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Sample records for oxygen reduction catalyzed

  1. 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

  2. Oxygen reduction catalyzed by a fluorinated tetraphenylporphyrin free base at liquid/liquid interfaces.

    PubMed

    Hatay, Imren; Su, Bin; Méndez, Manuel A; Corminboeuf, Clémence; Khoury, Tony; Gros, Claude P; Bourdillon, Mélanie; Meyer, Michel; Barbe, Jean-Michel; Ersoz, Mustafa; Zális, Stanislav; Samec, Zdenek; Girault, Hubert H

    2010-10-06

    The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB(-)) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.

  3. Proton-coupled oxygen reduction at liquid-liquid interfaces catalyzed by cobalt porphine.

    PubMed

    Hatay, Imren; Su, Bin; Li, Fei; Méndez, Manuel Alejandro; Khoury, Tony; Gros, Claude P; Barbe, Jean-Michel; Ersoz, Mustafa; Samec, Zdenek; Girault, Hubert H

    2009-09-23

    Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O(2) reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O(2). The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O(2).

  4. Single-Molecule Imaging of Iron-Phthalocyanine-Catalyzed Oxygen Reduction Reaction by in Situ Scanning Tunneling Microscopy.

    PubMed

    Gu, Jing-Ying; Cai, Zhen-Feng; Wang, Dong; Wan, Li-Jun

    2016-09-27

    We report herein an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of iron-phthalocyanine (FePc)-catalyzed oxygen reduction reaction (ORR). A highly ordered FePc adlayer is revealed on a Au(111) electrode. The center ions in the FePc adlayer show uniform high contrