrids and carbon nanotube–graphene complexes have shown respectable oxygen reduction reaction activity in alkaline media. Although certainly promising, the performance of these materials does not yet warrant implementation in the energy conversion/storage devices utilizing basic electrolytes, for example, alkaline fuel cells, metal-air batteries and certain electrolysers. Here we demonstrate a new type of nitrogen-doped carbon nanotube/nanoparticle composite oxygen reduction reaction electrocatalyst obtained from iron acetate as an iron precursor and from cyanamide as a nitrogen and carbon nanotube precursor in a simple, scalable and single-step method. The composite has the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts. When used at a sufficiently high loading, this catalyst also outperforms the most active platinum-based catalysts. PMID:23715281

  1. Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

    PubMed Central

    Gan, Patrick; Foord, John S; Compton, Richard G

    2015-01-01

    Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

  2. Reduction of lunar basalt 70035: Oxygen yield and reaction product analysis

    NASA Technical Reports Server (NTRS)

    Gibson, Michael A.; Knudsen, Christian W.; Bruenemen, David J.; Allen, Carlton C.; Kanamori, Hiroshi; Mckay, David S.

    1994-01-01

    Oxygen production from a lunar rock has been experimentally demonstrated for the first time. A 10 g sample of high-Ti basalt 70035 was reduced with hydrogen in seven experiments at temperatures of 900-1050 C and pressures of 14.7-150 psia. In all experiments, water evolution began almost immediately and was essentially complete in tens of minutes. Oxygen yields ranged from 2.93 to 4.61% of the starting sample weight, and showed weak dependence on temperature and pressure. Analysis of the solid samples demonstrated total reduction of Fe(2+) in ilmenite and small degrees of reduction in olivine and pyroxene. Ti O2 was also partially reduced to one or more suboxides. Data from these experiments provide a basis for predicting the yield of oxygen from lunar basalt as well as new constraints on natural reduction in the lunar regolith.

  3. The 1.5-Å Structure of XplA-heme, an Unusual Cytochrome P450 Heme Domain That Catalyzes Reductive Biotransformation of Royal Demolition Explosive*

    PubMed Central

    Sabbadin, Federico; Jackson, Rosamond; Haider, Kamran; Tampi, Girish; Turkenburg, Johan P.; Hart, Sam; Bruce, Neil C.; Grogan, Gideon

    2009-01-01

    XplA is a cytochrome P450 of unique structural organization, consisting of a heme- domain that is C-terminally fused to its native flavodoxin redox partner. XplA, along with flavodoxin reductase XplB, has been shown to catalyze the breakdown of the nitramine explosive and pollutant hexahydro-1,3,5-trinitro-1,3,5-triazine (royal demolition explosive) by reductive denitration. The structure of the heme domain of XplA (XplA-heme) has been solved in two crystal forms: as a dimer in space group P21 to a resolution of 1.9 Å and as a monomer in space group P21212 to a resolution of 1.5 Å, with the ligand imidazole bound at the heme iron. Although it shares the overall fold of cytochromes P450 of known structure, XplA-heme is unusual in that the kinked I-helix that traverses the distal face of the heme is broken by Met-394 and Ala-395 in place of the well conserved Asp/Glu plus Thr/Ser, important in oxidative P450s for the scission of the dioxygen bond prior to substrate oxygenation. The heme environment of XplA-heme is hydrophobic, featuring a cluster of three methionines above the heme, including Met-394. Imidazole was observed bound to the heme iron and is in close proximity to the side chain of Gln-438, which is situated over the distal face of the heme. Imidazole is also hydrogen-bonded to a water molecule that sits in place of the threonine side-chain hydroxyl exemplified by Thr-252 in Cyt-P450cam. Both Gln-438 → Ala and Ala-395 → Thr mutants of XplA-heme displayed markedly reduced activity compared with the wild type for royal demolition explosive degradation when combined with surrogate electron donors. PMID:19692330

  4. One Dimensional Graphitic Carbon Nitrides as Effective Metal-Free Oxygen Reduction Catalysts

    PubMed Central

    Tahir, Muhammad; Mahmood, Nasir; Zhu, Jinghan; Mahmood, Asif; Butt, Faheem K.; Rizwan, Syed; Aslam, Imran; Tanveer, M.; Idrees, Faryal; Shakir, Imran; Cao, Chuanbao; Hou, Yanglong

    2015-01-01

    To explore the effect of morphology on catalytic properties of graphitic carbon nitride (GCN), we have studied oxygen reduction reaction (ORR) performance of two different morphologies of GCN in alkaline media. Among both, tubular GCN react with dissolved oxygen in the ORR with an onset potential close to commercial Pt/C. Furthermore, the higher stability and excellent methanol tolerance of tubular GCN compared to Pt/C emphasizes its suitability for fuel cells. PMID:26201998

  5. Reduction of left ventricular epicardial segment length by 100% oxygen breathing in open-chest dogs.

    PubMed

    Ishikawa, K; Kanamasa, K; Yamakado, T; Katori, R

    1982-03-01

    We conducted this study in order to learn whether or nt oxygen inhalation reduces left ventricular size, one of the major determinants of myocardial oxygen demand. In 11 open-chest dogs, a Mercury-in-Silastic gauge was applied to measure left ventricular circumferential length while the dogs were being ventilated with either room air or 100% oxygen. Four characteristic notches were identified on the resulting length curve: L1, length at the beginning of ejection; L2, length at the end of ejection; L3, length in early diastole; and L4, length at end diastole, L1 was shortened from 24.9 +/- 10.5 to 24.4 +/- 9.9 mm (a decrease of 1.4 +/- 2.1%) by oxygen breathing, L2 was also shortened from 26.8 +/- 11.5 to 26.2 +/- 10.7 mm (a decrease of 1.5 +/- 2.9%), L3 from 17.5 +/- 4.4 to 17.4 +/- 4.3 mm (a decrease of 0.7 +/- 2.7%) and L4 from 17.7 +/- 4.8 to 17.5 +/- 4.7 mm (a decrease o 1.3 +/- 2.4%). These changes all disappeared when the inspiratory gas was changed from oxygen back to air. Heart rate and left ventricular end-diastolic pressure showed no significant changes but were accompanied by a slight reduction in aortic pressure and myocardial contractile force. This study demonstrated a small but consistent reduction in left ventricular circumferential length by oxygen breathing. This reduction in left ventricular size will reduce left ventricular tension and thus result in reduction of left ventricular myocardial oxygen demand when oxygen inhalation is applied to patients with ischemic heart disease. PMID:7071848

  6. Facet effects of palladium nanocrystals for oxygen reduction in ionic liquids and for sensing applications

    NASA Astrophysics Data System (ADS)

    Tang, Yongan; Chi, Xiaowei; Zou, Shouzhong; Zeng, Xiangqun

    2016-03-01

    Palladium nanocrystals enclosed by {100} and {110} crystal facets, were successfully synthesized through an aqueous one-pot synthesis method. A new thermal annealing approach was developed for fabricating these palladium nanocrystals as a working electrode on a gas permeable membrane to study the facet effects of the oxygen reduction process in an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpy][NTf2]). Results were compared with the same processes at a conventional platinum electrode. Our study shows that the structural difference between the two facets of Pd nanocrystals has little effect on the oxygen reduction process but significantly affects the oxidation process of the superoxide. It is found that the Pd{110}/IL interface can better stabilize superoxide radicals revealed by a more positive oxidation potential compared to that of Pd{100}. In addition, the analytical characteristic of utilizing both palladium nanocrystals as electrodes for oxygen sensing is comparable with a polycrystal platinum oxygen sensor, in which Pd{110} presents the best sensitivity and lowest detection limit. Our results demonstrate the facet-dependence of oxygen reduction in an ionic liquid medium and provide the fundamental information needed to guide the applications of palladium nanocrystals in electrochemical gas sensor and fuel cell research.Palladium nanocrystals enclosed by {100} and {110} crystal facets, were successfully synthesized through an aqueous one-pot synthesis method. A new thermal annealing approach was developed for fabricating these palladium nanocrystals as a working electrode on a gas permeable membrane to study the facet effects of the oxygen reduction process in an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpy][NTf2]). Results were compared with the same processes at a conventional platinum electrode. Our study shows that the structural difference between the two facets of Pd

  7. Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells.

    PubMed

    Renslow, Ryan; Donovan, Conrad; Shim, Matthew; Babauta, Jerome; Nannapaneni, Srilekha; Schenk, James; Beyenal, Haluk

    2011-12-28

    Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination. PMID:22052235

  8. Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells†

    PubMed Central

    Renslow, Ryan; Donovan, Conrad; Shim, Matthew; Babauta, Jerome; Nannapaneni, Srilekha; Schenk, James

    2012-01-01

    Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination. PMID:22052235

  9. Electrocatalytic Reactivity for Oxygen Reduction of Palladium-Modified Carbon Nanotubes Synthesized in Supercritical Fluid

    SciTech Connect

    Lin, Yuehe; Cui, Xiaoli; Ye, Xiangrong

    2005-02-02

    The electrocatalytic reactivity of palladium-modified carbon nanotubes (Pd-CNTs) for the oxygen reduction reaction (ORR) was investigated at the glassy carbon electrode surface in 1 M H2SO4 saturated by oxygen. Carbon nanotubes modified by palladium nanoparticles were synthesized in supercritical carbon dioxide and characterized by transmission electron micrograph. The electrocatalytic activity of the CNTs film and Pd–CNTs film toward oxygen reduction was studied using cyclic voltammetry and linear sweep voltammetry methods. The molecular oxygen reduction at the Pd-CNTs electrode started at a more positive potential than that at the CNTs electrode. A possible reaction mechanism was proposed in which the ORR may proceed through two-step two-electron processes for the Pd-CNTs modified electrode. Experimental results revealed that Pd-CNTs possess a remarkable activity and high stability for oxygen reduction in acid medium, which implies the potential applications of the Pd–CNTs for constructing electrodes of fuel cells.

  10. Oxygen reduction reaction on palladium-cobalt alloy catalysts for polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Oishi, Kentaro

    The Oxygen Reduction Reaction (ORR) activity in acid medium on Pd-Co was studied in this work. The catalysts were synthesized by two techniques; physical vapor deposition technique and ultrasonic spray reaction technique. The last technique was developed for the first time in our laboratory for the supported electro catalyst preparation and direct deposition onto the carbon paper or gas diffusion electrode the for PEMFC applications. The electrochemical properties such as the amount of hydrogen adsorption/desorption, the oxide formation/reduction of Pd-Co alloy catalyst have not been sufficiently studied before. Therefore these electrochemical properties were investigated by using the Pd-Co thin films prepared by sputtering method. A thin film catalyst cannot be directly used as an electrode of working PEMFCs, however the sputtering method is very useful since the chemical composition of alloy and surface area of the electrode can be controlled easily. Thus the fundamental electrochemical properties such as the amount of hydrogen adsorption/desorption, oxide formation/reduction and oxide reduction peak position on thin films of Pd-Co alloy, Pd and Pt catalysts were determined and their correlations to ORR catalytic activities in acid medium were studied. Enhancements of the catalytic activities for ORR by Pd-Co binary alloys were found to be in agreement with results obtained in previous studies. Ultrasonic spray reaction method was developed for the first time in our laboratory for carbon supported nano-scale catalyst for PEMFC application. Fine catalyst particles supported on high surface area carbon powder are required to apply the catalyst as the PEMFC cathode materials for the commercialization, but none of the studies done before were able to successfully obtain the Pd-Co fine particles which are comparable with the existing carbon supported platinum catalyst (ϕ2-4nm). Therefore the establishment of the catalyst synthesis method for Pd-Co fine particles are

  11. Copper-catalyzed asymmetric synthesis of tertiary α-hydroxy phosphonic acid derivatives with in situ generated nitrosocarbonyl compounds as the oxygen source.

    PubMed

    Maji, Biplab; Yamamoto, Hisashi

    2014-12-22

    α-Hydroxy phosphonic acids and their derivatives are highly bioactive structural motifs. It is now reported that these compounds can be accessed through the copper-catalyzed direct α-oxidation of β-ketophosphonates using in situ generated nitrosocarbonyl compounds as an electrophilic oxygen source. These reactions proceeded in high yields (up to 95 %) and enantioselectivities (up to >99 % ee) for both cyclic as well as acyclic substrates. This method was also applied for the synthesis of α,β-dihydroxy phosphonates and β-amino-α-hydroxy phosphonates. PMID:25348199

  12. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    PubMed

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process. PMID:25251943

  13. Method for oxygen reduction in a uranium-recovery process. [US DOE patent application

    DOEpatents

    Hurst, F.J.; Brown, G.M.; Posey, F.A.

    1981-11-04

    An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous iron and accumulation of complex iron phosphates or cruds.

  14. Oxygen reduction on Ni, Ag, and Cu meniscus electrodes in molten carbonate

    SciTech Connect

    Ogura, Hiroyuki; Shirogami, Tamotsu

    1994-12-31

    The oxygen reduction pathways in molten carbonates have been investigated by analyzing the charge transfer resistances of the i-V curves on the meniscus electrodes of Ni, Cu, and Ag screens at 550 C. The electrochemical reduction pathways of oxygen at the meniscus electrode were found to be different depending on the electrode materials. For the Ni meniscus electrode system, the reactive material of charge transfer is the lithium doped nickel oxide, for the Ag system that is the silver oxide ion, and for the Cu system that is peroxide ion, respectively.

  15. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

    NASA Astrophysics Data System (ADS)

    Verdaguer-Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E. L.; Chorkendorff, Ib; Dahl, Søren

    2012-12-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction is severely poisoned. Poisoning at the cathode explains the majority of the losses observed in polymer electrolyte membrane fuel cells contaminated with ammonia. Voltammetry in deaerated solution suggest that the poisoning can be attributed to either ammonium oxidation or increased binding to OH species.

  16. Unifying the 2e(-) and 4e(-) Reduction of Oxygen on Metal Surfaces.

    PubMed

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens K

    2012-10-18

    Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e(-) versus 4e(-) reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e(-) and 4e(-) reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e(-) reduction, this weak binding is optimal for the 2e(-) reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years. PMID:26292231

  17. Determination of reactive oxygen species generated in laccase catalyzed oxidation of wood fibers from Chinese fir (Cunninghamia lanceolata) by electron spin resonance spectrometry.

    PubMed

    Zhou, Guanwu; Li, Jianing; Chen, Yongsheng; Zhao, Baolu; Cao, Yongjian; Duan, Xinfang; Cao, Yuanlin

    2009-01-01

    The aim of the present study was to determine whether the radical reaction intermediates--reactive oxygen species (ROS) were formed during the laccase-catalyzed oxidation of wood fibers from Chinese fir (Cunninghamia lanceolata) and to quantify tentatively its production with electron spin resonance (ESR) spectrometry. To investigate the activation pathways triggered by laccase, ESR spin-trapping techniques using N-tert-butyl-alpha-phenylnitrone (PBN) as spin trap followed by ethyl acetate extraction were employed to identify and quantify the free radical intermediates. ROS such as the superoxide and hydroxyl radical was detected and quantified in the laccase catalyzed oxidation of wood fibers, suggesting that ROS is the main free radical intermediates for laccase reaction. Based on the findings of the presence of ROS and previous literature on the free radical reaction of laccase oxidation of wood fibers, a possible reaction mechanism involving ROS-mediated attack on the domains of lignin which is not directly accessible for the enzyme and solubilized low-molecular mass lignins which function as reactive compounds like adhesives and may cling back to the fiber surface, could accordingly describe laccase-catalyzed oxidation of Chinese fir wood fibers. PMID:18650080

  18. The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans)

    PubMed Central

    Šarlauskas, Jonas; Misevičienė, Lina; Marozienė, Audronė; Karvelis, Laimonas; Stankevičiūtė, Jonita; Krikštopaitis, Kastis; Čėnas, Narimantas; Yantsevich, Aleksey; Laurynėnas, Audrius; Anusevičius, Žilvinas

    2014-01-01

    The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs) towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R) and two-electron (hydride) transferring NAD(P)H:quinone oxidoreductase (NQO1) was examined in this work. Since the =N+ (→O)O− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs) whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs) of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride) transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary reductive

  19. Carbon nanotubes-gold nanohybrid as potent electrocatalyst for oxygen reduction in alkaline media.

    PubMed

    Morozan, Adina; Donck, Simon; Artero, Vincent; Gravel, Edmond; Doris, Eric

    2015-11-01

    A carbon nanotube-gold nanohybrid was used as catalyst for the reduction of molecular oxygen in acidic and alkaline media, the relevant cathode reaction in fuel cells. In alkaline medium, the nanohybrid exhibits excellent activity with a dominant 4e(-) reduction of O2 and low overpotential requirement compared to previously reported nano-gold materials. This property is linked to its capability to efficiently mediate HO2(-) dismutation. PMID:26439282

  20. Effect of carbon nanofiber surface functional groups on oxygen reduction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Zhong, Ren-Sheng; Qin, Yuan-Hang; Niu, Dong-Fang; Tian, Jing-Wei; Zhang, Xin-Sheng; Zhou, Xin-Gui; Sun, Shi-Gang; Yuan, Wei-Kang

    2013-03-01

    Carbon nanofibers (CNFs) with different content of surface functional groups which are carboxyl groups (CNF-OX), carbonyl groups (CNF-CO) and hydroxyl groups (CNF-OH) and nitrogen-containing groups (CNF-ON) are synthesized, and their electrocatalytic activities toward oxygen reduction reaction (ORR) in alkaline solution are investigated. The result of X-ray photoelectron spectroscopy (XPS) characterization indicates that a higher concentration of carboxyl groups, carbonyl groups and hydroxyl groups are imported onto the CNF-OX, CNF-CO and CNF-OH, respectively. Cyclic voltammetry shows that both the oxygen- and nitrogen-containing groups can improve the electrocatalytic activity of CNFs for ORR. The CNF-ON/GC electrode, which has nitrogen-containing groups, exhibits the highest current density of ORR. Rotating disk electrode (RDE) characterization shows that the oxygen reduction on CNF-ON/GC electrode proceeds almost entirely through the four-electron reduction pathway, the CNF-OX/GC, CNF-CO/GC and CNF-OH/GC electrodes proceed a two-electron reduction pathway at low potentials (-0.2 V to -0.6 V) followed by a gradual four-electron reduction pathway at more negative potentials, while the untreated carbon nanofiber (CNF-P/GC) electrode proceeds predominantly by a two-electron reduction pathway within the whole range of potential studied.

  1. Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Pan, Fuping; Cao, Zhongyue; Zhao, Qiuping; Liang, Hongyu; Zhang, Junyan

    2014-12-01

    The successful commercialization of fuel cells requires the efficient electrocatalyst to make the oxygen reduction reaction (ORR) fast because of the sluggish nature of ORR and the high cost of the platinum catalysts. In this work, we report the excellent performance of metal-free nitrogen-doped porous carbon nanosheets (NPCN) with hierarchical porous structure and a high surface area of 1436.02 m2 g-1 for catalyzing ORR. The active NPCN is synthesized via facile high-temperature carbonization of natural ginkgo leaves followed by purification and ammonia post-treatment without using additional supporting templates and activation processes. In O2-saturated 0.1 M KOH solution, the resultant NPCN exhibits a high kinetic-limiting current density of 13.57 mA cm-2 at -0.25 V (vs. Ag/AgCl) approaching that of the commercial Pt/C catalyst (14 mA cm-2) and long-term electrochemical stability. Notably, the NPCN shows a slightly negative ORR half-wave potential in comparison with Pt/C (ΔE1/2 = 19 mV). The excellent electrocatalytic properties of NPCN originate from the combined effect of optimal nitrogen doping, high surface area, and porous architecture, which induce the high-density distribution of highly active and stable catalytic sites.

  2. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

    PubMed Central

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  3. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction.

    PubMed

    Yuan, Xianxia; Hu, Xin-Xin; Ding, Xin-Long; Kong, Hai-Chuan; Sha, Hao-Dong; Lin, He; Wen, Wen; Shen, Guangxia; Guo, Zhi; Ma, Zi-Feng; Yang, Yong

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  4. Theoretical investigations on SiC2 siligraphene as promising metal-free catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Dong, Huilong; Lin, Bin; Gilmore, Keith; Hou, Tingjun; Lee, Shuit-Tong; Li, Youyong

    2015-12-01

    The design and discovery of high-performance metal-free catalytic materials for oxygen reduction reaction (ORR) electrocatalysis is vital for the development of fuel cells. By performing density functional theory (DFT) calculations, we investigate the potential applications of SiC2 siligraphene (g-SiC2) as metal-free ORR catalyst. The g-SiC2 exhibits higher adsorption affinity for the O2 molecule and other ORR intermediates than the traditional Pt (111), and shows good tolerance against CO poisoning. The detailed LH and ER mechanisms in catalyzing ORR by g-SiC2 are simulated and discussed, both in acidic and alkaline environment. We find that, in alkaline environment, the g-SiC2 presents a very low activation barrier (0.16 eV) for the rate determining step (RDS) and shows no overpotential at the equilibrium potential. Our theoretical simulations validate that the siligraphene with alternatively arranged Si and C atoms holds great potential as ORR catalyst in alkaline environment.

  5. Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability.

    PubMed

    Spanos, Ioannis; Dideriksen, Knud; Kirkensgaard, Jacob J K; Jelavic, Stanislav; Arenz, Matthias

    2015-11-14

    Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Pt(x)Co(1-x) colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal composition affects their electrocatalytic performance. The results show that upon contact with acid environment the Co leaches out of the particles leading to almost identical compositions, independent of the initial differences. Surprisingly the data show a clear trend in ORR activity, although the Pt(x)Co(1-x) nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process. PMID:25537262

  6. Graphene-based hollow spheres as efficient electrocatalysts for oxygen reduction.

    PubMed

    Wu, Longfei; Feng, Hongbin; Liu, Mengjia; Zhang, Kaixiang; Li, Jinghong

    2013-11-21

    A facile and straightforward approach is developed for the construction of graphene-based hollow spheres. An electron rich sodium-ammonia solution is used to effectively restore the π-conjugation of graphene. The hollow spheres exhibit excellent electrocatalytic activity towards oxygen reduction without catalyst deactivation. PMID:24089043

  7. N-doped graphene natively grown on hierarchical ordered porous carbon for enhanced oxygen reduction.

    PubMed

    Liang, Ji; Du, Xin; Gibson, Christopher; Du, Xi Wen; Qiao, Shi Zhang

    2013-11-20

    A novel nitrogen doped hybrid material composed of in situ-formed graphene natively grown on hierarchical ordered porous carbon is prepared, which successfully combines the advantages of both materials, such as high surface area, high mass transfer, and high conductivity. The outstanding structural properties of the resultant material render it an excellent metal-free catalyst for electrochemical oxygen reduction. PMID:23963824

  8. Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2013-03-14

    We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, induced by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  9. Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-10-10

    We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, induced by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.

  10. The 2010 Field Demonstration of the Solar Carbothermal Reduction of Regolith to Produce Oxygen

    NASA Technical Reports Server (NTRS)

    Gustafson, R. J.; White, B. C.; Fidler, M. J.; Muscatello, Anthony C.

    2010-01-01

    The Moon and other space exploration destinations are comprised of a variety of oxygen-bearing minerals, providing a virtually unlimited quantity of raw material which can be processed to produce oxygen. One attractive method to extract oxygen from the regolith is the carbothermal reduction process, which is not sensitive to variations in the mineral composition of the regolith. It also creates other valuable resources within the processed regolith, such as iron and silicon metals. Using funding from NASA, ORBITEC recently built and tested the Carbothermal Regolith Reduction Module to process lunar regolith simulants using concentrated solar energy. This paper summarizes the experimental test results obtained during a demonstration of the system at a lunar analog test site on the Mauna Kea volcano on Hawaii in February 2010.

  11. Synthesis of tertiary arylamines: Lewis acid-catalyzed direct reductive N-alkylation of secondary amines with ketones through an alternative pathway.

    PubMed

    Nayal, Onkar S; Thakur, Maheshwar S; Bhatt, Vinod; Kumar, Manoranjan; Kumar, Neeraj; Singh, Bikram; Sharma, Upendra

    2016-08-11

    We report herein a highly efficient, tin(ii)/PMHS catalyzed reductive N-alkylation of arylamines with ketones affording tertiary arylamines. A very wide substrate scope was observed for the current catalytic method as all six permutations of ketones/aldehydes/heterocyclic carbonyls and primary/secondary/heterocyclic amines were well tolerated, enabling access to secondary, tertiary and heterocyclic amines. The method is also convenient for the synthesis of N-substituted isoindolinones and phthalazinones via a tandem amination-amidation sequence. Mechanistic investigations revealed a carbocationic pathway instead of an ordinary direct reductive amination pathway. PMID:27363507

  12. EFFECT OF PRETREATMENT ON PT-CO/C CATHODE CATALYSTS FOR THE OXYGEN-REDUCTION REACTION

    SciTech Connect

    Fox, E.; Colon-Mercado, H.

    2010-01-19

    Carbon supported Pt and Pt-Co electrocatalysts for the oxygen reduction reaction in low temperature fuel cells were prepared by the reduction of the metal salts with sodium borohydride and sodium formate. The effect of surface treatment with nitric acid on the carbon surface and Co on the surface of carbon prior to the deposition of Pt was studied. The catalysts where Pt was deposited on treated carbon the ORR reaction preceded more through the two electron pathway and favored peroxide production, while the fresh carbon catalysts proceeded more through the four electron pathway to complete the oxygen reduction reaction. NaCOOH reduced Pt/C catalysts showed higher activity that NaBH{sub 4} reduced Pt/C catalysts. It was determined that the Co addition has a higher impact on catalyst activity and active surface area when used with NaBH{sub 4} as reducing agent as compared to NaCOOH.

  13. Electrodeposited noble metal particles in polyelectrolyte multilayer matrix as electrocatalyst for oxygen reduction studied using SECM.

    PubMed

    Shen, Yan; Träuble, Markus; Wittstock, Gunther

    2008-07-01

    Taking the advantage of the stability and penetrability of polyelectrolyte films formed by layer-by-layer (LbL) deposition, noble metal particles of Pd and Pt were fabricated in a preformed polyeletrolyte multilayer film by galvanic deposition. The metal deposition occurred as metal particles and they were tested for their properties as electrocatalyst for oxygen reduction. Atomic force microscopy (AFM) was used to characterize the morphology of the particle films. The noble metal particles were investigated by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) with respect to oxygen reduction. The results show that the electrocatalytic properties of the Pd particle film can be adjusted by the electrodeposition time. The hydrogen peroxide formed as an intermediate during electroreduction of dioxygen was conveniently measured in the SECM using the substrate-generation/tip-collection mode. The relevance of the main reduction pathways could be extracted from fitting the current transients to an analytical model. PMID:18563224

  14. Uranium- and thorium-doped graphene for efficient oxygen and hydrogen peroxide reduction.

    PubMed

    Sofer, Zdeněk; Jankovský, Ondřej; Šimek, Petr; Klímová, Kateřina; Macková, Anna; Pumera, Martin

    2014-07-22

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in the fields of energy generation and sensing. Metal-doped graphenes, where metal serves as the catalytic center and graphene as the high area conductor, have been used as electrocatalysts for such applications. In this paper, we investigated the use of uranium-graphene and thorium-graphene hybrids prepared by a simple and scalable method. The hybrids were synthesized by the thermal exfoliation of either uranium- or thorium-doped graphene oxide in various atmospheres. The synthesized graphene hybrids were characterized by high-resolution XPS, SEM, SEM-EDS, combustible elemental analysis, and Raman spectroscopy. The influence of dopant and exfoliation atmosphere on electrocatalytic activity was determined by electrochemical measurements. Both hybrids exhibited excellent electrocatalytic properties toward oxygen and hydrogen peroxide reduction, suggesting that actinide-based graphene hybrids have enormous potential for use in energy conversion and sensing devices. PMID:24979344

  15. Controlling Solution-Mediated Reaction Mechanisms of Oxygen Reduction Using Potential and Solvent for Aprotic Lithium-Oxygen Batteries.

    PubMed

    Kwabi, David G; Tułodziecki, Michał; Pour, Nir; Itkis, Daniil M; Thompson, Carl V; Shao-Horn, Yang

    2016-04-01

    Fundamental understanding of growth mechanisms of Li2O2 in Li-O2 cells is critical for implementing batteries with high gravimetric energies. Li2O2 growth can occur first by 1e(-) transfer to O2, forming Li(+)-O2(-) and then either chemical disproportionation of Li(+)-O2(-), or a second electron transfer to Li(+)-O2(-). We demonstrate that Li2O2 growth is governed primarily by disproportionation of Li(+)-O2(-) at low overpotential, and surface-mediated electron transfer at high overpotential. We obtain evidence supporting this trend using the rotating ring disk electrode (RRDE) technique, which shows that the fraction of oxygen reduction reaction charge attributable to soluble Li(+)-O2(-)-based intermediates increases as the discharge overpotential reduces. Electrochemical quartz crystal microbalance (EQCM) measurements of oxygen reduction support this picture, and show that the dependence of the reaction mechanism on the applied potential explains the difference in Li2O2 morphologies observed at different discharge overpotentials: formation of large (∼250 nm-1 μm) toroids, and conformal coatings (<50 nm) at higher overpotentials. These results highlight that RRDE and EQCM can be used as complementary tools to gain new insights into the role of soluble and solid reaction intermediates in the growth of reaction products in metal-O2 batteries. PMID:26949979

  16. A biosynthetic model of cytochrome c oxidase as an electrocatalyst for oxygen reduction.

    PubMed

    Mukherjee, Sohini; Mukherjee, Arnab; Bhagi-Damodaran, Ambika; Mukherjee, Manjistha; Lu, Yi; Dey, Abhishek

    2015-01-01

    Creating an artificial functional mimic of the mitochondrial enzyme cytochrome c oxidase (CcO) has been a long-term goal of the scientific community as such a mimic will not only add to our fundamental understanding of how CcO works but may also pave the way for efficient electrocatalysts for oxygen reduction in hydrogen/oxygen fuel cells. Here we develop an electrocatalyst for reducing oxygen to water under ambient conditions. We use site-directed mutants of myoglobin, where both the distal Cu and the redox-active tyrosine residue present in CcO are modelled. In situ Raman spectroscopy shows that this catalyst features very fast electron transfer rates, facile oxygen binding and O-O bond lysis. An electron transfer shunt from the electrode circumvents the slow dissociation of a ferric hydroxide species, which slows down native CcO (bovine 500 s(-1)), allowing electrocatalytic oxygen reduction rates of 5,000 s(-1) for these biosynthetic models. PMID:26455726

  17. A biosynthetic model of cytochrome c oxidase as an electrocatalyst for oxygen reduction

    PubMed Central

    Mukherjee, Sohini; Mukherjee, Arnab; Bhagi-Damodaran, Ambika; Mukherjee, Manjistha; Lu, Yi; Dey, Abhishek

    2015-01-01

    Creating an artificial functional mimic of the mitochondrial enzyme cytochrome c oxidase (CcO) has been a long-term goal of the scientific community as such a mimic will not only add to our fundamental understanding of how CcO works but may also pave the way for efficient electrocatalysts for oxygen reduction in hydrogen/oxygen fuel cells. Here we develop an electrocatalyst for reducing oxygen to water under ambient conditions. We use site-directed mutants of myoglobin, where both the distal Cu and the redox-active tyrosine residue present in CcO are modelled. In situ Raman spectroscopy shows that this catalyst features very fast electron transfer rates, facile oxygen binding and O–O bond lysis. An electron transfer shunt from the electrode circumvents the slow dissociation of a ferric hydroxide species, which slows down native CcO (bovine 500 s−1), allowing electrocatalytic oxygen reduction rates of 5,000 s−1 for these biosynthetic models. PMID:26455726

  18. Oxygen isotope effects of enzyme-catalyzed organophosphorus hydrolysis reactions: implications for interpretation of dissolved PO4 δ18O values in natural waters

    NASA Astrophysics Data System (ADS)

    Liang, Y.; Blake, R. E.

    2002-12-01

    The geochemical cycling of P in Earth surface environments is controlled largely by biota. It has been recently demonstrated that intracellular cycling of P in microbial cultures and biological turnover of P in natural waters leads to temperature-dependent O isotope equilibrium between dissolved inorganic PO4 (Pi) and ambient water, and that the δ18O of Pi can be a useful tracer of biological reactions and P cycling in aquatic systems/sediments. Oxygen isotope exchange between Pi and water during biological turnover of P is catalyzed by enzymes at low-temperature. Phosphoenzymes play a crucial role in the intracellular functions of all living organisms and also have important extracellular functions in aquatic ecosystems such as regeneration of Pi from organophosphorus compounds (e.g., phosphoesters). Laboratory experiments indicate that extracellular enzyme reactions may result in incomplete Pi turnover and non-equilibrium Pi-water O isotope exchange. Determination of the O isotope effects of phosphoenzyme-catalyzed reactions is fundamental to the understanding of mechanisms of PO4-water O isotope exchange, pathways of biogeochemical P cycling, and interpretation of PO4 δ18O values from natural systems. Here we report on the O isotope fractionation between enzymatically-released Pi and water, in cell-free abiotic systems. Alkaline phosphatase (Apase) is a non-specific phosphohydrolase commonly found in fresh and marine coastal waters that catalyzes the hydrolysis of Pi from phosphomonoesters. We examined the O isotope effects of Apase derived from both microbial and eukaryotic sources and acting on different phosphomonoester substrates (e.g., α-D-Glucose 1-Phosphate, β-Glycerophosphate, AMP) in 18O-labeled waters. Oxygen isotope ratios of Pi released by Apase indicate that only 1 of the 4 O atoms in PO4 is incorporated from water with little or no apparent O isotopic fractionation at the site of incorporation. This observation is consistent with

  19. Biological and chemical interaction of oxygen on the reduction of Fe(III)EDTA in a chemical absorption-biological reduction integrated NOx removal system.

    PubMed

    Zhang, Shi-Han; Shi, Yao; Li, Wei

    2012-03-01

    A promising chemical absorption-biological reduction integrated process has been proposed. A major problem of the process is oxidation of the active absorbent, ferrous ethylenediaminetetraacetate (Fe(II)EDTA), to the ferric species, leading to a significant decrease in NO removal efficiency. Thus the biological reduction of Fe(III)EDTA is vitally important for the continuous NO removal. Oxygen, an oxidizing agent and biological inhibitor, is typically present in the flue gas. It can significantly retard the application of the integrated process. This study investigated the influence mechanism of oxygen on the regeneration of Fe(II)EDTA in order to provide insight on how to eliminate or decrease the oxygen influence. The experimental results revealed that the dissolved oxygen and Fe(III)EDTA simultaneously served as electron acceptor for the microorganism. The Fe(III)EDTA reduction activity were directly inhibited by the dissolved oxygen. When the bioreactor was supplied with 3% and 8% oxygen in the gas phase, the concentration of initial dissolved oxygen in the liquid phase was 0.28 and 0.68 mg l(-1). Correspondingly, the instinct Fe(III)EDTA reduction activity of the microorganism determined under anoxic condition in a rotation shaker decreased from 1.09 to 0.84 and 0.49 mM h(-1). The oxidation of Fe(II)EDTA with dissolved oxygen prevented more dissolved oxygen access to the microorganism and eased the inhibition of dissolved oxygen on the microorganisms. PMID:21931973

  20. Studies of reductive elimination reactions to form carbon-oxygen bonds from Pt(IV) complexes.

    PubMed

    Williams, B S; Goldberg, K I

    2001-03-21

    The platinum(IV) complexes fac-L(2)PtMe(3)(OR) (L(2) = bis(diphenylphosphino)ethane, o-bis(diphenylphosphino)benzene, R = carboxyl, aryl; L = PMe(3), R = aryl) undergo reductive elimination reactions to form carbon-oxygen bonds and/or carbon-carbon bonds. The carbon-oxygen reductive elimination reaction produces either methyl esters or methyl aryl ethers (anisoles) and L(2)PtMe(2), while the carbon-carbon reductive elimination reaction affords ethane and L(2)PtMe(OR). Choice of reaction conditions allows the selection of either type of coupling over the other. A detailed mechanistic study of the reductive elimination reactions supports dissociation of the OR(-) ligand as the initial step for the C-O bond formation reaction. This is followed by a nucleophilic attack of OR(-) upon a methyl group bound to the Pt(IV) cation to produce the products MeOR and L(2)PtMe(2). C-C reductive elimination proceeds from L(2)PtMe(3)(OR) by initial L (L = PMe(3)) or OR(-) (L(2) = dppe, dppbz) dissociation, followed by C-C coupling from the resulting five-coordinate intermediate. Our studies demonstrate that both C-C and C-O reductive elimination reactions from Pt(IV) are more facile in polar solvents, in the presence of Lewis acids, and for OR(-) groups that contain electron withdrawing substituents. PMID:11456927

  1. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy

  2. A Micro-Scale Model for Oxygen Reduction on LSM-YSZ Cathode

    SciTech Connect

    Pakalapati, Suryanarayana Raju; Celik, Ismail; Finklea, Harry; Gong, Mingyang; Liu, Xingbo

    2011-05-01

    In this study, a micro-scale model is developed to simulate the oxygen reduction on LSM-YSZ composite cathode. The model incorporates the effects of cathode microstructural properties on the local transport phenomena and electrochemistry inside the cathode. A detailed reaction mechanism is used in the model which has two parallel routes for oxygen conversion into oxide ions, namely two-phase boundary and three-phase boundary pathways. The model predicts field distributions of local thermodynamic values, over-potential, Faradaic current and other parameters relevant to cathode performance. Electrochemical impedance simulations are performed using the current model to analyze the contribution of various processes to the overall impedance.

  3. Investigation into Oxygen-Enriched Bottom-Blown Stibnite and Direct Reduction

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Luo, Honglin; Qing, Wenqing; Zheng, Yongxing; Yang, Kang; Han, Junwei

    2014-08-01

    The direct oxidation of stibnite (Sb2S3) using a gas mixture of nitrogen-oxygen was investigated in a pilot plant. Steady-state pilot operation of 5 and 10 t/d was normally observed during the pilot test of 100 days, and a cleaning experiment of high-antimony molten slag from oxygen-enriched bottom-blown was tested by direct reduction in a laboratory-scale electric furnace. Autogenous smelting was achieved without adding any other fuel, which guaranteed the feasibility and advantage of oxygen-enriched bottom-blown stibnite. Through analysis and calculation, the sulfur dioxide concentration in offgas was more than 8 pct, which meets the requirement for the preparation of sulfuric acid. In the reduction experiment, the effects of added CaO, the ratio of coal ( ω = actual weight of coal/theoretical weight of coal), and the slag type on the reduction procedure were considered. The residual slag obtained after reduction averaged less than 1 g/ton Au and less than 1 wt pct Sb. The metal phase contained iron less than 3 wt pct, and the recoveries of Au in the metal phase were more than 98 pct. This process shows significant environmental and economic benefits compared with previous processes.

  4. A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes

    PubMed Central

    Gligorich, Keith M.; Iwai, Yasumasa; Cummings, Sarah A.; Sigman, Matthew S.

    2009-01-01

    Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization. PMID:20161306

  5. Co/CoO nanoparticles immobilized on Co-N-doped carbon as trifunctional electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions.

    PubMed

    Zhang, Xian; Liu, Rongrong; Zang, Yipeng; Liu, Guoqiang; Wang, Guozhong; Zhang, Yunxia; Zhang, Haimin; Zhao, Huijun

    2016-05-01

    Co/CoO nanoparticles immobilized on Co-N-doped carbon were successfully developed using shrimp-shell derived N-doped carbon nanodots as precursors by a combined approach of polymerization and pyrolysis, as electrocatalysts exhibiting trifunctional catalytic activities toward oxygen reduction, oxygen evolution and hydrogen evolution reactions and high performance in rechargeable zinc-air batteries. PMID:27056374

  6. Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides.

    PubMed

    Konev, Mikhail O; Hanna, Luke E; Jarvo, Elizabeth R

    2016-06-01

    Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions. A range of heterocycles and functional groups are tolerated under the reaction conditions. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described. PMID:27099968

  7. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction.

    PubMed

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P; Zhang, Jiujun

    2016-01-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

  8. Facile Fabrication of N-Doped Graphene as Efficient Electrocatalyst for Oxygen Reduction Reaction.

    PubMed

    Liao, Yongliang; Gao, Yuan; Zhu, Shenmin; Zheng, Junsheng; Chen, Zhixin; Yin, Chao; Lou, Xianghong; Zhang, Di

    2015-09-01

    A facile bottom-up method is reported here for the fabrication of N-doped graphene for oxygen reduction. It consists of a two-step calcination strategy and uses α-hydroxy acids (AHAs) as carbon source and melamine as nitrogen source. Three different AHAs, malic acid, tartaric acid, and citric acid, were chosen as the carbon sources. The prepared N-doped graphenes have a typical thin layered structure with a large specific surface area. It was found that the N content in the obtained N-doped graphenes varies from 4.12 to 8.11 at. % depending on the AHAs used. All of the samples showed high performance in oxygen reduction reaction (ORR). The N-doped graphene prepared from citric acid demonstrated the highest electrocatalytic activity, which is comparable to the commercial Pt/C and exhibited good durability, attributing to the high pyridinic N content in the composite. PMID:26291928

  9. Importance of interatomic spacing in catalytic reduction of oxygen in phosphoric acid

    NASA Technical Reports Server (NTRS)

    Jalan, V.; Taylor, E. J.

    1983-01-01

    A correlation between the nearest-neighbor distance and the oxygen reduction activity of various platinum alloys is reported. It is proposed that the distance between nearest-neighbor Pt atoms on the surface of a supported catalyst is not ideal for dual site absorption of O2 or 'HO2' and that the introduction of foreign atoms which reduce the Pt nearest-neighbor spacing would result in higher oxygen reduction activity. This may allow the critical 0-0 bond interatomic distance and hence the optimum Pt-Pt separation for bond rupture to be determined from quantum chemical calculations. A composite analysis shows that the data on supported Pt alloys are consistent with Appleby's (1970) data on bulk metals with respect to specific activity, activation energy, preexponential factor, and percent d-band character.

  10. High-Performance Pd3Pb Intermetallic Catalyst for Electrochemical Oxygen Reduction.

    PubMed

    Cui, Zhiming; Chen, Hao; Zhao, Mengtian; DiSalvo, Francis J

    2016-04-13

    Extensive efforts to develop highly active and strongly durable electrocatalyst for oxygen reduction are motivated by a need for metal-air batteries and fuel cells. Here, we report a very promising catalyst prototype of structurally ordered Pd-based alloys, Pd3Pb intermetallic compound. Such structurally ordered Pd3Pb/C exhibits a significant increase in mass activity. More importantly, compared to the conventional Pt/C catalysts, ordered Pd3Pb/C is highly durable and exhibits a much longer cycle life and higher cell efficiency in Zn-air batteries. Interestingly, ordered Pd3Pb/C possesses very high methanol tolerance during electrochemical oxygen reduction, which make it an excellent methanol-tolerant cathode catalyst for alkaline polymer electrolyte membrane fuel cells. This study provides a promising route to optimize the synthesis of ordered Pd-based intermetallic catalysts for fuel cells and metal-air batteries. PMID:26848634

  11. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

    PubMed Central

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

    2016-01-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

  12. Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

    2016-02-01

    A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst.

  13. Activation energies for oxygen reduction on platinum alloys: theory and experiment.

    PubMed

    Anderson, Alfred B; Roques, Jérôme; Mukerjee, Sanjeev; Murthi, Vivek S; Markovic, Nenad M; Stamenkovic, Vojislav

    2005-01-27

    A combined theoretical and experimental analysis of the electrode potential dependencies of activation energies is presented for the first step in oxygen reduction over platinum and platinum alloy catalysts in both polycrystalline and carbon supported form. Tafel data for several of the catalysts are used to predict potential-dependent activation energies for oxygen reduction over the 0.6-0.9 V range in strong and weak acid. Comparisons with the theoretical curve show good agreement above 0.8 V, suggesting a fairly constant preexponential factor. Arrhenius determinations of activation energies over the 0.7-0.9 V range yield little trend for weak acid, possibly because of the larger uncertainties in the Arrhenius fits, but the strong acid results have smaller uncertainties and for them the measured activation energies trend up with potential. PMID:16851081

  14. Hierarchical CO2-protective shell for highly efficient oxygen reduction reaction

    PubMed Central

    Zhou, Wei; Liang, Fengli; Shao, Zongping; Zhu, Zhonghua

    2012-01-01

    The widespread application of intermediate-temperature solid oxide fuel cells is mainly being hurdled by the cathode's low efficiency on oxygen reduction reaction and poor resistance to carbon dioxide impurity. Here we report the fabrication of a hierarchical shell-covered porous cathode through infiltration followed by microwave plasma treatment. The hierarchical shell consists of a dense thin-film substrate with cones on the top of the substrate, leading to a three-dimensional (3D) heterostructured electrode. The shell allows the cathode working stably in CO2-containing air, and significantly improving the cathode's oxygen reduction reactivity with an area specific resistance of ∼0.13 Ωcm2 at 575°C. The method is also suitable for fabricating functional shell on the irregularly shaped substrate in various applications. PMID:22439104

  15. Structural basis of the divergent oxygenation reactions catalyzed by the rieske nonheme iron oxygenase carbazole 1,9a-dioxygenase.

    PubMed

    Inoue, Kengo; Usami, Yusuke; Ashikawa, Yuji; Noguchi, Haruko; Umeda, Takashi; Yamagami-Ashikawa, Aiko; Horisaki, Tadafumi; Uchimura, Hiromasa; Terada, Tohru; Nakamura, Shugo; Shimizu, Kentaro; Habe, Hiroshi; Yamane, Hisakazu; Fujimoto, Zui; Nojiri, Hideaki

    2014-05-01

    Carbazole 1,9a-dioxygenase (CARDO), a Rieske nonheme iron oxygenase (RO), is a three-component system composed of a terminal oxygenase (Oxy), ferredoxin, and a ferredoxin reductase. Oxy has angular dioxygenation activity against carbazole. Previously, site-directed mutagenesis of the Oxy-encoding gene from Janthinobacterium sp. strain J3 generated the I262V, F275W, Q282N, and Q282Y Oxy derivatives, which showed oxygenation capabilities different from those of the wild-type enzyme. To understand the structural features resulting in the different oxidation reactions, we determined the crystal structures of the derivatives, both free and complexed with substrates. The I262V, F275W, and Q282Y derivatives catalyze the lateral dioxygenation of carbazole with higher yields than the wild type. A previous study determined the crystal structure of Oxy complexed with carbazole and revealed that the carbonyl oxygen of Gly178 hydrogen bonds with the imino nitrogen of carbazole. In these derivatives, the carbazole was rotated approximately 15, 25, and 25°, respectively, compared to the wild type, creating space for a water molecule, which hydrogen bonds with the carbonyl oxygen of Gly178 and the imino nitrogen of carbazole. In the crystal structure of the F275W derivative complexed with fluorene, C-9 of fluorene, which corresponds to the imino nitrogen of carbazole, was oriented close to the mutated residue Trp275, which is on the opposite side of the binding pocket from the carbonyl oxygen of Gly178. Our structural analyses demonstrate that the fine-tuning of hydrophobic residues on the surface of the substrate-binding pocket in ROs causes a slight shift in the substrate-binding position that, in turn, favors specific oxygenation reactions toward various substrates. PMID:24584240

  16. Non-aggregation based label free colorimetric sensor for the detection of Cu2+ based on catalyzing etching of gold nanorods by dissolve oxygen.

    PubMed

    Liu, Jia-Ming; Jiao, Li; Lin, Li-Ping; Cui, Ma-Lin; Wang, Xin-Xing; Zhang, Li-Hong; Zheng, Zhi-Yong; Jiang, Shu-Lian

    2013-12-15

    A label-free non-aggregation colorimetric sensor has been designed for the detection of Cu(2+), based on Cu(2+) catalyzing etching of gold nanorods (AuNRs) along longitudinal axis induced by dissolve oxygen in the presence of S2O3(2-), which caused the aspect ratio (length/width) of AuNRs to decrease and the color of the solution to distinctly change. The linear range and the detection limit (LD, calculated by 10 Sb/k, n=11) of this sensor were 0.080-4.8 µM Cu(2+) and 0.22 µM Cu(2+), respectively. This sensor has been utilized to detect Cu(2+) in tap water and human serum samples with the results agreeing well with those of inductively coupled plasma-mass spectroscopy (ICP-MS), showing its remarkable practicality. In order to prove the possibility of catalyzing AuNRs non-aggregation colorimetric sensor for the detection of Cu(2+), the morphological structures of AuNRs were characterized by high resolution transmission electron microscopy (HRTEM) and the sensing mechanism of colorimetric sensor for the detection of Cu(2+) was also discussed. PMID:24209363

  17. Highly branched PtCu bimetallic alloy nanodendrites with superior electrocatalytic activities for oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Fu, Shaofang; Zhu, Chengzhou; Shi, Qiurong; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-02-01

    Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst.Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07682j

  18. Coupled sulfur and oxygen isotope insight into bacterial sulfate reduction in the natural environment

    NASA Astrophysics Data System (ADS)

    Antler, Gilad; Turchyn, Alexandra V.; Rennie, Victoria; Herut, Barak; Sivan, Orit

    2013-10-01

    We present new sulfur and oxygen isotope data in sulfate (δ34SSO4 and δ18OSO4, respectively), from globally distributed marine and estuary pore fluids. We use this data with a model of the biochemical steps involved in bacterial sulfate reduction (BSR) to explore how the slope on a δ18OSO4 vs. δ34SSO4 plot relates to the net sulfate reduction rate (nSRR) across a diverse range of natural environments. Our data demonstrate a correlation between the nSRR and the slope of the relative evolution of oxygen and sulfur isotopes (δ18OSO4 vs. δ34SSO4) in the residual sulfate pool, such that higher nSRR results in a lower slope (sulfur isotopes increase faster relative to oxygen isotopes). We combine these results with previously published literature data to show that this correlation scales over many orders of magnitude of nSRR. Our model of the mechanism of BSR indicates that the critical parameter for the relative evolution of oxygen and sulfur isotopes in sulfate during BSR in natural environments is the rate of intracellular sulfite oxidation. In environments where sulfate reduction is fast, such as estuaries and marginal marine environments, this sulfite reoxidation is minimal, and the δ18OSO4 increases more slowly relative to the δ34SSO4. In contrast, in environments where sulfate reduction is very slow, such as deep sea sediments, our model suggests sulfite reoxidation is far more extensive, with as much as 99% of the sulfate being thus recycled; in these environments the δ18OSO4 increases much more rapidly relative to the δ34SSO4. We speculate that the recycling of sulfite plays a physiological role during BSR, helping maintain microbial activity where the availability of the electron donor (e.g. available organic matter) is low.

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

    PubMed

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

    2015-11-25

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

  20. Hydrogen-dependent oxygen reduction by homoacetogenic bacteria isolated from termite guts.

    PubMed

    Boga, Hamadi I; Brune, Andreas

    2003-02-01

    Although homoacetogenic bacteria are generally considered to be obligate anaerobes, they colonize the intestinal tracts of termites and other environments that are not entirely anoxic in space or time. In this study, we investigated how homoacetogenic bacteria isolated from the hindguts of various termites respond to the presence of molecular oxygen. All strains investigated formed growth bands in oxygen gradient agar tubes under a headspace of H(2)-CO(2). The position of the bands coincided with the oxic-anoxic interface and depended on the O(2) partial pressure in the headspace; the position of the bands relative to the meniscus remained stable for more than 1 month. Experiments with dense cell suspensions, performed with Clark-type O(2) and H(2) electrodes, revealed a large capacity for H(2)-dependent oxygen reduction in Sporomusa termitida and Sporomusa sp. strain TmAO3 (149 and 826 nmol min(-1) mg of protein(-1), respectively). Both strains also reduced O(2) with endogenous reductants, albeit at lower rates. Only in Acetonema longum did the basal rates exceed the H(2)-dependent rates considerably (181 versus 28 nmol min(-1) mg of protein)(-1)). Addition of organic substrates did not stimulate O(2) consumption in any of the strains. Nevertheless, reductive acetogenesis by cell suspensions of strain TmAO3 was inhibited even at the lowest O(2) fluxes, and growth in nonreduced medium occurred only after the bacteria had rendered the medium anoxic. Similar results were obtained with Acetobacterium woodii, suggesting that the results are not unique to the strains isolated from termites. We concluded that because of their tolerance to temporary exposure to O(2) at low partial pressures (up to 1.5 kPa in the case of strain TmAO3) and because of their large capacity for O(2) reduction, homoacetogens can reestablish conditions favorable for growth by actively removing oxygen from their environment. PMID:12570995

  1. Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions.

    PubMed

    Yan, Xuecheng; Jia, Yi; Odedairo, Taiwo; Zhao, Xiaojun; Jin, Zhao; Zhu, Zhonghua; Yao, Xiangdong

    2016-06-21

    We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution. PMID:27277286

  2. Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction.

    PubMed

    Liang, Yongye; Li, Yanguang; Wang, Hailiang; Zhou, Jigang; Wang, Jian; Regier, Tom; Dai, Hongjie

    2011-10-01

    Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable-energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low cost remains a great challenge. Here, we report a hybrid material consisting of Co₃O₄ nanocrystals grown on reduced graphene oxide as a high-performance bi-functional catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although Co₃O₄ or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen doping of graphene. The Co₃O₄/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high-performance non-precious metal-based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co₃O₄ and graphene. PMID:21822263

  3. Continuous-flow Mass Production of Silicon Nanowires via Substrate-Enhanced Metal-Catalyzed Electroless Etching of Silicon with Dissolved Oxygen as an Oxidant

    NASA Astrophysics Data System (ADS)

    Hu, Ya; Peng, Kui-Qing; Liu, Lin; Qiao, Zhen; Huang, Xing; Wu, Xiao-Ling; Meng, Xiang-Min; Lee, Shuit-Tong

    2014-01-01

    Silicon nanowires (SiNWs) are attracting growing interest due to their unique properties and promising applications in photovoltaic devices, thermoelectric devices, lithium-ion batteries, and biotechnology. Low-cost mass production of SiNWs is essential for SiNWs-based nanotechnology commercialization. However, economic, controlled large-scale production of SiNWs remains challenging and rarely attainable. Here, we demonstrate a facile strategy capable of low-cost, continuous-flow mass production of SiNWs on an industrial scale. The strategy relies on substrate-enhanced metal-catalyzed electroless etching (MCEE) of silicon using dissolved oxygen in aqueous hydrofluoric acid (HF) solution as an oxidant. The distinct advantages of this novel MCEE approach, such as simplicity, scalability and flexibility, make it an attractive alternative to conventional MCEE methods.

  4. Continuous-flow Mass Production of Silicon Nanowires via Substrate-Enhanced Metal-Catalyzed Electroless Etching of Silicon with Dissolved Oxygen as an Oxidant

    PubMed Central

    Hu, Ya; Peng, Kui-Qing; Liu, Lin; Qiao, Zhen; Huang, Xing; Wu, Xiao-Ling; Meng, Xiang-Min; Lee, Shuit-Tong

    2014-01-01

    Silicon nanowires (SiNWs) are attracting growing interest due to their unique properties and promising applications in photovoltaic devices, thermoelectric devices, lithium-ion batteries, and biotechnology. Low-cost mass production of SiNWs is essential for SiNWs-based nanotechnology commercialization. However, economic, controlled large-scale production of SiNWs remains challenging and rarely attainable. Here, we demonstrate a facile strategy capable of low-cost, continuous-flow mass production of SiNWs on an industrial scale. The strategy relies on substrate-enhanced metal-catalyzed electroless etching (MCEE) of silicon using dissolved oxygen in aqueous hydrofluoric acid (HF) solution as an oxidant. The distinct advantages of this novel MCEE approach, such as simplicity, scalability and flexibility, make it an attractive alternative to conventional MCEE methods. PMID:24413157

  5. A class of high performance metal-free oxygen reduction electrocatalysts based on cheap carbon blacks.

    PubMed

    Sun, Xiujuan; Song, Ping; Zhang, Yuwei; Liu, Changpeng; Xu, Weilin; Xing, Wei

    2013-01-01

    For the goal of practical industrial development of fuel cells, cheap, sustainable and high performance electrocatalysts for oxygen reduction reactions (ORR) which rival those based on platinum (Pt) and other rare materials are highly desirable. In this work, we report a class of cheap and high-performance metal-free oxygen reduction electrocatalysts obtained by co-doping carbon blacks with nitrogen and fluorine (CB-NF).The CB-NF electrocatalysts are highly active and exhibit long-term operation stability and tolerance to poisons during oxygen reduction process in alkaline medium. The alkaline direct methanol fuel cell with the best CB-NF as cathode (3 mg/cm(2)) outperforms the one with commercial platinum-based cathode (3 mg Pt/cm(2)). To the best of our knowledge, these are among the most efficient non-Pt based electrocatalysts. Since carbon blacks are 10,000 times cheaper than Pt, these CB-NF electrocatalysts possess the best price/performance ratio for ORR, and are the most promising alternatives to Pt-based ones to date. PMID:23974295

  6. Reduction kinetics of iron-based oxygen carriers using methane for chemical-looping combustion

    NASA Astrophysics Data System (ADS)

    Luo, Ming; Wang, Shuzhong; Wang, Longfei; Lv, Mingming

    2014-12-01

    The performance of three iron-based oxygen carriers (pure Fe2O3, synthetic Fe2O3/MgAl2O4 and iron ore) in reduction process using methane as fuel is investigated in thermo-gravimetric analyzer (TGA). The reaction rate and mechanism between three oxygen carriers and methane are investigated. On the basis of reactivity in reduction process, it may be concluded that Fe2O3/MgAl2O4 has the best reactivity with methane. The reaction rate constant is found to be in the following order: Fe2O3/MgAl2O4 > pure Fe2O3 > iron ore and the activation energy varies between 49 and 184 kJ mol-1. Reduction reactions for the pure Fe2O3 and synthetic Fe2O3/MgAl2O4 are well represented by the reaction controlling mechanism, and for the iron ore the phase-boundary controlled (contracting cylinder) model dominates. The particles of iron ore and synthetic Fe2O3/MgAl2O4 have better stability than that of pure Fe2O3 when the reaction temperature is limited to lower than 1223 K. These preliminary results suggest that iron-based mixed oxygen carrier particles are potential to be used in methane chemical looping process, but the reactivity of the iron ore needs to be increased.

  7. Amorphous nickel boride membrane on a platinum–nickel alloy surface for enhanced oxygen reduction reaction

    PubMed Central

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum–nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum–nickel catalyst, and this composite catalyst composed of crystalline platinum–nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

  8. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-09-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  9. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction.

    PubMed

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-01-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm(-2)) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst. PMID:25229121

  10. Reduction of chemical oxygen demand of industrial wastes using subcritical water oxidation

    SciTech Connect

    Lin, J.C.; Chang, C.J. )

    1992-10-01

    If wastes have strong toxicity, high organic content, and a deep hue, they are difficult to handle in the waste disposal. It is very practical that waste of this kind is treated by Subcritical Water Oxidation (SWO). In our work, caprolactum (CPL) waste, purged from a petrochemical plant, and dyeing waste, purged from a textile plant, were individually treated by a semi-batch SWO process. Within a one-hour treatment, Chemical Oxygen Demand (COD) reduction reached 89% for CPL waste (6.90 MPa, 260[degree]C) and 95% for dyeing waste (6.90 MPa, 240[degree]C). There is also a great improvement in hue, especially for the dyeing waste. When CPL wastewater was treated by the SWO process using a chromium metal powder as a catalyst, COD reduction improved further under the same operating conditions. A kinetic model was used to illustrate the oxidation mechanism and the effectiveness of the catalyst. The oxygen concentration in the effluent showed that oxygen consumption corresponded to COD reduction. With the monitoring of concentrations of total soluble chromium in the effluent, a suitable reaction period could be found in order to meet the standard of the Environmental Protection Agency (EPA). 12 refs., 11 figs., 2 tabs.

  11. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-08-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

  12. Low-Coordination Sites in Oxygen-Reduction Electrocatalysis: Their Roles and Methods for Removal

    SciTech Connect

    Cai, Y.; Ma, C.; Zhu, Y.; Wang, J.X.; Adzic, R.R.

    2011-07-05

    Low-coordination sites, including edges, kinks, and defects, play an important role in oxygen-reduction electrocatalysis. Their role was studied experimentally and theoretically for various Pt surfaces. However, the roughness effect on similar-sized nanoparticles that could elucidate the role of low-coordination sites has attracted much less attention, with no studies on Pd nanoparticles. Here, using Br- adsorption/desorption, we introduce an effective approach to reduce surface roughness, yielding Pd nanoparticles with smoother surfaces and an increased number of (111)-oriented facets. The resulting nanoparticles have a slightly contracted structure and narrow size distribution. Pt monolayer catalysts that contain such nanoparticles as the cores showed a 1.5-fold enhancement in specific and Pt mass activities for the oxygen reduction reaction compared with untreated ones. Furthermore, a dramatic increase in durability was observed with bromide-treated Pd{sub 3}Co cores. These results demonstrate a simple approach to preparing nanoparticles with smooth surfaces and confirm the adverse effect of low-coordination sites on the kinetics of the oxygen-reduction reaction.

  13. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  14. A Class of High Performance Metal-Free Oxygen Reduction Electrocatalysts based on Cheap Carbon Blacks

    NASA Astrophysics Data System (ADS)

    Sun, Xiujuan; Song, Ping; Zhang, Yuwei; Liu, Changpeng; Xu, Weilin; Xing, Wei

    2013-08-01

    For the goal of practical industrial development of fuel cells, cheap, sustainable and high performance electrocatalysts for oxygen reduction reactions (ORR) which rival those based on platinum (Pt) and other rare materials are highly desirable. In this work, we report a class of cheap and high-performance metal-free oxygen reduction electrocatalysts obtained by co-doping carbon blacks with nitrogen and fluorine (CB-NF).The CB-NF electrocatalysts are highly active and exhibit long-term operation stability and tolerance to poisons during oxygen reduction process in alkaline medium. The alkaline direct methanol fuel cell with the best CB-NF as cathode (3 mg/cm2) outperforms the one with commercial platinum-based cathode (3 mg Pt/cm2). To the best of our knowledge, these are among the most efficient non-Pt based electrocatalysts. Since carbon blacks are 10,000 times cheaper than Pt, these CB-NF electrocatalysts possess the best price/performance ratio for ORR, and are the most promising alternatives to Pt-based ones to date.

  15. Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

    PubMed

    He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

    2016-01-01

    The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon. PMID:27503412

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

    NASA Astrophysics Data System (ADS)

    Nallathambi, Vijayadurga

    2011-12-01

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

  17. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    PubMed

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. PMID:26247625

  18. The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

    1992-01-01

    The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

  19. Consecutive Cycloaddition/S(N)Ar/Reduction/Cyclization/Oxidation Sequences: A Copper-Catalyzed Multicomponent Synthesis of Fused N-Heterocycles.

    PubMed

    Jia, Feng-Cheng; Xu, Cheng; Zhou, Zhi-Wen; Cai, Qun; Li, Deng-Kui; Wu, An-Xin

    2015-06-01

    A highly efficient multicomponent domino protocol has been developed for the synthesis of 5-phenyl-[1,2,3]triazolo[1,5-c]quinazolines from simple and readily available (E)-1-bromo-2-(2-nitrovinyl)benzenes, aldehydes, and sodium azide. This elegant domino process involved consecutive [3 + 2] cycloaddition, copper-catalyzed S(N)Ar, reduction, cyclization, and oxidation sequences. Notably, sodium azide acted as a dual nitrogen source in the construction of this novel fused N-heterocycle. PMID:25996444

  20. Novel enzymatic activity of cell free extract from thermophilic Geobacillus sp. UZO 3 catalyzes reductive cleavage of diaryl ether bonds of 2,7-dichlorodibenzo-p-dioxin.

    PubMed

    Suzuki, Yuzoh; Nakamura, Masaya; Otsuka, Yuichiro; Suzuki, Nao; Ohyama, Keisuke; Kawakami, Takeshi; Sato, Kanna; Kajita, Shinya; Hishiyama, Shojiro; Fujii, Takeo; Takahashi, Atsushi; Katayama, Yoshihiro

    2011-04-01

    We characterized the ability of the cell free extract from polychlorinated dibenzo-p-dioxins degrading bacterium Geobacillus sp. UZO 3 to reduce even highly chlorinated dibenzo-p-dioxins such as octachlorodibenzo-p-dioxins in incineration fly ash. The degradation of 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) as a model dioxin catalyzed by the cell free extract from this strain implicates that the ether bonds of 2,7-DCDD molecule undergo reductive cleavage, since 4',5-dichloro-2-hydroxydiphenyl ether and 4-chlorophenol were detected as intermediate products of 2,7-DCDD degradation. PMID:21435685

  1. Impact of SO 2 poisoning of platinum nanoparticles modified glassy carbon electrode on oxygen reduction

    NASA Astrophysics Data System (ADS)

    Awad, M. I.; Saleh, M. M.; Ohsaka, T.

    An extraordinary recovery characteristic of Pt-nanoparticles from SO 2 poisoning is introduced in this study. Platinum nanoparticles (nano-Pt) modified glassy carbon electrode (nano-Pt/GC) has been compared with polycrystalline platinum (poly-Pt) electrode towards SO 2 poisoning. Two procedures of recovery of the poisoned electrodes were achieved by cycling the potential in the narrow potential range (NPR, 0-0.8 V vs. Ag/AgCl/KCl (sat.)) and wide potential range (WPR, -0.2 to 1.3 V). The extent of recovery was marked using oxygen reduction reaction (ORR) as a probing reaction. SO 2 poisoning of the electrodes changed the mechanism of the oxygen reduction from the direct reduction to water to the stepwise reduction involving the formation of H 2O 2 as an intermediate, as indicated by the rotating ring-disk voltammetry. Using the WPR recovery procedure, it was found that two potential cycles were enough to recover 100% of the activity of the ORR on the nano-Pt/GC electrode. At the poly-Pt electrode, however, four potential cycles of the WPR caused only 79% in the current recovery, while the peak potential of the ORR was 130 mV negatively shifted as compared with the fresh poly-Pt electrode. Interestingly, the NPR procedure at the nano-Pt/GC electrode was even more efficient in the recovery than the WPR procedure at the poly-Pt electrode.

  2. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts.

    PubMed

    Greeley, J; Stephens, I E L; Bondarenko, A S; Johansson, T P; Hansen, H A; Jaramillo, T F; Rossmeisl, J; Chorkendorff, I; Nørskov, J K

    2009-10-01

    The widespread use of low-temperature polymer electrolyte membrane fuel cells for mobile applications will require significant reductions in the amount of expensive Pt contained within their cathodes, which drive the oxygen reduction reaction (ORR). Although progress has been made in this respect, further reductions through the development of more active and stable electrocatalysts are still necessary. Here we describe a new set of ORR electrocatalysts consisting of Pd or Pt alloyed with early transition metals such as Sc or Y. They were identified using density functional theory calculations as being the most stable Pt- and Pd-based binary alloys with ORR activity likely to be better than Pt. Electrochemical measurements show that the activity of polycrystalline Pt(3)Sc and Pt(3)Y electrodes is enhanced relative to pure Pt by a factor of 1.5-1.8 and 6-10, respectively, in the range 0.9-0.87 V. PMID:21378936

  3. Covalent hybridization of thiolated graphene sheet and platinum nanoparticles for electrocatalytic oxygen reduction reaction.

    PubMed

    Ahmed, Mohammad Shamsuddin; Kim, Daekun; Han, Hyoung Soon; Jeong, Haesang; Jeon, Seungwon

    2012-11-01

    A covalently bonded thiolated graphene sheet-supported platinum electrocatalyst (GOS-Pt) has synthesized for electrochemical oxygen reduction reaction (ORR) in neutral media. The catalyst's structural features are characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). Its activity towards the ORR has investigated by using cyclic voltammetry (CV), rotating disk electrode (RDE), and rotating ring disk electrode (RRDE) in 0.1 mol l(-1) phosphate buffer solution (PBS) at pH 7, which is also used to assess the catalyst's kinetic parameters. On a glassy carbon electrode (GCE), the catalyst shows a significant catalytic activity, with its electrocatalysis of O2 reduction occurring via four-electron transfer reduction to H2O with minimal generation of H2O2. PMID:23421215

  4. An electrodeposited redox polymer-laccase composite film for highly efficient four-electron oxygen reduction

    NASA Astrophysics Data System (ADS)

    Shen, Wei; Deng, Huimin; Teo, Alan Kay Liang; Gao, Zhiqiang

    2013-03-01

    In this report, it is shown that novel thin films of Os(dcbpy)2 (dcbpy = 4,4‧-dicarboxylic acid-2,2‧-bipyridine)-based redox polymer-laccase composite can be electrodeposited onto carbon electrodes under mild conditions. In a nutshell, the exchange of the inner-sphere Cl- of the Os(dcbpy)2Cl+/2+ complex tethered to partially quaternized poly (4-vinylpyridine) (PVP) by a pyridine ligand of a second PVP chain leads to cross-linking and deposition of the redox polymer. Laccase, which has coordinatively linkable functions of amines and histidines, is readily incorporated in the electrodeposited redox polymer. Because the reaction centers of the co-deposited laccase are electrically connected to the electrode through the deposited redox polymer, the electrodeposited film can catalyze the electroreduction of O2 at 0.58 V (vs. Ag/AgCl) - the least reducing potential for highly efficient four-electron reduction of O2 in pH 5.5 0.10 M phosphate buffer solution. Furthermore, the electroreduction of O2 is found to be O2 transport-limited when the reduction potential is poised at ≥120 mV more reducing than that of the reversible O2/H2O couple. This composite film could be an excellent candidate for uses as cathode in enzymatic biofuel cells.

  5. Performance of catalyzed hydrazine in field applications

    SciTech Connect

    Allgood, T.B.

    1987-01-01

    The performance of newly developed oxygen scavengers for boilers is often compared to sulfite and hydrazine. Catalyzed hydrazine out-performs hydrazine and might be preferred when catalyzed sulfite cannot be used. Data from a Midwest Utility confirms that, under field conditions, catalyzed hydrazine out-performance hydrazine and carbohydrazine when feedwater oxygen and iron levels were critical. Catalyzed hydrazine might be preferred when high performance and economics are the primary concerns.

  6. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

    PubMed

    Cheng, Fangyi; Chen, Jun

    2012-03-21

    Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references). PMID:22254234

  7. Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

    NASA Astrophysics Data System (ADS)

    Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

    2014-01-01

    Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

  8. Carbon Nitrogen Nanotubes as Efficient Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reactions.

    PubMed

    Yadav, Ram Manohar; Wu, Jingjie; Kochandra, Raji; Ma, Lulu; Tiwary, Chandra Sekhar; Ge, Liehui; Ye, Gonglan; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M

    2015-06-10

    Oxygen reduction and evolution reactions are essential for broad range of renewable energy technologies such as fuel cells, metal-air batteries and hydrogen production through water splitting, therefore, tremendous effort has been taken to develop excellent catalysts for these reactions. However, the development of cost-effective and efficient bifunctional catalysts for both reactions still remained a grand challenge. Herein, we report the electrocatalytic investigations of bamboo-shaped carbon nitrogen nanotubes (CNNTs) having different diameter distribution synthesized by liquid chemical vapor deposition technique using different nitrogen containing precursors. These CNNTs are found to be efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. The electrocatalytic activity strongly depends on the nanotube diameter as well as nitrogen functionality type. The higher diameter CNNTs are more favorable for these reactions. The increase in nanotube diameter itself enhances the catalytic activity by lowering the oxygen adsorption energy, better conductivity, and further facilitates the reaction by increasing the percentage of catalytically active nitrogen moieties in CNNTs. PMID:25970133

  9. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    PubMed

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase. PMID:27054466

  10. The oxygen reduction pathway and heat shock stress response are both required for Entamoeba histolytica pathogenicity.

    PubMed

    Olivos-García, Alfonso; Saavedra, Emma; Nequiz, Mario; Santos, Fabiola; Luis-García, Erika Rubí; Gudiño, Marco; Pérez-Tamayo, Ruy

    2016-05-01

    Several species belonging to the genus Entamoeba can colonize the mouth or the human gut; however, only Entamoeba histolytica is pathogenic to the host, causing the disease amoebiasis. This illness is responsible for one hundred thousand human deaths per year worldwide, affecting mainly underdeveloped countries. Throughout its entire life cycle and invasion of human tissues, the parasite is constantly subjected to stress conditions. Under in vitro culture, this microaerophilic parasite can tolerate up to 5 % oxygen concentrations; however, during tissue invasion the parasite has to cope with the higher oxygen content found in well-perfused tissues (4-14 %) and with reactive oxygen and nitrogen species derived from both host and parasite. In this work, the role of the amoebic oxygen reduction pathway (ORP) and heat shock response (HSP) are analyzed in relation to E. histolytica pathogenicity. The data suggest that in contrast with non-pathogenic E. dispar, the higher level of ORP and HSPs displayed by E. histolytica enables its survival in tissues by diminishing and detoxifying intracellular oxidants and repairing damaged proteins to allow metabolic fluxes, replication and immune evasion. PMID:26589893

  11. Synergistic H4NI-AcOH Catalyzed Oxidation of the Csp(3)-H Bonds of Benzylpyridines with Molecular Oxygen.

    PubMed

    Ren, Lanhui; Wang, Lianyue; Lv, Ying; Li, Guosong; Gao, Shuang

    2015-05-01

    The oxidation of benzylpyridines forming benzoylpyridines was achieved based on a synergistic H4NI-AcOH catalyst and molecular oxygen in high yield under solvent-free conditions. This is the first nonmetallic catalytic system for this oxidation transformation using molecular oxygen as the oxidant. The catalytic system has a wide scope of substrates and excellent chemoselectivity, and this procedure can also be scaled up. The study of a preliminary reaction mechanism demonstrated that the oxidation of the Csp(3)-H bonds of benzylpyridines was promoted by the pyridinium salts formed by AcOH and benzylpyridines. The synergistic effect of H4NI-AcOH was also demonstrated by control experiments. PMID:25885281

  12. Detection of hydrogen peroxide produced during electrochemical oxygen reduction using scanning electrochemical microscopy.

    PubMed

    Shen, Yan; Träuble, Markus; Wittstock, Gunther

    2008-02-01

    The substrate-generation/tip-collection mode of scanning electrochemical microscopy was used to detect hydrogen peroxide formed as an intermediate during oxygen reduction at various electrodes. The experiment is conceptually similar to rotating ring-disk experiments but does not require the production of a ring-disk assembly for the specific electrode material in question. In order to limit the extension of the diffusion layer above the sample, the sample electrode potential is pulsed while the Pt ultramicroelectrode probe (UME) is held at a constant potential for oxidative amperometric detection of hydrogen peroxide. The signal at UME is influenced by the sample region within the diffusion length of hydrogen peroxide during the pulse of 2.5 s. The method is tested with three model electrodes showing different behavior with respect to the oxygen reduction reaction (ORR) in acidic solution. Simple analytical models were used to extract effective rate constants for the most important reaction paths of ORR at gold and palladium-cobalt samples from the chronoamperometric response of the UME to a reduction pulse at the sample electrode. PMID:18179180

  13. The bifurcation point of the oxygen reduction reaction on Au-Pd nanoalloys.

    PubMed

    Staszak-Jirkovský, Jakub; Ahlberg, Elisabet; Panas, Itai; Schiffrin, David J

    2016-07-01

    The oxygen reduction reaction is of major importance in energy conversion and storage. Controlling electrocatalytic activity and its selectivity remains a challenge of modern electrochemistry. Here, first principles calculations and analysis of experimental data unravel the mechanism of this reaction on Au-Pd nanoalloys in acid media. A mechanistic model is proposed from comparison of the electrocatalysis of oxygen and hydrogen peroxide reduction on different Au-Pd ensembles. A H2O production channel on contiguous Pd sites proceeding through intermediates different from H2O2 and OOH(σ) adsorbate is identified as the bifurcation point for the two reaction pathway alternatives to yield either H2O or H2O2. H2O2 is a leaving group, albeit reduction of H2O2 to H2O can occur by electrocatalytic HO-OH dissociation that is affected by the presence of adsorbed OOH(σ). Similarities and differences between electrochemical and direct synthesis from H2 + O2 reaction on Au-Pd nanoalloys are discussed. PMID:27089504

  14. Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

    SciTech Connect

    Shao, Yuyan; Zhang, Sheng; Kou, Rong; Wang, Xiqing; Wang, Chong M.; Dai, Sheng; Viswanathan, Vilayanur V.; Liu, Jun; Wang, Yong; Lin, Yuehe

    2010-01-01

    We report the facile synthesis of an extremely durable electrocatalyst for oxygen reduction with highly graphitized mesoporous carbon (GMPC) as support (Pt/GMPC). GMPC is prepared through graphitizing the self-assembled soft-template mesoporous carbon (MPC) under high temperature. Most of the mesoporous structures and the specific surface area of MPC are retained even after 2800 °C heat-treatment, and the graphitization degree is greatly improved. GMPC is then noncovalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) and then coated with Pt nanoparticles with ethylene glycol reduction method. Pt nanoparticles of ~3.0 nm in diameter are uniformly dispersed on GMPC. Pt/GMPC exhibits a higher activity towards oxygen reduction reaction (ORR) than Pt nanoparticles supported on Vulcan XC-72 carbon (Pt/XC-72). The durability of Pt/GMPC is improved by a factor of ~2 compared with Pt/XC-72. The enhanced activity and durability of Pt/GMPC are attributed to the graphitic structure of GMPC which makes GMPC more resistant to corrosion and the interaction between Pt nanoparticles and GMPC stronger. GMPC is promising as catalyst support. This provides a facile, eco-friendly promising strategy, avoiding the usually used chemical functionalization of carbon support with oxidizing strong acid, to synthesize electrocatalysts with high durability and activity for polymer electrolyte membrane fuel cells. This strategy can be widely applied in synthesizing metal nanoparticles on hydrophobic support materials.

  15. Assembly of Modified Ferritin Proteins on Carbon Nanotubes and its Electrocatalytic Activity for Oxygen Reduction

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo; Lillehei, Peter T.; Park, Cheol

    2012-01-01

    Highly effective dispersions of carbon nanotubes (CNTs) can be made using a commercially available buffer solution. Buffer solutions of 3-(N-morpholino)-propanesulfonic acid (MOPS), which consists of a cyclic ring with nitrogen and oxygen heteroatoms, a charged group, and an alkyl chain greatly enhance the dispersibility and stability of CNTs in aqueous solutions. Additionally, the ability of biomolecules, especially cationized Pt-cored ferritins, to adhere onto the well-dispersed CNTs in the aqueous buffer solution is also improved. This was accomplished without the use of surfactant molecules, which are detrimental to the electrical, mechanical, and other physical properties of the resulting products. The assembled Pt-cored ferritin proteins on the CNTs were used as an electrocatalyst for oxygen reduction

  16. Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction.

    PubMed

    Olaya, Astrid J; Schaming, Delphine; Brevet, Pierre-Francois; Nagatani, Hirohisa; Zimmermann, Tomas; Vanicek, Jiri; Xu, Hai-Jun; Gros, Claude P; Barbe, Jean-Michel; Girault, Hubert H

    2012-01-11

    The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning Electron Microscopy. Density functional theory calculations confirm the possibility of formation of the catalytic CoTMPyP(4+)/ CoTPPS(4-) complex and its capability to bind oxygen. PMID:22107335

  17. Role of LiCoO2 Surface Terminations in Oxygen Reduction and Evolution Kinetics.

    PubMed

    Han, Binghong; Qian, Danna; Risch, Marcel; Chen, Hailong; Chi, Miaofang; Meng, Ying Shirley; Shao-Horn, Yang

    2015-04-16

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003), while the tips were terminated largely with high-index surfaces such as (104), as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co(3+) prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co(3+). We correlated the electronic and atomic structure to higher specific ORR and OER activities at the tips as compared to the sides, which was accompanied by more facile redox of Co(2+/3+) and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition-metal oxides on the ORR and OER activity. PMID:26263135

  18. Utilizing in Situ Electrochemical SHINERS for Oxygen Reduction Reaction Studies in Aprotic Electrolytes.

    PubMed

    Galloway, Thomas A; Hardwick, Laurence J

    2016-06-01

    Spectroscopic detection of reaction intermediates upon a variety of electrode surfaces is of major interest within physical chemistry. A notable technique in the study of the electrochemical interface has been surface-enhanced Raman spectroscopy (SERS). The drawback of SERS is that it is limited to roughened gold and silver substrates. Herein we report that shell-isolated nanoparticles for enhanced Raman spectroscopy (SHINERS) can overcome the limitations of SERS and has followed the oxygen reduction reaction (ORR), within a nonaqueous electrolyte, on glassy carbon, gold, palladium, and platinum disk electrodes. The work presented demonstrates SHINERS for spectroelectrochemical studies for applied and fundamental electrochemistry in aprotic electrolytes, especially for the understanding and development of future metal-oxygen battery applications. In particular, we highlight that with the addition of Li(+), both the electrode surface and solvent influence the ORR mechanism, which opens up the possibility of tailoring surfaces to produce desired reaction pathways. PMID:27195529

  19. Selective nitrogen doping in graphene: Enhanced catalytic activity for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Huang, Sheng-Feng; Terakura, Kiyoyuki; Boero, Mauro; Oshima, Masaharu; Kakimoto, Masa-Aki; Miyata, Seizo

    2011-12-01

    The structural and electronic properties of N-doped zigzag graphene ribbons with various ratios of dihydrogenated to monohydrogenated edge carbons are investigated within the density functional theory framework. We find that the stability of graphitic N next to the edge, which is claimed to play important roles in the catalytic activity in our previous work, will be enhanced with increasing the concentration of dihydrogenated carbons. Furthermore, the dihydrogenated edge carbons turn out to be easily converted into monohydrogenated ones in the presence of oxygen molecules at room temperature. Based on our results, we propose a possible way to enhance the oxygen reduction catalytic activity of N-doped graphene by controlling the degrees of hydrogenation of edge carbons. The characteristic features in the x-ray absorption and emission spectra for each specific N site considered here will also be given.

  20. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability.

    PubMed

    Stamenkovic, Vojislav R; Fowler, Ben; Mun, Bongjin Simon; Wang, Guofeng; Ross, Philip N; Lucas, Christopher A; Marković, Nenad M

    2007-01-26

    The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption. PMID:17218494

  1. Increased Reactive Oxygen Species Production During Reductive Stress: The Roles of Mitochondrial Glutathione and Thioredoxin Reductases

    PubMed Central

    Korge, Paavo; Calmettes, Guillaume; Weiss, James N.

    2015-01-01

    Both extremes of redox balance are known to cause cardiac injury, with mounting evidence revealing that the injury induced by both oxidative and reductive stress is oxidative in nature. During reductive stress, when electron acceptors are expected to be mostly reduced, some redox proteins can donate electrons to O2 instead, which increases reactive oxygen species (ROS) production. However, the high level of reducing equivalents also concomitantly enhances ROS scavenging systems involving redox couples such as NADPH/NADP+ and GSH/GSSG. Here our objective was to explore how reductive stress paradoxically increases net mitochondrial ROS production despite the concomitant enhancement of ROS scavenging systems. Using recombinant enzymes and isolated permeabilized cardiac mitochondria, we show that two normally antioxidant matrix NADPH reductases, glutathione reductase and thioredoxin reductase, generate H2O2 by leaking electrons from their reduced flavoprotein to O2 when electron flow is impaired by inhibitors or because of limited availability of their natural electron acceptors, GSSG and oxidized thioredoxin. The spillover of H2O2 under these conditions depends on H2O2 reduction by peroxiredoxin activity, which may regulate redox signaling in response to endogenous or exogenous factors. These findings may explain how ROS production during reductive stress overwhelms ROS scavenging capability, generating the net mitochondrial ROS spillover causing oxidative injury. These enzymes could potentially targeted to increase cancer cell death or modulate H2O2-induced redox signaling to protect the heart against ischemia/reperfusion damage. PMID:25701705

  2. Direct growth of flower-like manganese oxide on reduced graphene oxide towards efficient oxygen reduction reaction.

    PubMed

    Zhang, Jintao; Guo, Chunxian; Zhang, Lianying; Li, Chang Ming

    2013-07-18

    Three-dimensional manganese oxide is directly grown on reduced graphene oxide (RGO) sheets, exhibiting comparable catalytic activity, higher selectivity and better stability towards oxygen reduction reaction than those of the commercial Pt/XC-72 catalyst. PMID:23745182

  3. Atomic-scale modeling of particle size effects for the oxygen reduction reaction on Pt.

    SciTech Connect

    Tritsaris, G. A.; Greeley, J.; Rossmeisl, J.; Norskov, J. K.

    2011-07-01

    We estimate the activity of the oxygen reduction reaction on platinum nanoparticles of sizes of practical importance. The proposed model explicitly accounts for surface irregularities and their effect on the activity of neighboring sites. The model reproduces the experimentally observed trends in both the specific and mass activities for particle sizes in the range between 2 and 30 nm. The mass activity is calculated to be maximized for particles of a diameter between 2 and 4 nm. Our study demonstrates how an atomic-scale description of the surface microstructure is a key component in understanding particle size effects on the activity of catalytic nanoparticles.

  4. Development of ruthenium-based bimetallic electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Lingyun; Lee, Jong-Won; Popov, Branko N.

    Ruthenium-based bimetallic electrocatalysts with non-noble metals such as Ti, Cr, Fe, Co and Pb were synthesized on a porous carbon support using a chelation process. Rotating ring disk electrode measurements indicated that RuFeN x/C showed the catalytic activity and selectivity toward the four-electron reduction of oxygen to water comparable to those of the conventional Pt/C catalysts. The performance of the membrane-electrode assembly prepared with the RuFeN x/C cathode catalyst was evaluated for 150 h of continuous operation.

  5. A Strategy to Promote the Electrocatalytic Activity of Spinels for Oxygen Reduction by Structure Reversal.

    PubMed

    Wu, Guangping; Wang, Jun; Ding, Wei; Nie, Yao; Li, Li; Qi, Xueqiang; Chen, Siguo; Wei, Zidong

    2016-01-22

    The electrocatalytic performance of a spinel for the oxygen reduction reaction (ORR) can be significantly promoted by reversing its crystalline structure from the normal to the inverse. As the spinel structure reversed, the activation and cleavage of O-O bonds are accelerated owing to a dissimilarity effect of the distinct metal atoms co-occupying octahedral sites. The Co(II)Fe(III)Co(III)O4 spinel with the Fe and Co co-occupying inverse structure exhibits an excellent ORR activity, which even exceeds that of the state-of-the-art commercial Pt/C by 42 mV in alkaline medium. PMID:26663768

  6. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    SciTech Connect

    Nandan, Ravi Nanda, Karuna Kar

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  7. Structure-activity relationship in high-performance iron-based electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Song, Ping; Wang, Ying; Pan, Jing; Xu, Weilin; Zhuang, Lin

    2015-12-01

    A sustainable Iron (Fe), Nitrogen (N) co-doped high performance Fe-Nx/C electrocatalyst for oxygen reduction reaction (ORR) is synthesized simply based on nitric acid oxidation of cheap carbon black. The obtained optimal nonprecious metal electrocatalyst shows high ORR performance in both alkaline and acidic conditions and possesses appreciable performance/price ratio due to its low cost. Furthermore, the structure-activity relationship of different active sites on Fe-Nx/C is revealed systematically: Fe-N4/2-C > Fe4-N-C > N-C >> Fe4-C ≥ C, from both experimental and theoretical points of view.

  8. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Nandan, Ravi; Nanda, Karuna Kar

    2015-06-01

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min-1. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  9. Kinetics of Oxygen Reduction in Aprotic Li-O2 Cells: A Model-Based Study.

    PubMed

    Safari, M; Adams, B D; Nazar, L F

    2014-10-16

    A comprehensive and general kinetic model is developed for the oxygen reduction reaction in aprotic Li-O2 cells. The model is based on the competitive uptake of lithium superoxide by the surface and solution. A demonstrative kinetic study is provided to demystify the origin of curvature in Tafel plots as well as the current dependency and aberrant diversity of the nature and morphology of discharge products in these systems. Our results are general and extend to any system where solubilization of superoxide is favored, such as where phase-transfer catalysts play an important role. PMID:26278597

  10. An ultrastable bimetallic carbide as platinum electrocatalyst support for highly active oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; Zhang, Mingmei; Xie, Jimin; Shen, Pei Kang

    2015-11-01

    Stable bimetallic carbide (Fe2MoC) with graphitized carbon (GC) as matrix has been synthesized through an ion-exchange method. The Pt nanoparticles are loaded on the GC-Fe2MoC composite to form Pt/GC-Fe2MoC electrocatalyst which shows much higher activity and stability than those of commercial Pt/C for oxygen reduction reaction in acidic media. The excellent performances of Pt/GC-Fe2MoC are mainly due to the inherent stability of GC-Fe2MoC and the promotion effect between Fe2MoC and Pt.

  11. Heazlewoodite, Ni3S2: A Potent Catalyst for Oxygen Reduction to Water under Benign Conditions.

    PubMed

    Falkowski, Joseph M; Concannon, Nolan M; Yan, Bing; Surendranath, Yogesh

    2015-07-01

    Electrodeposited thin films and nanoparticles of Ni3S2 are highly active, poison- and corrosion-resistant catalysts for oxygen reduction to water at neutral pH. In pH 7 phosphate buffer, Ni3S2 displays catalytic onset at 0.8 V versus the reversible hydrogen electrode, a Tafel slope of 109 mV decade(-1), and high faradaic efficiency for four-electron reduction of O2 to water. Under these conditions, the activity and stability of Ni3S2 exceeds that of polycrystalline platinum and manganese, nickel, and cobalt oxides, illustrating the catalytic potential of pairing labile first-row transition metal active sites with a more covalent sulfide host lattice. PMID:26101848

  12. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction.

    PubMed

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-10-21

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag(+)/Pd(2+) is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. PMID:25155648

  13. Oxygen Reduction Reaction on Cobalt--(6)Pyrrole Cluster: Density Functional Theory Study

    NASA Astrophysics Data System (ADS)

    Saputro, Adhitya G.; Rusydi, Febdian; Kasai, Hideaki; Dipojono, Hermawan K.

    2012-03-01

    We investigate the potential energy surface profile for various water formation reaction schemes on an unsupported cobalt--(6)pyrrole [Co--(6)Ppy] cluster in the vacuum state by density functional theory (DFT) calculations. We find that in the Co--(6)Ppy cluster, the formation of H2O2 is energetically not favorable. Instead of forming H2O2ad, the \\text{HO\\text{2ad} + H reaction forms 2OHad or \\text{O\\text{ad} + H2O immediately. The adsorption of H2O2 on the Co--(6)Ppy cluster is possible only if the H2O2 molecule comes from or forms outside of the cluster. The formation of two OH molecules instead of H2O2 on the Co--(6)Ppy cluster suggests that the oxygen reduction reaction (ORR) mechanism on the unsupported Co--(6)Ppy cluster in the vacuum state prefers the direct four-electron reduction to water.

  14. Triangular Ag-Pd alloy nanoprisms: rational synthesis with high-efficiency for electrocatalytic oxygen reduction

    NASA Astrophysics Data System (ADS)

    Xu, Lin; Luo, Zhimin; Fan, Zhanxi; Zhang, Xiao; Tan, Chaoliang; Li, Hai; Zhang, Hua; Xue, Can

    2014-09-01

    We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems.We report the generation of triangular Ag-Pd alloy nanoprisms through a rationally designed synthetic strategy based on silver nanoprisms as sacrificial templates. The galvanic replacement between Ag nanoprisms and H2PdCl4 along with co-reduction of Ag+/Pd2+ is responsible for the formation of final prismatic Ag-Pd alloy nanostructures. Significantly, these Ag-Pd alloy nanoprisms exhibited superior electrocatalytic activity for the oxygen reduction reaction (ORR) as compared with the commercial Pd/C catalyst. Such a high catalytic activity is attributed to not only the alloyed Ag-Pd composition but also the dominant {111} facets of the triangular Ag-Pd nanoprisms. This work demonstrates the rational design of bimetallic alloy nanostructures with control of selective crystal facets that are critical to achieve high catalytic activity for fuel cell systems. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03600j

  15. The reversibility of dissimilatory sulphate reduction and the cell-internal multi-step reduction of sulphite to sulphide: insights from the oxygen isotope composition of sulphate.

    PubMed

    Brunner, Benjamin; Einsiedl, Florian; Arnold, Gail L; Müller, Inigo; Templer, Stefanie; Bernasconi, Stefano M

    2012-01-01

    Dissimilatory sulphate reduction (DSR) leads to an overprint of the oxygen isotope composition of sulphate by the oxygen isotope composition of water. This overprint is assumed to occur via cell-internally formed sulphuroxy intermediates in the sulphate reduction pathway. Unlike sulphate, the sulphuroxy intermediates can readily exchange oxygen isotopes with water. Subsequent to the oxygen isotope exchange, these intermediates, e.g. sulphite, are re-oxidised by reversible enzymatic reactions to sulphate, thereby incorporating the oxygen used for the re-oxidation of the sulphur intermediates. Consequently, the rate and expression of DSR-mediated oxygen isotope exchange between sulphate and water depend not only on the oxygen isotope exchange between sulphuroxy intermediates and water, but also on cell-internal forward and backward reactions. The latter are the very same processes that control the extent of sulphur isotope fractionation expressed by DSR. Recently, the measurement of multiple sulphur isotope fractionation has successfully been applied to obtain information on the reversibility of individual enzymatically catalysed steps in DSR. Similarly, the oxygen isotope signature of sulphate has the potential to reveal complementary information on the reversibility of DSR. The aim of this work is to assess this potential. We derived a mathematical model that links sulphur and oxygen isotope effects by DSR, assuming that oxygen isotope effects observed in the oxygen isotopic composition of ambient sulphate are controlled by the oxygen isotope exchange between sulphite and water and the successive cell-internal oxidation of sulphite back to sulphate. Our model predicts rapid DSR-mediated oxygen isotope exchange for cases where the sulphur isotope fractionation is large and slow exchange for cases where the sulphur isotope fractionation is small. Our model also demonstrates that different DSR-mediated oxygen isotope equilibrium values are observed, depending on the

  16. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    PubMed Central

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s −0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol−1s−1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  17. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction.

    PubMed

    Parnell, Charlette M; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A; Mudalige, Thilak K; Biris, Alexandru S; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material's -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 10(6) mol(-1)s(-1) was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  18. ATOMIC SCALE CHARACTERIZATION OF OXYGEN VACANCY DYNAMICS BY IN SITU REDUCTION AND ANALYTICAL ATOMIC RESOLUTION STEM.

    SciTech Connect

    KLIE,R.F.; BROWNING,N.D.; ZHU,Y.

    2002-08-04

    In this study, we present nano-scale investigations of point defect dynamics in perovskite oxides by correlated atomic resolution high angle annular dark field imaging (HAADF) and electron energy loss spectroscopy (EELS). The point defect dynamics and interactions during in-situ reduction in the microscope column are analyzed. In particular, oxygen vacancy creation, diffusion and clustering are studied, as oxygen vacancies comprise the majority of the point defects present in these perovskite oxide systems [1]. The results have been acquired using the JEOL2010F, a STEM/TEM, equipped with a 200 keV field emission gun, a high angle annular dark field detector and a post column Gatan imaging filter (GIF). The combination of the Z-contrast and EELS techniques [2] allows us to obtain direct images (spatial resolution of 2 {angstrom}) of the atomic structure and to correlate this information with the atomically resolved EELS information (3s acquisition time, 1.2 eV energy resolution). In-situ heating of the material is performed in a Gatan double tilt holder with a temperature range of 300 K-773 K at an oxygen partial pressure of P{sub O{sub 2}} = 5 * 10{sup -8} Pa.

  19. Reduction in Cerebral Oxygenation After Prolonged Exercise in Hypoxia is Related to Changes in Blood Pressure.

    PubMed

    Horiuchi, Masahiro; Dobashi, Shohei; Kiuchi, Masataka; Endo, Junko; Koyama, Katsuhiro; Subudhi, Andrew W

    2016-01-01

    We investigated the relation between blood pressure and cerebral oxygenation (COX) immediately after exercise in ten healthy males. Subjects completed an exercise and recovery protocol while breathing either 21% (normoxia) or 14.1% (hypoxia) O2 in a randomized order. Each exercise session included four sets of cycling (30 min/set, 15 min rest) at 50% of altitude-adjusted peak oxygen uptake, followed by 60 min of recovery. After exercise, mean arterial pressure (MAP; 87±1 vs. 84±1 mmHg, average values across the recovery period) and COX (68±1% vs. 58±1%) were lower in hypoxia compared to normoxia (P<0.001). Changes in MAP and COX were correlated during the recovery period in hypoxia (r=0.568, P<0.001) but not during normoxia (r=0.028, not significant). These results demonstrate that reductions in blood pressure following exercise in hypoxia are (1) more pronounced than in normoxia, and (2) associated with reductions in COX. Together, these results suggest an impairment in cerebral autoregulation as COX followed changes in MAP more passively in hypoxia than in normoxia. These findings could help explain the increased risk for postexercise syncope at high altitude. PMID:26782200

  20. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  1. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  2. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination

    NASA Astrophysics Data System (ADS)

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

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

    PubMed

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

    2015-09-15

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

  4. In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles.

    PubMed

    Hernández, J; Solla-Gullón, J; Herrero, E; Feliu, J M; Aldaz, A

    2009-04-01

    Gold nanoparticles of different shapes/surface structures were synthesized and electrochemically characterized. An in-situ surface characterization of the Au nanoparticles, which was able to obtain qualitative information about the type and relative sizes of the different facets present in the surface of the Au nanoparticles, was carried out by using Pb Under Potential Deposition (UPD) in alkaline solutions as a surface sensitive tool. The results obtained show that the final atomic arrangement on the surface can be different from that expected from the bulk structure of the well-defined shape Au nanoparticles. In this way, the development of precise in-situ methods to measure the distribution of the different sites on the nanoparticle surface, as lead UPD on gold surfaces, is highlighted. Oxygen Reduction Reaction (ORR) was performed on the different Au nanoparticles. In agreement with the particular sensitivity of the oxygen reduction to the presence of Au(100) surface domains, cubic Au nanoparticles show much better electrocatalytic activity for ORR than small spherical particles and long nanorods, in agreement with the presence of a great fraction of (100) terrace sites on the surface of cubic gold nanoparticles. PMID:19437963

  5. Stabilization of Platinum Nanoparticle Electrocatalysts for Oxygen Reduction Using Poly(diallyldimethylammonium chloride)

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2009-10-29

    A long-chain polyelectrolyte, poly(diallyldimethylammonium chloride) (PDDA), has been employed to stabilize platinum nanoparticles for oxygen reduction in polymer electrolyte membrane (PEM) fuel cells. Pt nanoparticles were synthesized by reducing H2PtCl6 with NaBH4 in the presence of PDDA and then deposited on carbon support (PDDA-Pt/C). Transmission electron microscope images showed that Pt nanoparticles of PDDA-Pt/C are uniformly dispersed on carbon support with a mean size of about 2.2 nm (2.1 nm for commercial Etek-Pt/C). PDDA-Pt/C exhibited a higher activity towards oxygen reduction reaction (ORR) than Etek-Pt/C. The durability of PDDA-Pt/C was improved by a factor of 2 as compared with Etek-Pt/C. X-ray photoelectron spectroscopy characterization of PDDA-Pt/C revealed the interaction between Pt nanoparticles and PDDA, which increased Pt oxidation potential. PDDA-Nafion ionic crosslinking "entraps" Pt nanoparticles and prevents Pt nanoparticles from migrating/agglomerating on or detaching from carbon support. This provides a promising strategy to improve both the durability and activity of electrocatalysts for fuel cells.

  6. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    NASA Astrophysics Data System (ADS)

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-11-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology.

  7. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    PubMed Central

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-01-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology. PMID:24264379

  8. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes.

    PubMed

    Li, Yanguang; Zhou, Wu; Wang, Hailiang; Xie, Liming; Liang, Yongye; Wei, Fei; Idrobo, Juan-Carlos; Pennycook, Stephen J; Dai, Hongjie

    2012-06-01

    Oxygen reduction reaction catalysts based on precious metals such as platinum or its alloys are routinely used in fuel cells because of their high activity. Carbon-supported materials containing metals such as iron or cobalt as well as nitrogen impurities have been proposed to increase scalability and reduce costs, but these alternatives usually suffer from low activity and/or gradual deactivation during use. Here, we show that few-walled carbon nanotubes, following outer wall exfoliation via oxidation and high-temperature reaction with ammonia, can act as an oxygen reduction reaction electrocatalyst in both acidic and alkaline solutions. Under a unique oxidation condition, the outer walls of the few-walled carbon nanotubes are partially unzipped, creating nanoscale sheets of graphene attached to the inner tubes. The graphene sheets contain extremely small amounts of irons originated from nanotube growth seeds, and nitrogen impurities, which facilitate the formation of catalytic sites and boost the activity of the catalyst, as revealed by atomic-scale microscopy and electron energy loss spectroscopy. Whereas the graphene sheets formed from the unzipped part of the outer wall of the nanotubes are responsible for the catalytic activity, the inner walls remain intact and retain their electrical conductivity, which facilitates charge transport during electrocatalysis. PMID:22635099

  9. Hydrothermal synthesis of vanadium nitride and modulation of its catalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Huang, Taizhong; Mao, Shun; Zhou, Guihua; Wen, Zhenhai; Huang, Xingkang; Ci, Suqin; Chen, Junhong

    2014-07-01

    A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts.A creative hydrothermal synthesis method followed by calcination for vanadium nitride (VN) is reported. The oxygen reduction reaction (ORR) study of the catalyst shows that VN possesses a comparable catalytic performance to commercial Pt/C catalyst. The ORR catalytic activity study of vanadium nitride, vanadium carbonitride, and vanadium carbide reveals that tuning anions offers a promising route for the activity enhancement of the non-precious metal catalysts. Electronic supplementary information (ESI) available: Experimental methods; SEM characterization of the catalysts; Tafel test of Pt/C catalyst; BET and cyclic performance tests of VN. See DOI: 10.1039/c4nr02646b

  10. Structural and Electrocatalytic Properties of PtIrCo/C Catalysts for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Wanjala, Bridgid N.; Yin, Jun; Fang, Bin; Luo, Jin; Shao, Minhua; Protsailo, Lesia; Kawamura, Tetsuo; Chen, Yongsheng; Petkov, Valeri; Zhong, Chuan-Jian

    2015-10-15

    This paper describes the results of an investigation of the synthesis of PtIrCo nanoparticles (2-3 nm) for electrocatalytic oxygen reduction reaction. The carbon-supported PtIrCo catalysts (PtIrCo/C) were thermally treated at temperatures ranging from 400 to 900 C. The size, composition, and atomic-scale structures of the PtIrCo/C catalysts were characterized for establishing their correlation with the electrocatalytic activity toward oxygen reduction reaction. The specific activity was found to increase by a factor of 3-5 for the PtIrCo/C catalysts in comparison with Pt/C catalysts. A correlation was identified between the specific activity and the nanoparticle's fcc-type lattice parameter. The specific activity increases whereas the fcc-type lattice parameter decreases with the thermal treatment temperature. This correlation was further substantiated by analyzing the interatomic spatial parameters in the trimetallic nanoparticles based on X-ray absorption fine structure spectroscopic and high-energy XRD experiments. Implications of these findings, along with the durability of the catalysts, to the design of active electrocatalysts were also discussed.

  11. Polypyrrole/carbon black composite as a novel oxygen reduction catalyst for microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Yuan, Yong; Zhou, Shungui; Zhuang, Li

    A polypyrrole/carbon black (Ppy/C) composite has been employed as an electrocatalyst for the oxygen reduction reaction (ORR) in an air-cathode microbial fuel cell (MFC). The electrocatalytic activity of the Ppy/C is evaluated toward the oxygen reduction using cyclic voltammogram and linear sweep voltammogram methods. In comparison with that at the carbon black electrode, the peak potential of the ORR at the Pp/C electrode shifts by approximate 260 mV towards positive potential, demonstrating the electrocatalytic activity of Ppy toward ORR. Additionally, the results of the MFC experiments show that the Ppy/C is well suitable to fully substitute the traditional cathode materials in MFCs. The maximum power density of 401.8 mW m -2 obtained from the MFC with a Ppy/C cathode is higher than that of 90.9 mW m -2 with a carbon black cathode and 336.6 mW m -2 with a non-pyrolysed FePc cathode. Although the power output with a Ppy/C cathode is lower than that with a commercial Pt cathode, the power per cost of a Ppy/C cathode is 15 times greater than that of a Pt cathode. Thus, the Ppy/C can be a good alternative to Pt in MFCs due to the economic advantage.

  12. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

    PubMed Central

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  13. Oxygen reduction at platimun/ionomer interface: effects of phase separation of ionomer

    SciTech Connect

    Chlistunoff, Jerzy

    2008-01-01

    Oxygen reduction reaction (ORR) at the interface between platinum and recast ionomers (Nafion EW 1100 and 950 and 6F-40) was studied at different temperatures (20--80{sup o}C) and humidities (10--100%) employing smooth Pt and Pt-black-covered ultramicroelectrodes. ORR was strongly inhibited on smooth electrodes. The inhibition increased with the reduction time, temperature and humidity, but was absent for Nafion EW 1100 in contact with liquid water. It was attributed to the hydrophobic component of ionomer blocking both active sites and oxygen transport. It was postulated that the dynamic changes in interfacial phase separation of ionomer are facilitated by the attractive interactions between the hydrophobic component of ionomer and bare platinum and between oxide-covered Pt and the hydrophilic component of ionomer. These interactions were also proposed to be responsible for the differences in ORR voltammetry for films prepared and equilibrated under different conditions. The decrease in ORR inhibition, Nafion EW 950> Nafion EW 1100> 6F-40, was correlated with physical and molecular properties of the ionomers. The lack of inhibition for Pt-black-covered electrodes was attributed to the more random distribution of ionomer chains and the high activation barriers for the ionomer restructuring at rough interfaces.

  14. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  15. Small palladium islands embedded in palladium-tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Hu, Guangzhi; Nitze, Florian; Gracia-Espino, Eduardo; Ma, Jingyuan; Barzegar, Hamid Reza; Sharifi, Tiva; Jia, Xueen; Shchukarev, Andrey; Lu, Lu; Ma, Chuansheng; Yang, Guang; Wågberg, Thomas

    2014-10-01

    The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten=1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are ~1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.

  16. Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid.

    PubMed

    Brown, Katherine A; Harris, Derek F; Wilker, Molly B; Rasmussen, Andrew; Khadka, Nimesh; Hamby, Hayden; Keable, Stephen; Dukovic, Gordana; Peters, John W; Seefeldt, Lance C; King, Paul W

    2016-04-22

    The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3 The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3. PMID:27102481

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

    SciTech Connect

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

    2008-01-01

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

  18. Nitrogen- and boron-co-doped core-shell carbon nanoparticles as efficient metal-free catalysts for oxygen reduction reactions in microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Zhong, Shengkui; Zhou, Lihua; Wu, Ling; Tang, Lianfeng; He, Qiyi; Ahmed, Jalal

    2014-12-01

    The most severe bottleneck hindering the widespread application of fuel cell technologies is the difficulty in obtaining an inexpensive and abundant oxygen reduction reaction (ORR) catalyst. The concept of a heteroatom-doped carbon-based metal-free catalyst has recently attracted interest. In this study, a metal-free carbon nanoparticles-based catalyst hybridized with dual nitrogen and boron components was synthesized to catalyze the ORR in microbial fuel cells (MFCs). Multiple physical and chemical characterizations confirmed that the synthetic method enabled the incorporation of both nitrogen and boron dopants. The electrochemical measurements indicated that the co-existence of nitrogen and boron could enhance the ORR kinetics by reducing the overpotential and increasing the current density. The results from the kinetic studies indicated that the nitrogen and boron induced an oxygen adsorption mechanism and a four-electron-dominated reaction pathway for the as-prepared catalyst that was very similar to those induced by Pt/C. The MFC results showed that a maximum power density of ∼642 mW m-2 was obtained using the as-prepared catalyst, which is comparable to that obtained using expensive Pt catalyst. The prepared nitrogen- and boron-co-doped carbon nanoparticles might be an alternative cathode catalyst for MFC applications if large-scale applications and price are considered.

  19. Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N,N-Dimethylformamide

    SciTech Connect

    Pegis, Michael L.; Roberts, John A.; Wasylenko, Derek J.; Mader, Elizabeth A.; Appel, Aaron M.; Mayer, James M.

    2015-12-21

    A variety of energy processes utilize the electrochemical interconversions of dioxygen and water, the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the equilibrium reduction potential of the O2 + 4e– + 4H+ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc+/0) in the respective solvent (as are all the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water from aqueous solution to organic solvent, -0.43 kcal mol-1 for MeCN and -1.47 kcal mol-1 for DMF, and the potential of the H+/H2 couple, –0.028 V in MeCN and –0.662 V in DMF. The H+/H2 couple in DMF has been directly measured electrochemically, using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple can also be extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 V and +0.15 V in MeCN, and -0.73 V and -0.48 V in DMF. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is roughly estimated as +14 kcal mol-1 for acetonitrile and +0.6 kcal mol-1 for dimethylformamide. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  20. Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst.

    PubMed

    Dutta, Indrajit; Carpenter, Michael K; Balogh, Michael P; Ziegelbauer, Joseph M; Moylan, Thomas E; Atwan, Mohammed H; Irish, Nicholas P

    2010-10-01

    A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12-25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a "Swiss cheese" type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report. PMID:23807900

  1. Reduction in Post-Marathon Peak Oxygen Consumption: Sign of Cardiac Fatigue in Amateur Runners?

    PubMed Central

    Sierra, Ana Paula Rennó; da Silveira, Anderson Donelli; Francisco, Ricardo Contesini; Barretto, Rodrigo Bellios de Mattos; Sierra, Carlos Anibal; Meneghelo, Romeu Sergio; Kiss, Maria Augusta Peduti Dal Molin; Ghorayeb, Nabil; Stein, Ricardo

    2016-01-01

    Background Prolonged aerobic exercise, such as running a marathon, produces supraphysiological stress that can affect the athlete's homeostasis. Some degree of transient myocardial dysfunction ("cardiac fatigue") can be observed for several days after the race. Objective To verify if there are changes in the cardiopulmonary capacity, and cardiac inotropy and lusitropy in amateur marathoners after running a marathon. Methods The sample comprised 6 male amateur runners. All of them underwent cardiopulmonary exercise testing (CPET) one week before the São Paulo Marathon, and 3 to 4 days after that race. They underwent echocardiography 24 hours prior to and immediately after the marathon. All subjects were instructed not to exercise, to maintain their regular diet, ingest the same usual amount of liquids, and rest at least 8 hours a day in the period preceding the CPET. Results The athletes completed the marathon in 221.5 (207; 250) minutes. In the post-marathon CPET, there was a significant reduction in peak oxygen consumption and peak oxygen pulse compared to the results obtained before the race (50.75 and 46.35 mL.kg-1 .min-1; 19.4 and 18.1 mL.btm, respectively). The echocardiography showed a significant reduction in the s' wave (inotropic marker), but no significant change in the E/e' ratio (lusitropic marker). Conclusions In amateur runners, the marathon seems to promote changes in the cardiopulmonary capacity identified within 4 days after the race, with a reduction in the cardiac contractility. Such changes suggest that some degree of "cardiac fatigue" can occur. PMID:26760783

  2. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  3. Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N,N-Dimethylformamide.

    PubMed

    Pegis, Michael L; Roberts, John A S; Wasylenko, Derek J; Mader, Elizabeth A; Appel, Aaron M; Mayer, James M

    2015-12-21

    A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e(-) + 4H(+) ⇋ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc(+/0)) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water from aqueous solution to organic solvent, -0.43 kcal mol(-1) for MeCN and -1.47 kcal mol(-1) for DMF, and the potential of the H(+)/H2 couple, - 0.028 V in MeCN and -0.662 V in DMF. The H(+)/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol(-1) for acetonitrile and +0.6 kcal mol(-1) for DMF. PMID:26640971

  4. Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst

    PubMed Central

    Dutta, Indrajit; Carpenter, Michael K; Balogh, Michael P; Ziegelbauer, Joseph M; Moylan, Thomas E; Atwan, Mohammed H; Irish, Nicholas P

    2013-01-01

    A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multi-step synthetic procedure. Material produced at each step was characterized using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS) mapping, x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and cyclic voltammetry (CV), and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode (TF-RDE) technique. The initial synthetic step, a co-reduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. TEM shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12–25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete coreshell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a “Swiss cheese” type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report. PMID:23807900

  5. Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

    2013-12-01

    Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

  6. Nickel-Catalyzed Reductive Cross-Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides: A One-Pot Synthesis of Diarylmethanes.

    PubMed

    Zhang, Jie; Lu, Gusheng; Xu, Jin; Sun, Hongmei; Shen, Qi

    2016-06-17

    The first nickel-catalyzed, magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl chlorides or fluorides is reported. A variety of diarylmethanes can be prepared in good to excellent yields in a one-pot manner using easy-to-access mixed PPh3/NHC Ni(II) complexes of Ni(PPh3)(NHC)Br2 (NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, IPr, 1a; 1,3-di-tert-butylimidazol-2-ylidene, ItBu, 1b) as catalyst precursors. Activation of polychloroarenes or chemoselective cross-coupling based on the difference in catalytic activity between 1a and 1b is used to construct oligo-diarylmethane motifs. PMID:27268781

  7. Extending the Scope of the B(C6 F5 )3 -Catalyzed C=N Bond Reduction: Hydrogenation of Oxime Ethers and Hydrazones.

    PubMed

    Mohr, Jens; Porwal, Digvijay; Chatterjee, Indranil; Oestreich, Martin

    2015-12-01

    The B(C6 F5 )3 -catalyzed hydrogenation is applied to aldoxime triisopropylsilyl ethers and hydrazones bearing an easily removable phthaloyl protective group. The CN reduction of aldehyde-derived substrates (oxime ethers and hydrazones) is enabled by using 1,4-dioxane as the solvent known to participate as the Lewis-basic component in FLP-type heterolytic dihydrogen splitting. More basic ketone-derived hydrazones act as Lewis bases themselves in the FLP-type dihydrogen activation and are therefore successfully hydrogenated in nondonating toluene. The difference in reactivity between aldehyde- and ketone-derived substrates is also reflected in the required catalyst loading and dihydrogen pressure. PMID:26489785

  8. Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes.

    PubMed

    Zayas Pérez, Teresa; Geissler, Gunther; Hernandez, Fernando

    2007-01-01

    The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes (AOP) had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H2O2, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand (COD) and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater. PMID:17918591

  9. Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

    NASA Astrophysics Data System (ADS)

    O'Laoire, Cormac Micheal

    Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

  10. Some reflections on the understanding of the oxygen reduction reaction at Pt(111)

    PubMed Central

    Gómez-Marín, Ana M; Rizo, Ruben

    2013-01-01

    Summary The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments. PMID:24455454

  11. Some reflections on the understanding of the oxygen reduction reaction at Pt(111).

    PubMed

    Gómez-Marín, Ana M; Rizo, Ruben; Feliu, Juan M

    2013-12-27

    The oxygen reduction reaction (ORR) is a pivotal process in electrochemistry. Unfortunately, after decades of intensive research, a fundamental knowledge about its reaction mechanism is still lacking. In this paper, a global and critical view on the most important experimental and theoretical results regarding the ORR on Pt(111) and its vicinal surfaces, in both acidic and alkaline media, is taken. Phenomena such as the ORR surface structure sensitivity and the lack of a reduction current at high potentials are discussed in the light of the surface oxidation and disordering processes and the possible relevance of the hydrogen peroxide reduction and oxidation reactions in the ORR mechanism. The necessity to build precise and realistic reaction models, which are deducted from reliable experimental results that need to be carefully taken under strict working conditions is shown. Therefore, progress in the understanding of this important reaction on a molecular level, and the choice of the right approach for the design of the electrocatalysts for fuel-cell cathodes is only possible through a cooperative approach between theory and experiments. PMID:24455454

  12. Visual detection of trace copper ions based on copper-catalyzed reaction of ascorbic acid with oxygen

    NASA Astrophysics Data System (ADS)

    Hou, Xin Yan; Chen, Shu; Shun, Lian Ju; Zhao, Yi Ni; Zhang, Zhi Wu; Long, Yun Fei; Zhu, Li

    2015-10-01

    A visual detection method for trace Cu2+ in aqueous solutions using triangular silver nanoplates (abbreviated as TAgNPs) as the probe was developed. The method is based on that TAgNPs could be corroded in sodium thiosulfate (Na2S2O3) solutions. The absorption spectrum of TAgNPs solution changed when it is corroded by Na2S2O3. The reaction of oxygen with ascorbic acid (Vc) in the presence of a low concentration of Cu2+ generates hydrogen peroxide that reacts with Na2S2O3, which leads the concentration of Na2S2O3 in the solution to be decreased. Therefore, the reaction between TAgNPs and the reacted mixture of Na2S2O3/Vc/Cu2+ was prevented efficiently. When the Na2S2O3 concentration and reaction time are constant, the decrease in the concentration of Na2S2O3 is directly proportional to the Cu2+ concentration. Thus, morphology, color, and maximum absorption wavelength of TAgNPs changed with the change of Cu2+ concentration. The changed maximum absorption wavelength of TAgNPs (Δλ) is proportional to Cu2+ concentration in the range from 7.5 × 10-9 to 5.0 × 10-7 M with a correlation coefficient of r = 0.9956. Moreover, color change of TAgNP solution was observed clearly over a Cu2+ concentration range from 7.5 × 10-8 to 5.0 × 10-7 M. This method has been used to detect the Cu2+ content of a human hair sample, and the result is in agreement with that obtained by the atomic absorption spectroscopy (AAS) method.

  13. Fe/N/C hollow nanospheres by Fe(iii)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction.

    PubMed

    Zhou, Dan; Yang, Liping; Yu, Linghui; Kong, Junhua; Yao, Xiayin; Liu, Wanshuang; Xu, Zhichuan; Lu, Xuehong

    2015-01-28

    In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe(3+)-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ∼10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O. Moreover, it displays better electrochemical durability and tolerance to methanol crossover effect in an alkaline medium than the Pt/C. The excellent catalytic performance of Fe/N/C HNSs-750 towards ORR can be ascribed to their high specific surface area, mesoporous morphology, homogeneous distribution of abundant active sites, high pyridinic nitrogen content, graphitic nitrogen and graphitic carbon, as well as the synergistic effect of nitrogen and iron species for catalyzing ORR. PMID:25500995

  14. In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

    PubMed Central

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-01-01

    Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an “electron reservoir”, we suggest that rGO serves as “peroxide cleaner” in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

  15. In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-07-01

    Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an ``electron reservoir'', we suggest that rGO serves as ``peroxide cleaner'' in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion.

  16. In-situ formation of cobalt-phosphate oxygen-evolving complex-anchored reduced graphene oxide nanosheets for oxygen reduction reaction.

    PubMed

    Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

    2013-01-01

    Oxygen conversion process between O₂ and H₂O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an "electron reservoir", we suggest that rGO serves as "peroxide cleaner" in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

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

    DOEpatents

    Zelenay, Piotr; Wu, Gang

    2014-04-29

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

  18. Enhanced electrocatalytic activity of nitrogen-doped olympicene/graphene hybrids for the oxygen reduction reaction.

    PubMed

    Hou, Xiuli; Zhang, Peng; Li, Shuang; Liu, Wei

    2016-08-17

    Developing inexpensive and non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) is among the major goals in fuel cells. Herein, by using density-functional theory calculations, we show that N-doped olympicene/graphene hybrids exhibit unexpectedly high ORR catalytic activity-even comparable to that of the Pt(111) surface. Both graphitic-type and pyridine-type N-doped olympicene/graphene hybrids are highly active for the ORR and have good CO tolerance. The formation of the second H2O molecule is the rate-determining step for the ORR with the graphitic-type hybrid, whereas on the pyridine-type hybrid, it is the formation of OOH. Note that N-doped olympicene/graphene hybrid materials combine the high reactivity of olympicene and the high electrical conductivity of graphene, which allows them to be potentially used as low-cost and non-precious-metal ORR catalysts. PMID:27499058

  19. Elucidating the activity of stepped Pt single crystals for oxygen reduction.

    PubMed

    Bandarenka, Aliaksandr S; Hansen, Heine A; Rossmeisl, Jan; Stephens, Ifan E L

    2014-07-21

    The unexpectedly high measured activity of Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystal surfaces towards the oxygen reduction reaction (ORR) is explained utilizing the hydroxyl binding energy as the activity descriptor. Using this descriptor (estimated using experimental data obtained by different groups), a well-defined Sabatier-type volcano is observed for the activities measured for the Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystals, in remarkable agreement with earlier theoretical studies. We propose that the observed destabilisation of *OH species at these surfaces is due to the decreased solvation of the adsorbed hydroxyl intermediates on adjacent terrace sites. PMID:24643715

  20. The Pt(111)/electrolyte interface under oxygen reduction reaction conditions: an electrochemical impedance spectroscopy study.

    PubMed

    Bondarenko, Alexander S; Stephens, Ifan E L; Hansen, Heine A; Pérez-Alonso, Francisco J; Tripkovic, Vladimir; Johansson, Tobias P; Rossmeisl, Jan; Nørskov, Jens K; Chorkendorff, Ib

    2011-03-01

    The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO(4) using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange between the adsorbate and Pt surface atoms (0.45-1.15 V vs RHE). An equivalent electric circuit is proposed to model the Pt(111)/electrolyte interface under ORR conditions within the selected potential window. This equivalent circuit reflects three processes with different time constants, which occur simultaneously during the ORR at Pt(111). Density functional theory (DFT) calculations were used to correlate and interpret the results of the measurements. The calculations indicate that the coadsorption of ClO(4)* and Cl* with OH* is unlikely. Our analysis suggests that the two-dimensional (2D) structures formed in O(2)-free solution are also formed under ORR conditions. PMID:21244087

  1. PdNi hollow nanoparticles for improved electrocatalytic oxygen reduction in alkaline environments.

    PubMed

    Wang, Meng; Zhang, Weimin; Wang, Jiazhao; Wexler, David; Poynton, Simon D; Slade, Robert C T; Liu, Huakun; Winther-Jensen, Bjorn; Kerr, Robert; Shi, Dongqi; Chen, Jun

    2013-12-11

    Palladium-nickel (PdNi) hollow nanoparticles were synthesized via a modified galvanic replacement method using Ni nanoparticles as sacrificial templates in an aqueous medium. X-ray diffraction and transmission electron microscopy show that the as-synthesized nanoparticles are alloyed nanostructures and have hollow interiors with an average particle size of 30 nm and shell thickness of 5 nm. Compared with the commercially available Pt/C or Pd/C catalysts, the synthesized PdNi/C has superior electrocatalytic performance towards the oxygen reduction reaction, which makes it a promising electrocatalyst for alkaline anion exchange membrane fuel cells and alkali-based air-batteries. The electrocatalyst is finally examined in a H2/O2 alkaline anion exchange membrane fuel cell; the results show that such electrocatalysts could work in a real fuel cell application as a more efficient catalyst than state-of-the-art commercially available Pt/C. PMID:24199836

  2. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  3. Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction

    DOE PAGESBeta

    Gong, Yongji; Fei, Huilong; Zou, Xiaolong; Zhou, Wu; Yang, Shubin; Ye, Gonglan; Liu, Zheng; Peng, Zhiwei; Lou, Jun; Vajtai, Robert; et al

    2015-02-02

    Here, we show that nanoribbons of boron- and nitrogen-substituted graphene can be used as efficient electrocatalysts for the oxygen reduction reaction (ORR). Optimally doped graphene nanoribbons made into three-dimensional porous constructs exhibit the highest onset and half-wave potentials among the reported metal-free catalysts for this reaction and show superior performance compared to commercial Pt/C catalyst. Moreover, this catalyst possesses high kinetic current density and four-electron transfer pathway with low hydrogen peroxide yield during the reaction. Finally, first-principles calculations suggest that such excellent electrocatalytic properties originate from the abundant edges of boron- and nitrogen-codoped graphene nanoribbons, which significantly reduce the energymore » barriers of the rate-determining steps of the ORR reaction.« less

  4. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    SciTech Connect

    Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

    2013-11-28

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  5. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    PubMed Central

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells. PMID:24448069

  6. Combinatorial density functional theory-based screening of surface alloys for the oxygen reduction reaction.

    SciTech Connect

    Greeley, J.; Norskov, J.; Center for Nanoscale Materials; Technical Univ. of Denmark

    2009-03-26

    A density functional theory (DFT) -based, combinatorial search for improved oxygen reduction reaction (ORR) catalysts is presented. A descriptor-based approach to estimate the ORR activity of binary surface alloys, wherein alloying occurs only in the surface layer, is described, and rigorous, potential-dependent computational tests of the stability of these alloys in aqueous, acidic environments are presented. These activity and stability criteria are applied to a database of DFT calculations on nearly 750 binary transition metal surface alloys; of these, many are predicted to be active for the ORR but, with few exceptions, they are found to be thermodynamically unstable in the acidic environments typical of low-temperature fuel cells. The results suggest that, absent other thermodynamic or kinetic mechanisms to stabilize the alloys, surface alloys are unlikely to serve as useful ORR catalysts over extended periods of operation.

  7. Solution-processed PEDOT:PSS/graphene composites as the electrocatalyst for oxygen reduction reaction.

    PubMed

    Zhang, Miao; Yuan, Wenjing; Yao, Bowen; Li, Chun; Shi, Gaoquan

    2014-03-12

    Composites of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and reduced graphene oxide (rGO) have been prepared by solution mixing and applied as electrocatalysts for oxygen reduction reaction (ORR) after treatment with concentrated H2SO4. The blending of rGO induces the conformational change of PEDOT chains from benzoid to quionoid structure and charge transfer from rGO to PEDOT. H2SO4 post-treatment can remove part of insulating PSS from the surface of the PEDOT:PSS/rGO composite film, resulting in a significant conductivity enhancement of the composite. This synergistic effect makes the H2SO4-treated PEDOT:PSS/rGO composite a promising catalyst for ORR. It exhibits enhanced electrocatalytic activity, better tolerance to a methanol crossover effect and CO poisoning, and longer durability than those of the platinum/carbon catalyst. PMID:24456474

  8. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    PubMed

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode. PMID:25686380

  9. Nanosheets Co3O4 Interleaved with Graphene for Highly Efficient Oxygen Reduction.

    PubMed

    Odedairo, Taiwo; Yan, Xuecheng; Ma, Jun; Jiao, Yalong; Yao, Xiangdong; Du, Aijun; Zhu, Zhonghua

    2015-09-30

    Efficient yet inexpensive electrocatalysts for oxygen reduction reaction (ORR) are an essential component of renewable energy devices, such as fuel cells and metal-air batteries. We herein interleaved novel Co3O4 nanosheets with graphene to develop a first ever sheet-on-sheet heterostructured electrocatalyst for ORR, whose electrocatalytic activity outperformed the state-of-the-art commercial Pt/C with exceptional durability in alkaline solution. The composite demonstrates the highest activity of all the nonprecious metal electrocatalysts, such as those derived from Co3O4 nanoparticle/nitrogen-doped graphene hybrids and carbon nanotube/nanoparticle composites. Density functional theory (DFT) calculations indicated that the outstanding performance originated from the significant charge transfer from graphene to Co3O4 nanosheets promoting the electron transport through the whole structure. Theoretical calculations revealed that the enhanced stability can be ascribed to the strong interaction generated between both types of sheets. PMID:26345714

  10. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction.

    PubMed

    Nie, Yao; Li, Li; Wei, Zidong

    2015-04-21

    Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is key to the fabrication of commercially viable fuel cell devices and metal-air batteries for future energy applications. Herein, we review the most recent advances in the development of Pt-based and Pt-free materials in the field of fuel cell ORR catalysis. This review covers catalyst material selection, design, synthesis, and characterization, as well as the theoretical understanding of the catalysis process and mechanisms. The integration of these catalysts into fuel cell operations and the resulting performance/durability are also discussed. Finally, we provide insights into the remaining challenges and directions for future perspectives and research. PMID:25652755

  11. Porous Dendritic Platinum Nanotubes with Extremely High Activity and Stability for Oxygen Reduction Reaction

    PubMed Central

    Zhang, Gaixia; Sun, Shuhui; Cai, Mei; Zhang, Yong; Li, Ruying; Sun, Xueliang

    2013-01-01

    Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts. PMID:23524665

  12. High-performance oxygen reduction catalyst derived from porous, nitrogen-doped carbon nanosheets.

    PubMed

    Wang, Hao; Chen, Kai; Cao, Yingjie; Zhu, Juntong; Jiang, Yining; Feng, Lai; Dai, Xiao; Zou, Guifu

    2016-10-01

    A facile, self-foaming strategy is reported to synthesize porous, nitrogen-doped carbon nanosheets (N-CNSs) as a metal-free electrocatalyst for oxygen reduction reaction (ORR). Benefiting from the synergistic functions of N-induced active sites, a highly specific surface area and continuous structure, the optimal N-CNS catalyst exhibits Pt-like ORR activity (positive onset potential of ∼0 V versus Ag/AgCl and limiting current density of 5 mA cm(-2)) through a four-electron transfer process in alkaline media with excellent cycle stability and methanol tolerance. This work not only provides a promising metal-free ORR catalyst but also opens up a new path for designing carbon-based materials towards broad applications. PMID:27575594

  13. Following the Reduction of Oxygen on TiO2 Anatase (101) Step by Step.

    PubMed

    Setvin, Martin; Aschauer, Ulrich; Hulva, Jan; Simschitz, Thomas; Daniel, Benjamin; Schmid, Michael; Selloni, Annabella; Diebold, Ulrike

    2016-08-01

    We have investigated the reaction between O2 and H2O, coadsorbed on the (101) surface of a reduced TiO2 anatase single crystal by scanning tunneling microscopy, density functional theory, temperature-programmed desorption, and X-ray photoelectron spectroscopy. While water adsorbs molecularly on the anatase (101) surface, the reaction with O2 results in water dissociation and formation of terminal OH groups. We show that these terminal OHs are the final and stable reaction product on reduced anatase. We identify OOH as a metastable intermediate in the reaction. The water dissociation reaction runs as long as the surface can transfer enough electrons to the adsorbed species; the energy balance and activation barriers for the individual reaction steps are discussed, depending on the number of electrons available. Our results indicate that the presence of donor dopants can significantly reduce activation barriers for oxygen reduction on anatase. PMID:27374609

  14. Dramatic increase in the oxygen reduction reaction for platinum cathodes from tuning the solvent dielectric constant.

    PubMed

    Fortunelli, Alessandro; Goddard, William A; Sha, Yao; Yu, Ted H; Sementa, Luca; Barcaro, Giovanni; Andreussi, Oliviero

    2014-06-23

    Hydrogen fuel cells (FC) are considered essential for a sustainable economy based on carbon-free energy sources, but a major impediment are the costs. First-principles quantum mechanics (density functional theory including solvation) is used to predict how the energies and barriers for the mechanistic steps of the oxygen reduction reaction (ORR) over the fcc(111) platinum surface depend on the dielectric constant of the solvent. The ORR kinetics can be strongly accelerated by decreasing the effective medium polarizability from the high value it has in water. Possible ways to realize this experimentally are suggested. The calculated volcano structure for the dependence of rate on solvent polarization is considered to be general, and should be observed in other electrochemical systems. PMID:24828005

  15. Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction

    SciTech Connect

    Gong, Yongji; Fei, Huilong; Zou, Xiaolong; Zhou, Wu; Yang, Shubin; Ye, Gonglan; Liu, Zheng; Peng, Zhiwei; Lou, Jun; Vajtai, Robert; Yakobson, Boris I.; Tour, James M.; Ajayan, Pulickel M.

    2015-02-02

    Here, we show that nanoribbons of boron- and nitrogen-substituted graphene can be used as efficient electrocatalysts for the oxygen reduction reaction (ORR). Optimally doped graphene nanoribbons made into three-dimensional porous constructs exhibit the highest onset and half-wave potentials among the reported metal-free catalysts for this reaction and show superior performance compared to commercial Pt/C catalyst. Moreover, this catalyst possesses high kinetic current density and four-electron transfer pathway with low hydrogen peroxide yield during the reaction. Finally, first-principles calculations suggest that such excellent electrocatalytic properties originate from the abundant edges of boron- and nitrogen-codoped graphene nanoribbons, which significantly reduce the energy barriers of the rate-determining steps of the ORR reaction.

  16. Nitride stabilized PtNi core-shell nanocatalyst for high oxygen reduction activity.

    PubMed

    Kuttiyiel, Kurian A; Sasaki, Kotaro; Choi, Yongman; Su, Dong; Liu, Ping; Adzic, Radoslav R

    2012-12-12

    We describe a route to the development of novel PtNiN core-shell catalysts with low Pt content shell and inexpensive NiN core having high activity and stability for the oxygen reduction reaction (ORR). The PtNiN synthesis involves nitriding Ni nanoparticles and simultaneously encapsulating it by 2-4 monolayer-thick Pt shell. The experimental data and the density functional theory calculations indicate nitride has the bifunctional effect that facilitates formation of the core-shell structures and improves the performance of the Pt shell by inducing both geometric and electronic effects. Synthesis of inexpensive NiN cores opens up possibilities for designing of various transition metal nitride based core-shell nanoparticles for a wide range of applications in energy conversion processes. PMID:23194259

  17. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    NASA Astrophysics Data System (ADS)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  18. Multicopper models for the laccase active site: effect of nuclearity on electrocatalytic oxygen reduction.

    PubMed

    Tse, Edmund C M; Schilter, David; Gray, Danielle L; Rauchfuss, Thomas B; Gewirth, Andrew A

    2014-08-18

    Cu complexes of 2,2'-dipicolylamine (DPA) were prepared and tested as electrocatalysts for the oxygen reduction reaction (ORR). To study the effect of multinuclearity on the ORR, two Cu-DPA units were connected with a flexible linker, and a third metal-binding pocket was installed in the ligand framework. ORR onset potentials and the diffusion-limited current densities of di- and tricopper complexes of DPA derivatives were found to be comparable to those of the simpler Cu-DPA system. Electrochemical analyses, crystallographic data, and metal-substitution studies suggested that Cu complexes of DPA derivatives reacted with O2 via a binuclear intermolecular pathway but that the Cu center in the third binding site did not participate in the ORR process. This study highlights the viability of Cu-DPA complexes to mimic the T3-site of laccase, and serves as a guide for designing future laccase models. PMID:25072935

  19. Heterocarbon nanosheets incorporating iron phthalocyanine for oxygen reduction reaction in both alkaline and acidic media.

    PubMed

    Hyun, Koangyong; Ueno, Tomonaga; Panomsuwan, Gasidit; Li, Oi Lun; Saito, Nagahiro

    2016-04-28

    Heterocarbon nanosheets incorporating iron phthalocyanine (FP-NCNs-SP) have been successfully synthesized by a facile one-pot solution plasma process at high repetition frequency. It was found that the Fe-N4 catalytic active sites could be preserved on the FP-NCNs-SP without degradation. The FP-NCNs-SP also possessed large surface area, good conductivity and high degree of graphitization. Electrochemical evaluations demonstrated that NCNs-SP had excellent electrocatalytic activity and selectivity toward oxygen reduction reaction (ORR) in alkaline medium through a direct four-electron pathway. Although the significant improvement in ORR activity was clearly observed in acidic medium, it was much poorer than in alkaline medium. We believe that the results presented in this work will shed light on the advanced synthesis and design of ORR electrocatalysts at room temperature with an abundance of catalytically active sites and high ORR performance. PMID:27055883

  20. Synergy among transition element, nitrogen, and carbon for oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Li, Zhou Peng; Liu, Zi Xuan; Zhu, Kun Ning; Li, Zhuo; Liu, Bin Hong

    2012-12-01

    A series of M-doped polypyrrole (PPy)-modified BP2000 catalysts (M = Mn, Fe, Co, Ni, and Cu) are synthesized using the hydrothermal method. The synergy among a transition element, nitrogen, and carbon for oxygen reduction reaction (ORR) in alkaline medium is discussed based on the physical characterization and electrochemical analyses of the Co-doped PPy-modified BP2000. PPy is found to adhere carbon black particles together to form a porous 3D network during the PPy modification on BP2000. PPy reconfiguration occurs during the hydrothermal treatment process. The individual interactions between BP and PPy, BP and Co, and Co and PPy exhibit insignificant effects on the enhancement of ORR. The cooperative interaction among Co, N, and C plays a very important role in the enhancement of ORR. The doping effect of transition-metal salt on ORR enhancement depends on the nature of the transition element and the corresponding anion.

  1. Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions.

    PubMed

    Wei, Ping-Jie; Yu, Guo-Qiang; Naruta, Yoshinori; Liu, Jin-Gang

    2014-06-23

    The oxygen reduction reaction (ORR) is one of the most important reactions in both life processes and energy conversion systems. The replacement of noble-metal Pt-based ORR electrocatalysts by nonprecious-metal catalysts is crucial for the large-scale commercialization of automotive fuel cells. Inspired by the mechanisms of dioxygen activation by metalloenzymes, herein we report a structurally well-defined, bio-inspired ORR catalyst that consists of a biomimetic model compound-an axial imidazole-coordinated porphyrin-covalently attached to multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired electrocatalyst demonstrates superior ORR activity and stability compared to those of the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions, thus making it a promising alternative as an ORR electrocatalyst for application in fuel-cell technology. PMID:24842193

  2. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    SciTech Connect

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  3. Electrochemical Fluorographane: Hybrid Electrocatalysis of Biomarkers, Hydrogen Evolution, and Oxygen Reduction.

    PubMed

    Gusmão, Rui; Sofer, Zdeněk; Šembera, Filip; Janoušek, Zbyněk; Pumera, Martin

    2015-11-01

    Fluorographane (C1 Hx F1-x+δ )n is a new member of the graphene family that exhibits hydrophobicity and a large band gap that is tunable based on the level of fluorination. Herein, sensing and energy applications of fluorographane are reported. The results reveal that the carbon-to-fluoride ratio of fluorographane has a great impact on the electrochemical performance of the materials. Lowered oxidation potentials for ascorbic and uric acids, in addition to a catalytic effect for hydroquinone and dopamine redox processes, are obtained with a high fluoride content. Moreover, fluorographane, together with residual copper- and nickel-based doping, acted as a hybrid electrocatalyst to promote hydrogen evolution and oxygen reduction reactions with considerably lower onset potentials than those of graphane (starting material), which makes this a promising material for a broad range of applications. PMID:26442653

  4. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA were more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.

  5. Nanoelectrochemical approach to detecting short-lived intermediates of electrocatalytic oxygen reduction.

    PubMed

    Zhou, Min; Yu, Yun; Hu, Keke; Mirkin, Michael V

    2015-05-27

    Development of better catalysts for the oxygen reduction reaction (ORR) and other electrocatalytic processes requires detailed knowledge of reaction pathways and intermediate species. Here we report a new methodology for detecting charged reactive intermediates and its application to the mechanistic analysis of ORR. A nanopipette filled with an organic phase that is immiscible with the external aqueous solution was used as a tip in the scanning electrochemical microscope to detect and identify a short-lived superoxide (O2(●-)) intermediate and to determine the rate of its generation at the catalytic Pt substrate and its lifetime in neutral aqueous solution. The voltammogram of the O2(●-) anion transfer to the organic phase provides a unique signature for unambiguous identification of superoxide. The extremely short attainable separation distance between the pipette tip and substrate surface (∼1 nm) makes this technique suitable for detecting and identifying charged intermediates of catalytic processes with a lifetime of a few nanoseconds. PMID:25978070

  6. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  7. Metal molybdate nanorods as non-precious electrocatalysts for the oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wu, Tian; Zhang, Lieyu

    2015-12-01

    Development of non-precious electrocatalysts with applicable electrocatalytic activity towards the oxygen reduction reaction (ORR) is important to fulfill broad-based and large-scale applications of metal/air batteries and fuel cells. Herein, nickel and cobalt molybdates with uniform nanorod morphology are synthesized using a facile one-pot hydrothermal method. The ORR activity of the prepared metal molybdate nanorods in alkaline media are investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperomety in rotating disk electrode (RDE) techniques. The present study suggests that the prepared metal molybdate nanorods exhibit applicable electrocatalytic activities towards the ORR in alkaline media, promising the applications as non-precious cathode in fuel cells and metal-air batteries.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  10. Electrocatalytic performances of N-doped graphene with anchored iridium species in oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Choi, Kwangrok; Lee, Seungjun; Shim, Yeonjun; Oh, Junghoon; Kim, Sujin; Park, Sungjin

    2015-09-01

    Development of new systems with high catalytic performances in the oxygen reduction reaction (ORR) for practical applications in fuel cells and metal-air batteries is a challenge. We develop a one-pot solution method for producing a novel hybrid material consisting of Ir species anchored on N-doped graphene. The hybrid is synthesized by reacting graphene oxide with IrCl3 · xH2O in dimethylformamide under reflux. Chemical and structural analyses confirm the attachment of Ir atoms to the N and O atoms of the N-doped graphene-based materials. The hybrid shows a good electrocatalytic performance for the ORR in alkaline media, with an onset potential of 0.88 V (versus the reversible hydrogen electrode), high long-term durability, and good tolerance for methanol poisoning.

  11. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    PubMed Central

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (−0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm−2 at −0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  12. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm(-2) at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  13. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-05-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm-2 at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries.

  14. Layered SiC Sheets: A Potential Catalyst for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Zhang, P.; Xiao, B. B.; Hou, X. L.; Zhu, Y. F.; Jiang, Q.

    2014-01-01

    The large-scale practical application of fuel cells cannot come true if the high-priced Pt-based electrocatalysts for oxygen reduction reaction (ORR) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, based on density functional theory (DFT), we exploited the potentials of layered SiC sheets as a novel catalyst for ORR. From our DFT results, it can be predicted that layered SiC sheets exhibit excellent ORR catalytic activity without CO poisoning, while the CO poisoning is the major drawback in conventional Pt-based catalysts. Furthermore, the layered SiC sheets in alkaline media has better catalytic activity than Pt(111) surface and have potential as a metal-free catalyst for ORR in fuel cells.

  15. Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

    DOE PAGESBeta

    Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong; Yang, Tae -Hyun; Park, Gu -Gon; Zhang, Chengxu; Chen, Guangyu; Adzic, Radoslav R.

    2015-07-22

    The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC). Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared PtMLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability of themore » PtMLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.« less

  16. Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

    SciTech Connect

    Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong; Yang, Tae -Hyun; Park, Gu -Gon; Zhang, Chengxu; Chen, Guangyu; Adzic, Radoslav R.

    2015-07-22

    The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC). Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared PtMLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability of the PtMLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.

  17. Design of Laccase-Metal Organic Framework-Based Bioelectrodes for Biocatalytic Oxygen Reduction Reaction.

    PubMed

    Patra, Snehangshu; Sene, Saad; Mousty, Christine; Serre, Christian; Chaussé, Annie; Legrand, Ludovic; Steunou, Nathalie

    2016-08-10

    Laccase in combination with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator is a well-known bioelectrocatalyst for the 4-electron oxygen reduction reactions (ORR). The present work deals with the first exploitation of mesoporous iron(III) trimesate-based metal organic frameworks (MOF) MIL-100(Fe) (MIL stands for materials from Institut Lavoisier) as a new and efficient immobilization matrix of laccase for the building up of biocathodes for ORR. First, the immobilization of ABTS in the pores of the MOF was studied by combining micro-Raman spectroscopy, X-ray powder diffraction (XRPD), and N2 porosimetry. The ABTS-MIL-100(Fe)-based modified electrode presents excellent properties in terms of charge transfer kinetics and ionic conductivity as well as a very stable and reproducible electrochemical response, showing that MIL-100(Fe) provides a suitable and stabilizing microenvironment for electroactive ABTS molecules. In a second step, laccase was further immobilized on the MIL-100(Fe)-ABTS matrix. The Lac-ABTS-MIL-100(Fe)-CIE bioelectrode presents a high electrocatalytic current density of oxygen reduction and a reproducible electrochemical response characterized by a high stability over a long period of time (3 weeks). These results constitute a significant advance in the field of laccase-based bioelectrocatalysts for ORR. According to our work, it appears that the high catalytic efficiency of Lac-ABTS-MIL-100(Fe) for ORR may result from a synergy of chemical and catalytic properties of MIL-100(Fe) and laccase. PMID:27447023

  18. Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Shan, Shiyao; Petkov, Valeri; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-10-01

    For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

  19. Electrochemical and Structural Study of a Chemically Dealloyed PtCu Oxygen Reduction Catalyst

    SciTech Connect

    Dutta, Indrajit; Carpenter, Michael K.; Balogh, Michael P.; Ziegelbauer, Joseph M.; Moylan, Thomas E.; Atwan, Mohammed H.; Irish, Nicholas P.

    2010-10-22

    A carbon-supported, dealloyed platinum-copper (Pt-Cu) oxygen reduction catalyst was prepared using a multistep synthetic procedure. Material produced at each step was characterized using high-angle annular dark-field scanning transmission electron microscopy, electron energy loss spectroscopy mapping, X-ray absorption spectroscopy, X-ray diffraction, and cyclic voltammetry, and its oxygen reduction reaction (ORR) activity was measured by a thin-film rotating disk electrode technique. The initial synthetic step, a coreduction of metal salts, produced a range of poorly crystalline Pt, Cu, and Pt-Cu alloy nanoparticles that nevertheless exhibited good ORR activity. Annealing this material alloyed the metals and increased particle size and crystallinity. Transmission electron microscopy shows the annealed catalyst to include particles of various sizes, large (>25 nm), medium (12-25 nm), and small (<12 nm). Most of the small and medium-sized particles exhibited a partial or complete core-shell (Cu-rich core and Pt shell) structure with the smaller particles typically having more complete shells. The appearance of Pt shells after annealing indicates that they are formed by a thermal diffusion mechanism. Although the specific activity of the catalyst material was more than doubled by annealing, the concomitant decrease in Pt surface area resulted in a drop in its mass activity. Subsequent dealloying of the catalyst by acid treatment to partially remove the copper increased the Pt surface area by changing the morphology of the large and some medium particles to a 'Swiss cheese' type structure having many voids. The smaller particles retained their core-shell structure. The specific activity of the catalyst material was little reduced by dealloying, but its mass activity was more than doubled due to the increase in surface area. The possible origins of these results are discussed in this report.

  20. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

    2015-03-01

    Nanoparticles of PdRu, Pd3Ru, and Pd9Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x = 1/3/9), suggest successful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd9Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd9Ru surface (Pd9Ru@Pt). The Pd9Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). The mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd9Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  1. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGESBeta

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  2. Density functional studies of functionalized graphitic materials with late transition metals for Oxygen Reduction Reactions.

    PubMed

    Calle-Vallejo, Federico; Martínez, José Ignacio; Rossmeisl, Jan

    2011-09-14

    Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the cathode. In this contribution, on the basis of Density Functional Theory (DFT) calculations, we show that graphitic materials with active sites composed of 4 nitrogen atoms and transition metal atoms belonging to groups 7 to 9 in the periodic table are active towards ORR, and also towards Oxygen Evolution Reaction (OER). Spin analyses suggest that the oxidation state of those elements in the active sites should in general be +2. Moreover, our results verify that the adsorption behavior of transition metals is not intrinsic, since it can be severely altered by changes in the local geometry of the active site, the chemical nature of the nearest neighbors, and the oxidation states. Nonetheless, we find that these catalysts trend-wise behave as oxides and that their catalytic activity is limited by exactly the same universal scaling relations. PMID:21796295

  3. Optimization of catalyst layer composition for PEMFC using graphene-based oxygen reduction reaction catalysts

    NASA Astrophysics Data System (ADS)

    Park, Jong Cheol; Park, Sung Hyeon; Chung, Min Wook; Choi, Chang Hyuck; Kho, Back Kyun; Woo, Seong Ihl

    2015-07-01

    The focus in recent years is on developing high performance non-precious metal catalysts (NPMCs) to reduce the catalyst cost in fuel cells. However, little attention has been paid to improve the utilization of NPMCs. Thus, this study focuses on the optimization of electrode component, particularly the Nafion content. With the synthesized graphene based oxygen reduction reaction (ORR) catalyst, the catalyst inks were prepared at various Nafion contents with suitable amounts of catalysts sprayed on the gas diffusion media. Twenty different single cells were assembled and measured for polarization, resistance and electrochemical impedance. Electrodes of 66.7 and 50.0% Nafion contents showed the highest performance for hydrogen/oxygen and hydrogen/air operation, respectively. These results were explained using the electrochemical impedance spectra, where the highest performance electrode resulted with the lowest charge transfer resistance. Moreover, negligible change in performance was observed during the 80 h of stability test. The optimization compositions of NPMC-based MEAs were very different to Pt-based MEAs, indicating the importance of optimization studies for the practical use of NPMCs.

  4. Role of LiCoO2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

    DOE PAGESBeta

    Han, Binghong; Qian, Danna; Risch, Marcel; Chi, Miaofang; Meng, Ying Shirley; Yang, Shao-horn

    2015-03-22

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at the tips as comparedmore » to the sides, which was accompanied by more facile redox of Co2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

  5. Multifunctional Co3S4/graphene composites for lithium ion batteries and oxygen reduction reaction.

    PubMed

    Mahmood, Nasir; Zhang, Chenzhen; Jiang, Jie; Liu, Fei; Hou, Yanglong

    2013-04-15

    Cobalt sulfide is a good candidate for both lithium ion batteries (LIBs) and cathodic oxygen reduction reaction (ORR), but low conductivity, poor cyclability, capacity fading, and structural changes hinder its applications. The incorporation of graphene into Co3S4 makes it a promising electrode by providing better electrochemical coupling, enhanced conductivity, fast mobility of ions and electrons, and a stabilized structure due to its elastic nature. With the objective of achieving high-performance composites, herein we report a facile hydrothermal process for growing Co3S4 nanotubes (NTs) on graphene (G) sheets. Electrochemical impedance spectroscopy (EIS) verified that graphene dramatically increases the conductivity of the composites to almost twice that of pristine Co3S4. Electrochemical measurements indicated that the as-synthesized Co3S4/G composites exhibit good cyclic stability and a high discharge capacity of 720 mA h g(-1) up to 100 cycles with 99.9% coulombic efficiency. Furthermore, the composites react with dissolved oxygen in the ORR by four- and two-electron mechanisms in both acidic and basic media with an onset potential close to that of commercial Pt/C. The stability of the composites is much higher than that of Pt/C, and exhibit high methanol tolerance. Thus, these properties endorse Co3 S4 /G composites as auspicious candidates for both LIBs and ORR. PMID:23447515

  6. Oxygen reduction and evolution reactions of air electrodes using a perovskite oxide as an electrocatalyst

    NASA Astrophysics Data System (ADS)

    Nishio, Koji; Molla, Sergio; Okugaki, Tomohiko; Nakanishi, Shinji; Nitta, Iwao; Kotani, Yukinari

    2015-03-01

    The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) of air electrodes consisting of La0.5Sr0.5CoO3 and/or carbon in the electrocatalyst layer are studied by using two types of gas diffusion electrodes. Cyclic voltammetry and square wave voltammetry studies reveal very low ORR activity of carbon-free perovskite and remarkably enhanced ORR of perovskite-carbon composites. The ORR current density at -0.5 V vs. Hg/HgO is higher than 200 mA cm-2 in a wide range of perovskite-carbon composition, suggesting good peroxide reducing capability of the perovskite. The ORR mechanisms of perovskite-carbon composites are consistent with the 2+2-electron mechanisms. The ORR and OER properties of perovskite-carbon composite electrodes are significantly influenced by the carbon species. The electrode exhibits a higher ORR current density, but inferior cycling performances when a carbon material with a higher specific surface area is used, and vice versa. Under a current density of 20 mA cm-2 and ORR and OER durations of 30 min, a gas diffusion type electrode consists of La0.5Sr0.5CoO3 and a low surface area carbon are capable of more than 150 cycles.

  7. Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

    PubMed Central

    Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

    2013-01-01

    The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

  8. Observations of Oxygen Ion Behavior in the Lithium-Based Electrolytic Reduction of Uranium Oxide

    SciTech Connect

    Steven D. Herrmann; Shelly X. Li; Brenda E. Serrano-Rodriguez

    2009-09-01

    Parametric studies were performed on a lithium-based electrolytic reduction process at bench-scale to investigate the behavior of oxygen ions in the reduction of uranium oxide for various electrochemical cell configurations. Specifically, a series of eight electrolytic reduction runs was performed in a common salt bath of LiCl – 1 wt% Li2O. The variable parameters included fuel basket containment material (i.e., stainless steel wire mesh and sintered stainless steel) and applied electrical charge (i.e., 75 – 150% of the theoretical charge for complete reduction of uranium oxide in a basket to uranium metal). Samples of the molten salt electrolyte were taken at regular intervals throughout each run and analyzed to produce a time plot of Li2O concentrations in the bulk salt over the course of the runs. Following each run, the fuel basket was sectioned and the fuel was removed. Samples of the fuel were analyzed for the extent of uranium oxide reduction to metal and for the concentration of salt constituents, i.e., LiCl and Li2O. Extents of uranium oxide reduction ranged from 43 – 70% in stainless steel wire mesh baskets and 8 – 33 % in sintered stainless steel baskets. The concentrations of Li2O in the salt phase of the fuel product from the stainless steel wire mesh baskets ranged from 6.2 – 9.2 wt%, while those for the sintered stainless steel baskets ranged from 26 – 46 wt%. Another series of tests was performed to investigate the dissolution of Li2O in LiCl at 650 °C across various cathode containment materials (i.e., stainless steel wire mesh, sintered stainless steel and porous magnesia) and configurations (i.e., stationary and rotating cylindrical baskets). Dissolution of identical loadings of Li2O particulate reached equilibrium within one hour for stationary stainless steel wire mesh baskets, while the same took several hours for sintered stainless steel and porous magnesia baskets. Rotation of an annular cylindrical basket of stainless steel

  9. Characterization of a transient intermediate formed in the liver alcohol dehydrogenase catalyzed reduction of 3-hydroxy-4-nitrobenzaldehyde

    SciTech Connect

    MacGibbon, A.K.H.; Koerber, S.C.; Pease, K.; Dunn, M.F.

    1987-06-02

    The compounds 3-hydroxy-4-nitrobenzaldehyde and 3-hydroxy-4-nitrobenzyl alcohol are introduced as new chromophoric substrates for probing the catalytic mechanism of horse liver alcohol dehydrogenase (LADH). Ionization of the phenolic hydroxyl group shifts the spectrum of the aldehyde from 360 to 433 nm (pK/sub a/ = 6.0), whereas the spectrum of the alcohol shifts from 350 to 417 nm (pK/sub a/ = 6.9). Rapid-scanning, stopped-flow (RSSF) studies at alkaline pH show that the LADH-catalyzed interconversion of these compounds occurs via the formation of an enzyme-bound intermediate with a blue-shifted spectrum. When reaction is limited to a single turnover of enzyme sites, the formation and decay of the intermediate when aldehyde reacts with enzyme-bound reduced nicotinamide adenine dinucleotide E(NADH) are characterized by two relaxations. Detailed stopped-flow kinetic studies were carried out to investigate the disappearance of aldehyde and NADH, the formation and decay of the intermediate, the displacement of Auramine O by substrate, and /sup 2/H kinetic isotope effects. It was found that (1) NADH oxidation takes place at the rate of the slower relaxation (2) when NADD is substituted for NADH, lambda/sub s/ is subject to a small primary isotope effect; and (3) the events that occur in lambda/sub s/ precede lambda/sub f/. These findings identify the intermediate as a ternary complex containing bound oxidized nicotinamide adenine dinucleotide (NAD/sup +/) and some form of 3-hydroxy-4-nitrobenzyl alcohol. The authors conclude that the LADH substrate site can be divided into two subsites: a highly polar, electropositive subsite in the vicinity of the active-site zinc and, just a few angstroms away, a rather nonpolar region.

  10. A General and Selective Rhodium-Catalyzed Reduction of Amides, N-Acyl Amino Esters, and Dipeptides Using Phenylsilane.

    PubMed

    Das, Shoubhik; Li, Yuehui; Lu, Liang-Qiu; Junge, Kathrin; Beller, Matthias

    2016-05-17

    This article describes a selective reduction of functionalized amides, including N-acyl amino esters and dipeptides, to the corresponding amines using simple [Rh(acac)(cod)]. The catalyst shows excellent chemoselectivity in the presence of different sensitive functional moieties. PMID:26991132

  11. Selenium catalyzed Fe(III)-EDTA reduction by Na2SO3: a reaction-controlled phase transfer catalysis.

    PubMed

    Xiang, Kaisong; Liu, Hui; Yang, Bentao; Zhang, Cong; Yang, Shu; Liu, Zhilou; Liu, Cao; Xie, Xiaofeng; Chai, Liyuan; Min, Xiaobo

    2016-04-01

    Fe(II)-EDTA, a typical chelated iron, is able to coordinate with nitric oxide (NO) which accelerates the rates and kinetics of the absorption of flue gas. However, Fe(II)-EDTA can be easily oxidized to Fe(III)-EDTA which is unable to absorb NO. Therefore, the regeneration of fresh Fe(II)-EDTA, which actually is the reduction of Fe(III)-EDTA to Fe(II)-EDTA, becomes a crucial step in the denitrification process. To enhance the reduction rate of Fe(III)-EDTA, selenium was introduced into the SO3 (2-)/Fe(III)-EDTA system as catalyst for the first time. By comparison, the reduction rate was enhanced by four times after adding selenium even at room temperature (25 °C). Encouragingly, elemental Se could precipitate out when SO3 (2-) was consumed up by oxidation to achieve self-separation. A catalysis mechanism was proposed with the aid of ultraviolet-visible (UV-Vis) spectroscopy, Tyndall scattering, horizontal attenuated total reflection Fourier transform infrared (HATR-FTIR) spectroscopy, and X-ray diffraction (XRD). In the catalysis process, the interconversion between SeSO3 (2-) and nascent Se formed a catalysis circle for Fe(III)-EDTA reduction in SO3 (2-) circumstance. PMID:26888642

  12. Regioselective Copper-Catalyzed Dicarbonylation of Imidazo[1,2-a]pyridines with N,N-Disubstituted Acetamide or Acetone: An Approach to 1,2-Diketones Using Molecular Oxygen.

    PubMed

    Wang, Changcheng; Lei, Sai; Cao, Hua; Qiu, Shuxian; Liu, Jingyun; Deng, Hao; Yan, Caijuan

    2015-12-18

    A novel copper-catalyzed regioselective double carbonylation of imidazo[1,2-a]pyridines with N,N-disubstituted acetamide or acetone using molecular oxygen has been described. It has provided a new approach to synthesize 1,2-carbonyl imidazo[1,2-a]pyridines, which are important substrates and intermediates in preparation of fine chemicals. The product shares a skeleton similar to that of Zolpidem, one of the most prescribed drugs in the world. (18)O-labeling experiments unambiguously established that the oxygen source of products originated from O2 rather than H2O. PMID:26595127

  13. Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Srinivasan, Supramanian; Appleby, A. J.; Martin, Charles R.

    1992-01-01

    Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

  14. Band gap engineered, oxygen-rich TiO2 for visible light induced photocatalytic reduction of CO2.

    PubMed

    Tan, Lling-Lling; Ong, Wee-Jun; Chai, Siang-Piao; Mohamed, Abdul Rahman

    2014-07-01

    A facile and dopant-free strategy was employed to fabricate oxygen-rich TiO2 (O2-TiO2) with enhanced visible light photoactivity. Such properties were achieved by the in situ generation of oxygen through the thermal decomposition of the peroxo-titania complex. The O2-TiO2 photocatalyst exhibited high photoactivity towards CO2 reduction under visible light. PMID:24841282

  15. Large faceted Pd nanocrystals supported small Pt nanoparticles as highly durable electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Zhang, Geng; Lu, Wangting; Cao, Longsheng; Qin, Xiaoping; Ding, Fei; Tang, Shun; Shao, Zhi-Gang; Yi, Baolian

    2016-09-01

    The reduction of Pt content together with the improvement of the durability of the catalyst for oxygen reduction reaction (ORR) is required to the large-scale commercialization of proton exchange membrane fuel cells. In this work, a novel ORR catalyst consisting of large Pd nanocrystal as the core with small Pt nanoparticles supported on the Pd core is prepared by a facile one-step synthesis method. The Pd substrate is presented in the form of well-defined cuboctahedrons and icosahedrons. The type of metal precursors and Pt/Pd molar ratio are important factors to obtain this Pd-supporting-Pt structure. The Pd2-s-Pt1 catalyst with a nominal Pt/Pd atomic ratio at 1/2 shows improved ORR activity: its mass specific activity and area specific activity is 2.5 and 3.5 times that of commercial Pt/C, respectively. More importantly, the Pd2-s-Pt1 catalyst demonstrates outstanding durability against potential cycling which can be ascribed to the slow dissolution of Pd core and the structure transformation from Pd@Pt to hollow PdPt alloyed nanocages. This exciting result provides a new pathway to the design of ORR catalyst with excellent durability.

  16. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

    PubMed Central

    Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

    2015-01-01

    A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells. PMID:26100367

  17. Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts.

    PubMed

    Cheng, Fangyi; Shen, Jian; Peng, Bo; Pan, Yuede; Tao, Zhanliang; Chen, Jun

    2011-01-01

    Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal-air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M(x)Mn(3-x)O(4) (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M(x)Mn(3-x)O(4) from the reduction of amorphous MnO(2) in aqueous M(2+) solution. The prepared Co(x)Mn(3-x)O(4) nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co-Mn-O spinels are also interpreted by experiment and first-principle theoretical studies. PMID:21160522

  18. Electrocatalytic reduction of oxygen on modified oxide surfaces. M.S. Thesis

    NASA Technical Reports Server (NTRS)

    Chaffins, Scott A.; Srinivasan, Vakula S.; Singer, Joseph

    1988-01-01

    A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

  19. Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

    NASA Technical Reports Server (NTRS)

    Miller, R. O.

    1975-01-01

    With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

  20. Microwave-assisted polyol synthesis of PtCu/carbon nanotube catalysts for electrocatalytic oxygen reduction

    NASA Astrophysics Data System (ADS)

    El-Deeb, Heba; Bron, Michael

    2015-02-01

    PtCu/CNT alloy electrocatalysts were prepared by microwave assisted polyol synthesis. The influence of preparation pH and the presence of polyvinylpyrrolidone (PVP) as stabilizer on catalysts nanostructure and activity towards electrocatalytic oxygen reduction was evaluated. The catalysts were alloyed at 400-600 °C for 6 h in reductive atmosphere, and characterized by TEM and XRD. The XRD patterns display a positive shift in 2θ of the Pt 111 peak, which is a good evidence for Pt-Cu alloy formation. Alloy nanoparticles already form at temperatures as low as 400 °C. Highly agglomerated PtCu nanoparticles were obtained in the absence of PVP while PVP addition resulted in dispersed and uniform nanoparticles with a mean particle size of 3.7 nm. Such small particles are a result of the considerably low temperature used during the heat treatment/alloying step. However, while Pt is nearly completely deposited on the CNTs, only smaller fractions of Cu are found in the final catalyst. A high extent of agglomeration was also noticed when the pH during polyol synthesis was increased, which is attributed to Cu-hydroxides precipitation. Pt-Cu core shell catalysts were obtained after voltammetric dealloying. Catalyst prepared at higher pH in the presence of PVP display the highest electrocatalytic activity.

  1. Hybrid binuclear-cobalt-phthalocyanine as oxygen reduction reaction catalyst in single chamber microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Baitao; Zhou, Xiuxiu; Wang, Xiujun; Liu, Bingchuan; Li, Baikun

    2014-12-01

    A novel hybrid binuclear-cobalt-phthalocyanine (Bi-CoPc) is developed as the cathode catalyst to replace the costly platinum (Pt) in single chamber microbial fuel cells (SCMFCs). Bi-CoPc/C is integrated with metal oxides (NiO and CoO) to form macrocyclic complex for enhanced oxygen reduction rate (ORR). The characteristics of hybrid catalysts (Bi-CoPc/C-CoO and Bi-CoPc/C-NiO) are compared with Co-contained catalysts (CoPc/C and Bi-CoPc/C) and metal oxide catalysts (NiO and CoO). The increase in O and N functional groups indicates the benefits of NiO and CoO to the cathode catalysts. The cyclic voltammetry (CV) shows the reduction peak for Bi-CoPc/C-NiO and Bi-CoPc/C-CoO at -0.12 V and -0.22 V, respectively. The power densities (368 mW m-2 and 400 mW m-2) of SCMFCs with Bi-CoPc/C-CoO and Bi-CoPc-NiO/C are the highest among the cathodes tested, and close to that of Pt (450 mW m-2). This study demonstrates that hybrid Bi-CoPc/C with metal oxides has a great potential as a cost-effective catalyst in MFCs.

  2. One-pot synthesis of platinum3cobalt nanoflowers with enhanced oxygen reduction and methanol oxidation

    NASA Astrophysics Data System (ADS)

    Zheng, Jie-Ning; He, Li-Li; Chen, Chen; Wang, Ai-Jun; Ma, Ke-Fu; Feng, Jiu-Ju

    2014-12-01

    Herein, a simple one-pot approach is developed for preparation of Pt3Co nanoflowers by co-reduction of Pt (II) acetylacetonate (Pt(acac)2) and Co (III) acetylacetonate (Co(acac)3) in oleylamine, without any seed or template. It is found that hexadecylpyridinium chloride monohydrate (HDPC) is served as both the stabilizing and structuring-directing agent that plays an important role in the formation of well-dispersed flower-like Pt3Co nanoparticles. The as-prepared Pt3Co nanoflowers show the enhanced catalytic performance for oxygen reduction reaction (ORR) in comparison with solid Pt3Co nanoparticles and commercial Pt black catalysts, dominated by a four-electron pathway based on the Koutecky-Levich equation. Meanwhile, Pt3Co nanoflowers exhibit the improved catalytic activity and long-term stability towards methanol oxidation reaction (MOR), using solid Pt3Co nanoparticles and commercial Pt black catalysts as references. The improved catalytic features of Pt3Co nanoflowers are mainly attributed to the porous three-dimensionally interconnected structures, enlarged specific surface area, ligand effect and bifunctional mechanism between Pt and Co. The as-developed method provides a promising pathway for preparation of highly efficient electrocatalysts for ORR and MOR.

  3. Supportless silver nanowires as oxygen reduction reaction catalysts for hydroxide-exchange membrane fuel cells.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2012-08-01

    Silver nanowires (AgNWs) and nanoparticles (AgNPs) have been synthesized to facilitate hydroxide-exchange membrane fuel cell development and commercialization. AgNWs and AgNPs with variable diameters (25-60 nm AgNWs, 2.4-30 nm AgNPs) have been studied with rotating-disk electrode experiments to examine the impact of size and morphology on the oxygen reduction reaction (ORR). Although a detrimental particle size effect is observed, AgNWs exceed the specific activity of bulk polycrystalline Ag. AgNWs with a diameter of 25 nm further exceed the ORR specific and mass activity of 2.4 nm AgNPs 5.3 times and by 16 %, respectively. Rotating ring-disk electrode testing demonstrates minimal peroxide formation on AgNWs; peroxide production increases with the use of AgNPs by as much as an order of magnitude and further increases with particle size reduction. Silver catalysts demonstrate alcohol tolerance for ORR, illustrating the benefit of silver and AgNWs as catalysts in hydroxide and alcohol hydroxide-based fuel cells. PMID:22887923

  4. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte.

    PubMed

    Huang, K; Bi, K; Liang, C; Lin, S; Zhang, R; Wang, W J; Tang, H L; Lei, M

    2015-01-01

    A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells. PMID:26100367

  5. Enhancing stability of octahedral PtNi nanoparticles for oxygen reduction reaction by halide treatment

    NASA Astrophysics Data System (ADS)

    Choi, Juhyuk; Lee, Youhan; Kim, Jihan; Lee, Hyunjoo

    2016-03-01

    Because a reduction in the amount of Pt catalysts is essential for the commercialization of fuel cells, various approaches have been tested to maximize the mass activity of Pt-based catalysts. Among these, the most successful results so far were obtained using shaped PtNi alloy nanoparticles, preferably with PtNi(111) facets. However, these nanoparticles typically suffer from much lower activity after the durability tests due to the leaching out of the surface Ni during the oxygen reduction reaction (ORR), which leads to the disappearance of the activity-enhancing effect caused by electronic structure modification. Here, we showed that halide treatment of the octahedral PtNi nanoparticles could significantly enhance their durability. Halides are adsorbed on surface Ni more strongly than on surface Pt, and the surface halides are found to preserve the surface Ni that induces the ORR activity enhancement. Especially, Br can preserve the surface Ni effectively. Durability testing by repeating cyclic voltammetry 10,000 times in the 0.6-1.1 V range showed that the mass activity decreased by 52.6% for the as-prepared PtNi octahedral nanoparticles, whereas the mass activity decreased by only 15.0% for the Br-treated PtNi nanoparticles. The simple treatment significantly enhanced the long-term stability of the highly active PtNi alloy nano-octahedra.

  6. Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays

    SciTech Connect

    Carver, Colin T.; Matson, Benjamin D.; Mayer, James M.

    2012-03-28

    Fe(III)meso-tetra(2-carboxyphenyl)porphine chloride (1) was investigated as an electrocatalyst for the oxygen reduction reaction (ORR). Rotating ring-disk voltammetry and independent reactions with hydrogen peroxide indicate that 1 has very high selectivity for reduction of O2 to H2O, without forming significant amounts of H2O2. Cyclic voltammetric measurements at high substrate/catalyst ratios allowed the determination of the turnover frequency (TOF) of 1, TOF = 103 s-1. The 4-carboxyphenyl isomer of 1, in which the carboxylic acids point away from the iron center, is a substantially slower and less selective catalyst. This direct comparison demonstrates that the value of the carboxylate groups positioned to act as proton delivery relays to enhance both the TOF and selectivity of 1 as a catalyst for the ORR. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  7. Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

    NASA Astrophysics Data System (ADS)

    Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

    2015-06-01

    A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells.

  8. Electrocatalytic activities of alkyne-functionalized copper nanoparticles in oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Liu, Ke; Song, Yang; Chen, Shaowei

    2014-12-01

    Stable alkyne-capped copper nanoparticles were prepared by chemical reduction of copper acetate with sodium borohydride in the presence of alkyne ligands. Transmission electron microscopic measurements showed that nanoparticles were well dispersed with a diameter in the range of 4-6 nm. FTIR and photoluminescence spectroscopic measurements confirmed the successful attachment of the alkyne ligands onto the nanoparticle surface most likely forming Cu-Ctbnd interfacial bonds. XPS measurements indicated the formation of a small amount of CuO in the nanoparticles with a satellite peak where the binding energy red-shifted with increasing Cu(II) concentration. Cu2O was also detected in the nanoparticles. Similar results were observed with commercial CuO nanoparticles. Electrochemical studies showed that the as-prepared alkyne-capped copper nanoparticles exhibited apparent electrocatalytic activity in oxygen reduction in alkaline media, a performance that was markedly better than those reported earlier with poly- or single-crystalline copper electrodes; and the fraction of peroxides in the final products decreased with decreasing concentration of oxide components in the nanoparticles.

  9. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGESBeta

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; et al

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  10. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  11. Soft Landing of Bare PtRu Nanoparticles for Electrochemical Reduction of Oxygen

    SciTech Connect

    Johnson, Grant E.; Colby, Robert J.; Engelhard, Mark H.; Moon, DaeWon; Laskin, Julia

    2015-08-07

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu alloy nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 x 104 ions µm-2 and that their average height is centered at 4 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (STEM-HAADF) further confirm that the soft-landed PtRu alloy nanoparticles are uniform in size and have a Ru core decorated with small regions of Pt on the surface. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in relative atomic concentrations of ~9% and ~33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt4f and Ru3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the alloy nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He+ and O+ ions. The activity of electrodes containing 7 x 104 ions µm-2 of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the alloy nanoparticles supported on glassy

  12. Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Johnson, Grant E.; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

    2015-07-01

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 104 ions μm-2 and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ~9% and ~33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He+ and O+ ions. The activity of electrodes containing 7 × 104 ions μm-2 of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was evaluated by

  13. Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

    PubMed

    Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

    2015-08-01

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was

  14. Experimental reduction of simulated lunar glass by carbon and hydrogen and implications for lunar base oxygen production

    NASA Technical Reports Server (NTRS)

    Mckay, David S.; Morris, Richard V.; Jurewicz, Amy J.

    1991-01-01

    The most abundant element in lunar rocks and soils is oxygen which makes up approximately 45 percent by weight of the typical lunar samples returned during the Apollo missions. This oxygen is not present as a gas but is tightly bound to other elements in mineral or glass. When people return to the Moon to explore and live, the extraction of this oxygen at a lunar outpost may be a major goal during the early years of operation. Among the most studied processes for oxygen extraction is the reduction of ilmenite by hydrogen gas to form metallic iron, titanium oxide, and oxygen. A related process is proposed which overcomes some of the disadvantages of ilmenite reduction. It is proposed that oxygen can be extracted by direct reduction of native lunar pyroclactic glass using either carbon, carbon monoxide, or hydrogen. In order to evaluate the feasibility of this proposed process a series of experiments on synthetic lunar glass are presented. The results and a discussion of the experiments are presented.

  15. Monitoring Cr Intermediates and Reactive Oxygen Species with Fluorescent Probes during Chromate Reduction

    PubMed Central

    2015-01-01

    Cr(VI) genotoxicity is caused by products of its reductive metabolism inside the cells. Reactive oxygen species (ROS) and Cr(V,IV) intermediates are potential sources of oxidative damage by Cr(VI). Here, we investigated seven fluorescent probes for the detection of ROS and non-ROS oxidants in Cr(VI) reactions with its main reducers. We found that Cr(V)-skipping metabolism of Cr(VI) by ascorbate in vitro gave no responses with all tested dyes, indicating nonreactivity of Cr(IV) and absence of ROS. Cr(VI) reduction with glutathione (GSH) or Cys strongly enhanced the fluorescence of dichlorofluorescein (DCF) and dihydrorhodamine 123 (DHR123) but produced minimal fluorescence with dihydroethidium and no increases with aminophenylfluorescein and CellRox Green, Orange, and Red. Several tests showed that Cr(VI)-thiol reactions lacked ROS and that Cr(V) caused oxidation of DCF and DHR123. DCF reacted only with free Cr(V), whereas DHR123 detected both the free Cr(V) and Cr(V)-GSH complex. We estimated that Cr(VI)-GSH reactions generated approximately 75% Cr(V)-GSH and 25% free Cr(V), whereas Cys reactions appeared to produce only free Cr(V). DHR123 measurements in H460 cells showed that reduction of Cr(VI) was complete within 20 min postexposure, but it lasted at least 1 h without GSH. Cells with restored ascorbate levels exhibited no DCF or DHR123 oxidation by Cr(VI). Overall, our results demonstrated that Cr(VI) metabolism with its biological reducers lacked ROS and that DHR123 and DCF responses were indicators of total and free Cr(V), respectively. CellRox dyes, dihydroethidium and aminophenylfluorescein, are insensitive to Cr(V,IV) and can be used for monitoring ROS during coexposure to Cr(VI) and oxidants. PMID:24646070

  16. Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions.

    PubMed

    Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

    2014-10-01

    Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. PMID:25141067

  17. Nitrogen-doped and simultaneously reduced graphene oxide with superior dispersion as electrocatalysts for oxygen reduction reaction

    SciTech Connect

    Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Yoo, Sung Jong; Cho, Eun Ae; Khil, Myung-Seob; Joh, Han-Ik

    2014-11-15

    Nitrogen doped graphene oxide (Nr-GO) with properties suitable for electrocatalysts is easily synthesized using phenylhydrazine as a reductant at relatively low temperature. The reducing agent removes various oxygen functional groups bonded to graphene oxide and simultaneously dope the nitrogen atoms bonded with phenyl group all over the basal planes and edge sites of the graphene. The Nr-GO exhibits remarkable electrocatalytic activities for oxygen reduction reaction compared to the commercial carbon black and graphene oxide due to the electronic modification of the graphene structure. In addition, Nr-GO shows excellent dispersibility in various solvent due to the dopant molecules.

  18. Oxygen indicator composed of an organic/inorganic hybrid compound of methylene blue, reductant, surfactant and saponite.

    PubMed

    Sumitani, Makoto; Takagi, Shinsuke; Tanamura, Yoshihiko; Inoue, Haruo

    2004-08-01

    An organic/inorganic hybrid compound consisting of methylene blue, a cationic surfactant and a reductant intercalated into saponite was found to serve as an oxygen indicator that changes color in the presence of oxygen. A mixture of a blue colored dye, methylene blue, a reductant in the form of ascorbic acid or reducing sugar, and cetyltrimethylammonium ion intercalated into synthetic saponite became colorless in an atmosphere having an oxygen concentration of less than 0.1 vol%, and then returned to its blue color as a result of subsequent exposure to air. An oxygen indicator, in the form of a thin film coated on paper prepared by adding a pigment, phloxine B, to the above organic/inorganic hybrid compound, exhibited a pink color at oxygen concentrations of less than 0.1 vol%, and a blue color at oxygen concentrations of higher than 0.5 vol%. In addition, this oxygen indicator exhibited superior photo-fading resistance and storage stability compared with indicators using only methylene blue as the functional dye. PMID:15352503

  19. Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea

    PubMed Central

    2014-01-01

    Background A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report on the anaerobic nitrate metabolism of the fungus Aspergillus terreus (isolate An-4) that was obtained from sediment in the seasonal oxygen minimum zone in the Arabian Sea, a globally important site of oceanic nitrogen loss and nitrous oxide emission. Results Axenic incubations of An-4 in the presence and absence of oxygen and nitrate revealed that this fungal isolate is capable of dissimilatory nitrate reduction to ammonium under anoxic conditions. A 15N-labeling experiment proved that An-4 produced and excreted ammonium through nitrate reduction at a rate of up to 175 nmol 15NH4+ g-1 protein h-1. The products of dissimilatory nitrate reduction were ammonium (83%), nitrous oxide (15.5%), and nitrite (1.5%), while dinitrogen production was not observed. The process led to substantial cellular ATP production and biomass growth and also occurred when ammonium was added to suppress nitrate assimilation, stressing the dissimilatory nature of nitrate reduction. Interestingly, An-4 used intracellular nitrate stores (up to 6–8 μmol NO3- g-1 protein) for dissimilatory nitrate reduction. Conclusions Our findings expand the short list of microbial eukaryotes that store nitrate intracellularly and carry out dissimilatory nitrate reduction when oxygen is absent. In the currently spreading oxygen-deficient zones in the ocean, an as yet unexplored diversity of fungi may recycle nitrate to ammonium and nitrite, the substrates of the major nitrogen loss process anaerobic ammonium oxidation, and the potent greenhouse gas nitrous oxide. PMID:24517718

  20. Pd-Catalyzed oxidative isomerization of propargylic acetates: highly efficient access to α-acetoxyenones via alkenyl Csp(2)-O bond-forming reductive elimination from Pd(IV).

    PubMed

    Li, Jun; Yang, Wenjie; Yan, Fachao; Liu, Qing; Wang, Ping; Li, Yueyun; Zhao, Yi; Dong, Yunhui; Liu, Hui

    2016-08-23

    A Pd(ii)/(iv)-catalyzed oxidative isomerization of propargylic acetates developed for the synthesis of polysubstituted alkenyl acetates is described. The reductive elimination of alkenyl Csp(2)-OAc bonds from Pd(IV) intermediates is achieved. Mechanistic studies indicate that the reaction mechanism consists of trans acetoxypalladation of a triple bond, isomerization, oxidative addition with PhI(OAc)2 and alkenyl C-OAc bond reductive elimination. PMID:27500292

  1. Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

    PubMed Central

    Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

    2014-01-01

    Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

  2. Molybdenum reduction to molybdenum blue in Serratia sp. Strain DRY5 is catalyzed by a novel molybdenum-reducing enzyme.

    PubMed

    Shukor, M Y; Halmi, M I E; Rahman, M F A; Shamaan, N A; Syed, M A

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction. PMID:24724104

  3. Molybdenum Reduction to Molybdenum Blue in Serratia sp. Strain DRY5 Is Catalyzed by a Novel Molybdenum-Reducing Enzyme

    PubMed Central

    Shukor, M. Y.; Halmi, M. I. E.; Rahman, M. F. A.; Shamaan, N. A.; Syed, M. A.

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a Vmax for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent Km for NADH was 0.79 mM. At 5 mM NADH, the apparent Vmax and apparent Km values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (kcat/Km) of the Mo-reducing enzyme was 5.47 M−1 s−1. The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction. PMID:24724104

  4. Oxygen-Dependent Photocatalytic Water Reduction with a Ruthenium(imidazolium) Chromophore and a Cobaloxime Catalyst.

    PubMed

    Petermann, Lydia; Staehle, Robert; Pfeifer, Maxim; Reichardt, Christian; Sorsche, Dieter; Wächtler, Maria; Popp, Jürgen; Dietzek, Benjamin; Rau, Sven

    2016-06-01

    Detailed investigations of a photocatalytic system capable of producing hydrogen under pre-catalytic aerobic conditions are reported. This system consists of the NHC precursor chromophore [Ru(tbbpy)2 (RR'ip)][PF6 ]3 (abbreviated as Ru(RR'ip)[PF6 ]3 ; tbbpy=4,4'-di-tert-butyl-2,2'-bipyridine, RR'ip=1,3-disubstituted-1H-imidazo[4,5-f][1,10]phenanthrolinium), the reduction catalyst Co(dmgH)2 (dmgH=dimethylglyoximato), and the electron donor ascorbic acid (AA). Screening studies with respect to solvent, cobaloxime catalyst, electron donor, pH, and concentrations of the individual components yielded optimized photocatalytic conditions. The system shows high activity based on Ru, with turnover numbers up to 2000 under oxygen-free and pre-catalytic aerobic conditions. The turnover frequency in the latter case was even higher than that for the oxygen-free catalyst system. The Ru complexes show high photostability and their first excited state is primarily located on the RR'ip ligand. X-ray crystallographic analysis of the rigid cyclophane-type ligand dd(ip)2 (Br)2 (dd(ip)2 =1,1',3,3'-bis(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(1H-imidazo[4,5-f][1,10]phenanthrolinium)) and the catalytic activity of its Ru complex [{(tbbpy)2 Ru}2 (μ-dd(ip)2 )][PF6 ]6 (abbreviated as Ru2 (dd(ip)2 )[PF6 ]6 ) suggest an intermolecular catalytic cycle. PMID:27135804

  5. Watershed Influences on Residence Time and Oxygen Reduction Rates in an Agricultural Landscape

    NASA Astrophysics Data System (ADS)

    Shope, C. L.; Tesoriero, A. J.

    2015-12-01

    Agricultural use of synthetic fertilizers and animal manure has led to increased crop production, but also elevated nitrogen concentrations in groundwater, resulting in impaired water quality. Groundwater oxygen concentrations are a key indicator of potential biogeochemical processes, which control water/aquifer interactions and contaminant transport. The U.S. Geological Survey's National Water-Quality Assessment Program has a long-history of studying nutrient transport and processing across the United States and the Glacial Aquifer system in particular. A series of groundwater well networks in Eastern Wisconsin is being used to evaluate the distribution of redox reaction rates over a range of scales with a focus on dissolved O2 reduction rates. An analysis of these multi-scale networks elucidates the influence of explanatory variables (i.e.: soil type, land use classification) on reduction rates and redox reactions throughout the Fox-Wolf-Peshtigo watersheds. Multiple tracers including dissolved gasses, tritium, helium, chlorofluorocarbons, sulfur hexafluoride, and carbon-14 were used to estimate groundwater ages (0.8 to 61.2 yr) at over 300 locations. Our results indicate O2 reduction rates along a flowpath study area (1.2 km2) of 0.15 mg O2 L-1 yr-1 (0.12 to 0.18 mg O2 L-1 yr-1) up to 0.41 mg O2 L-1 yr-1 (0.23 to 0.89 mg O2 L-1 yr-1) for a larger scale land use study area (3,300 km2). Preliminary explanatory variables that can be used to describe the variability in reduction rates include soil type (hydrologic group, bulk density) and chemical concentrations (nitrite plus nitrate, silica). The median residence time expected to reach suboxic conditions (≤ 0.4 mg O2 L-1) for the flowpath and the land use study areas was 66 and 25 yr, respectively. These results can be used to elucidate and differentiate the impact of residence time on groundwater quality vulnerability and sustainability in agricultural regions without complex flow models.

  6. Simultaneous synthesis of gold nanoparticle/graphene nanocomposite for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Govindhan, Maduraiveeran; Chen, Aicheng

    2015-01-01

    We report here on a novel and facile technique for the simultaneous synthesis of a highly active and stable gold (Au) nanoparticle/reduced graphene oxide (rGO) sheet nanocomposite as an efficient electrocatalyst to facilitate the oxygen reduction reaction (ORR). X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy and electrochemical methods were employed to characterize the Au and rGO nanocomposites formed on the electrode surface. The major advantage of the simultaneous synthetic method is the integration of the superb properties of both Au nanoparticles and graphene in a single-step with a 100% usage of the precursors. The Au/rGO nanocomposites exhibited pronounced electrocatalytic performance towards ORR with approximately three times higher than that of Au nanoparticles. The nanocomposites show the ORR onset peak potentials at 0.12 and -0.03 V (vs Ag/AgCl), with reduction peaks at -0.06 and -0.16 V (vs Ag/AgCl) in 0.1 M H2SO4 and KOH media, which is ∼120-190 mV more positive than that of Au nanoparticles and a commercial Pt/C catalyst. Moreover, the nanocomposites exhibit excellent methanol tolerance and high durability in comparison with the commercial Pt/C. The new method demonstrated in this study provides an efficient route for the generation of ultrafine and highly dense Au nanoparticles that are homogeneously dispersed on rGO sheets for ORR.

  7. Extending cassava root shelf life via reduction of reactive oxygen species production.

    PubMed

    Zidenga, Tawanda; Leyva-Guerrero, Elisa; Moon, Hangsik; Siritunga, Dimuth; Sayre, Richard

    2012-08-01

    One of the major constraints facing the large-scale production of cassava (Manihot esculenta) roots is the rapid postharvest physiological deterioration (PPD) that occurs within 72 h following harvest. One of the earliest recognized biochemical events during the initiation of PPD is a rapid burst of reactive oxygen species (ROS) accumulation. We have investigated the source of this oxidative burst to identify possible strategies to limit its extent and to extend cassava root shelf life. We provide evidence for a causal link between cyanogenesis and the onset of the oxidative burst that triggers PPD. By measuring ROS accumulation in transgenic low-cyanogen plants with and without cyanide complementation, we show that PPD is cyanide dependent, presumably resulting from a cyanide-dependent inhibition of respiration. To reduce cyanide-dependent ROS production in cassava root mitochondria, we generated transgenic plants expressing a codon-optimized Arabidopsis (Arabidopsis thaliana) mitochondrial alternative oxidase gene (AOX1A). Unlike cytochrome c oxidase, AOX is cyanide insensitive. Transgenic plants overexpressing AOX exhibited over a 10-fold reduction in ROS accumulation compared with wild-type plants. The reduction in ROS accumulation was associated with a delayed onset of PPD by 14 to 21 d after harvest of greenhouse-grown plants. The delay in PPD in transgenic plants was also observed under field conditions, but with a root biomass yield loss in the highest AOX-expressing lines. These data reveal a mechanism for PPD in cassava based on cyanide-induced oxidative stress as well as PPD control strategies involving inhibition of ROS production or its sequestration. PMID:22711743

  8. Core-shell Au@Pd nanoparticles with enhanced catalytic activity for oxygen reduction reaction via core-shell Au@Ag/Pd constructions

    PubMed Central

    Chen, Dong; Li, Chengyin; Liu, Hui; Ye, Feng; Yang, Jun

    2015-01-01

    Core-shell nanoparticles often exhibit improved catalytic properties due to the lattice strain created in these core-shell particles. Herein, we demonstrate the synthesis of core-shell Au@Pd nanoparticles from their core-shell Au@Ag/Pd parents. This strategy begins with the preparation of core-shell Au@Ag nanoparticles in an organic solvent. Then, the pure Ag shells are converted into the shells made of Ag/Pd alloy by galvanic replacement reaction between the Ag shells and Pd2+ precursors. Subsequently, the Ag component is removed from the alloy shell using saturated NaCl solution to form core-shell Au@Pd nanoparticles with an Au core and a Pd shell. In comparison with the core-shell Au@Pd nanoparticles upon directly depositing Pd shell on the Au seeds and commercial Pd/C catalysts, the core-shell Au@Pd nanoparticles via their core-shell Au@Ag/Pd templates display superior activity and durability in catalyzing oxygen reduction reaction, mainly due to the larger lattice tensile effect in Pd shell induced by the Au core and Ag removal. PMID:26144550

  9. Simultaneous formation of nitrogen and sulfur-doped transition metal catalysts for oxygen reduction reaction through pyrolyzing carbon-supported copper phthalocyanine tetrasulfonic acid tetrasodium salt

    NASA Astrophysics Data System (ADS)

    Qing, Xin; Shi, Jingjing; Ma, Chengyu; Fan, Mengyang; Bai, Zhengyu; Chen, Zhongwei; Qiao, Jinli; Zhang, Jiujun

    2014-11-01

    In this work, we report a spontaneous formation of copper (Cu-N-S/C) catalysts containing both nitrogen (N) and sulfur (S) elements using a one-step pyrolysis of carbon supported copper phthalocyanine tetrasulfonic acid tetrasodium salt (CuTSPc/C). The obtained catalysts exhibit high catalytic activities for oxygen reduction reaction (ORR) in alkaline media. Through electrochemical measurements and physical characterizations, several observations are reached as follows: (1) different pyrolysis temperatures can result in different catalyst structures and performances, and the optimum pyrolysis temperature is found to be 700 °C; (2) the electron transfer number of the ORR process catalyzed by the unpyrolyzed catalyst is about 2.5, after the pyrolysis, this number is increased to 3.5, indicating that the pyrolysis process can change the ORR pathway from a 2-electron transfer dominated process to a 4-electron transfer dominated one; (3) increasing catalyst loading from 40 μg cm-2 to 505 μg cm-2 can effectively improve the catalytic ORR activity, under which the percentage of H2O2 produced decreases sharply from 39.5% to 7.8%; and (4) the Cu ion can bond on pyridinic-N, graphite-N and C-Sn-C to form Cu-N-S/C catalyst active sites, which play the key role in the ORR activity.

  10. Experimental identification of the active sites in pyrolyzed carbon-supported cobalt-polypyrrole-4-toluenesulfinic acid as electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sha, Hao-Dong; Yuan, Xianxia; Li, Lin; Ma, Zhong; Ma, Zi-Feng; Zhang, Lei; Zhang, Jiujun

    2014-06-01

    A series of carbon supported cobalt-polypyrrole-4-toluenesulfinic acid have been pyrolyzed in an argon atmosphere at 800 °C, then structurally characterized and electrochemically evaluated as oxygen reduction reaction (ORR) catalysts in aqueous 0.5 M sulfuric acid. The structures are cobalt bonded to nitrogen species (Co-Nx) along with metallic cobalt and cobalt oxide. When the cobalt loading in the compound is less than 1.0 wt%, the predominate form is Co-Nx, when the loading is higher than 1.0 wt%, metallic Co and Co oxide particles co-exist with the Co-Nx compound. At a Co loading of ∼1.0 wt%, the catalyst gives the best ORR activity. Both metallic Co and Co oxide are not active for catalyzing ORR, and block the catalytically active Co-Nx species from the surface and reduce the catalytic activity since the diffusion limiting current density on a rotating disk electrode (RDE) increases when the electrode blocking agents are washed away with acid.

  11. Increased stability toward oxygen reduction products for lithium-air batteries with oligoether-functionalized silane electrolytes.

    SciTech Connect

    Zhang, Z.; Lu, J.; Assary, R. S.; Du, P.; Wang, H-H.; Sun, Y-K.; Qin, Y.; Lau, K. C.; Greeley, J.; Redfern, P. C.; Iddir, H.; Curtiss, L. A.; Amine, K.

    2011-01-01

    The successful development of Li-air batteries would significantly increase the possibility of extending the range of electric vehicles. There is much evidence that typical organic carbonate based electrolytes used in lithium ion batteries form lithium carbonates from reaction with oxygen reduction products during discharge in lithium-air cells so more stable electrolytes need to be found. This combined experimental and computational study of an electrolyte based on a tri(ethylene glycol)-substituted trimethylsilane (1NM3) provides evidence that the ethers are more stable toward oxygen reduction discharge species. X-ray photoelectron spectroscopy (XPS) and FTIR experiments show that only lithium oxides and no carbonates are formed when 1NM3 electrolyte is used. In contrast XPS shows that propylene carbonate (PC) in the same cell configuration decomposes to form lithium carbonates during discharge. Density functional calculations of probable decomposition reaction pathways involving solvated oxygen reduction species confirm that oligoether substituted silanes, as well as other ethers, are more stable to the oxygen reduction products than propylene carbonate. These results indicate that the choice of electrolyte plays a key role in the performance of Li-air batteries.

  12. Synthesis, characterization and electrochemical studies of nanostructured CaWO{sub 4} as platinum support for oxygen reduction reaction

    SciTech Connect

    Farsi, Hossein; Barzgari, Zahra

    2014-11-15

    Highlights: • Nanostructured CaWO{sub 4} was fabricated by co-precipitation method. • Platinum was electrodeposited onto the surface prepared nanostructured CaWO{sub 4}. • Pt/CaWO{sub 4}-graphite demonstrate good oxygen reduction reaction activity. - Abstract: In the present work, we employed nanostructured calcium tungstate as a supporting material for platinum, a well-known electrocatalyst for oxygen reduction. The co-precipitation method has been utilized to synthesize nanostructured calcium tungstate from aqueous solution. The structure and morphology of the obtained CaWO{sub 4} were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Preparation of the Pt/CaWO{sub 4}-graphite catalyst was carried out by electrodeposition of Pt onto the surface of CaWO{sub 4}/graphite electrode. The physical properties of the catalyst were determined by scanning electron microscopy analysis and energy dispersive X-ray (SEM/EDX). The electrochemical activity of the Pt/CaWO{sub 4}-graphite for the oxygen reduction reaction (ORR) was investigated in acid solution by cyclic voltammetry measurements, linear sweep voltammetry, and electrochemical impedance spectroscopy. The results revealed that the Pt/CaWO{sub 4}-graphite has higher electrocatalytic activity for oxygen reduction in comparison with Pt/graphite catalyst.

  13. Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes

    SciTech Connect

    Zhang, Zhengcheng; Lu, Jun; Assary, Rajeev S.; Du, Peng; Wang, Hsien-Hau; Sun, Yang-Kook; Qin, Yan; Lau, Kah Chun; Greeley, Jeffrey P.; Redfern, Paul C.; Iddir, Hakim; Curtiss, Larry A.; Amine, Khalil

    2011-12-29

    The successful development of Li-air batteries would significantly increase the possibility of extending the range of electric vehicles. There is much evidence that typical organic carbonate based electrolytes used in lithium ion batteries form lithium carbonates from reaction with oxygen reduction products during discharge in lithium-air cells so more stable electrolytes need to be found. This combined experimental and computational study of an electrolyte based on a tri(ethylene glycol)-substituted trimethylsilane (1NM3) provides evidence that the ethers are more stable toward oxygen reduction discharge species. X-ray photoelectron spectroscopy (XPS) and FTIR experiments show that only lithium oxides and no carbonates are formed when 1NM3 electrolyte is used. In contrast XPS shows that propylene carbonate (PC) in the same cell configuration decomposes to form lithium carbonates during discharge. Density functional calculations of probable decomposition reaction pathways involving solvated oxygen reduction species confirm that oligoether substituted silanes, as well as other ethers, are more stable to the oxygen reduction products than propylene carbonate. These results indicate that the choice of electrolyte plays a key role in the performance of Li-air batteries.

  14. Aminothiazole-derived N,S,Fe-doped graphene nanosheets as high performance electrocatalysts for oxygen reduction.

    PubMed

    Chen, Chi; Yang, Xiao-Dong; Zhou, Zhi-You; Lai, Yu-Jiao; Rauf, Muhammad; Wang, Ying; Pan, Jing; Zhuang, Lin; Wang, Qiang; Wang, Yu-Cheng; Tian, Na; Zhang, Xin-Sheng; Sun, Shi-Gang

    2015-12-14

    N,S,Fe-doped graphene nanosheets were directly synthesized from aminothiazole, a precursor molecule that contains N and S atoms, through Fe catalysis under heat treatment. The graphene nanosheets exhibited high electrocatalytic activity toward oxygen reduction reaction in both acidic and alkaline media during rotating disk electrode half-cell and fuel cell tests. PMID:26451800

  15. A Facile Route to Bimetal and Nitrogen-Codoped 3D Porous Graphitic Carbon Networks for Efficient Oxygen Reduction.

    PubMed

    Zhang, Zhengping; Dou, Meiling; Liu, Haijing; Dai, Liming; Wang, Feng

    2016-08-01

    Bimetal nitrogen-doped carbon with both Fe and Co, derived from the pyrolysis carbon of iron and cobalt phthalocyanine-based conjugated polymer networks, possesses a few-layer graphene-like texture with hierarchical porosity in meso/micro multimodal pore size distribution. The novel electrocatalyst exhibits Pt-like catalytic activity and much higher catalytic durability for oxygen reduction. PMID:27389707

  16. Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

    2014-09-01

    Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. Electronic supplementary information (ESI) available: Detailed RDE and RRDE experiments, additional tables and figures. See DOI: 10.1039/c4nr03185g

  17. Aligned carbon nanotubes with built-in FeN{sub 4} active sites for electrocatalytic reduction of oxygen.

    SciTech Connect

    Yang, J.; Liu, D. J.; Chemical Engineering

    2008-01-01

    The electrocatalytic site FeN{sub 4}, which is active towards the oxygen reduction reaction, is incorporated into the graphene layer of aligned carbon nanotubes prepared through a chemical vapor deposition process, as is confirmed by X-ray absorption spectroscopy and other characterization techniques.

  18. Manageable N-doped graphene for high performance oxygen reduction reaction.

    PubMed

    Zhang, Yuewei; Ge, Jun; Wang, Lu; Wang, Donghong; Ding, Feng; Tao, Xiaoming; Chen, Wei

    2013-01-01

    Catalysts for oxygen reduction reaction (ORR) are at the heart of key green-energy fuel cell technology. N-doped graphene is a potential metal-free electrode with much better electrocatalytic activity, long-term stability, and tolerance to crossover effect than expensive platinum-based electrocatalysts. Here, we report a feasible direct-synthesis method in preparing N-graphene with manageable N contents in a large scale. The resultant N-graphene used as electrocatalysts exhibits similar catalytic activity but superior stability compared to commercial Pt/C for ORR in an alkaline solution. It was found that their electrocatalytic activities were demonstrated to depend largely on N-doping content. When nitrogen content reaches a high value at about 24-25%, ORR reaction exhibits a favorable formation of water via a four-electron pathway. Furthermore, the effect of pyrolysis temperature and precursor on the activity of N-graphene is systematically analyzed, and may shed some light on the principle of choosing appropriate way for preparing N-graphene. PMID:24067782

  19. Progress in the Development of Oxygen Reduction Reaction Catalysts for Low-Temperature Fuel Cells.

    PubMed

    Li, Dongguo; Lv, Haifeng; Kang, Yijin; Markovic, Nenad M; Stamenkovic, Vojislav R

    2016-06-01

    We present a brief summary on the most recent progress in the design of catalysts for electrochemical reduction of oxygen. The main challenge in the wide spread of fuel cell technology is to lower the content of, or even eliminate, Pt and other precious metals in catalysts without sacrificing their performance. Pt-based nanosized catalysts with novel and refined architectures continue to dominate in catalytic performance, and formation of Pt-skin-like surfaces is key to achieving the highest values in activity. Moreover, durability has also been improved in Pt-based systems with addition of Au, which plays an important role in stabilizing the Pt topmost layers against dissolution. However, various carbon-based materials without precious metal have shown improvement in activity and durability and have been explored to serve as catalyst supports. Understanding how the doped elements interact with each other and/or carbon is challenging and necessary in the design of robust fuel cell catalysts. PMID:27070766

  20. Nitrogen-doped carbon nanotubes as catalysts for the oxygen reduction reaction in alkaline medium

    NASA Astrophysics Data System (ADS)

    Yang, Mei; Yang, Duangguang; Chen, Hongbiao; Gao, Yong; Li, Huaming

    2015-04-01

    A novel electrocatalyst for the oxygen reduction reaction (ORR) is fabricated by directly annealing oxidized carbon nanotubes and tripyrrolyl[1,3,5]triazine in nitrogen. The structural and chemical properties of the resultant N-doped carbon nanotubes (NCNTs) are systematically investigated. The electrocatalytic activity of the NCNTs towards ORR in O2-saturated 0.1 M KOH electrolyte is evaluated using rotating disk electrode voltammetry. The results demonstrate that the as-prepared NCNT-900 (annealed at 900 °C) exhibits excellent electrochemical performance towards ORR in alkaline medium with an onset potential of -0.038 V (vs Ag/AgCl), a high kinetic current density of 31.26 mA cm-2 at -0.25 V, a dominant four-electron transfer mechanism (n = 3.88 at -0.25 V), and excellent methanol tolerance and durability. The results obtained are significant for the development of N-doped carbon-based electrocatalysts for alkaline fuel cells.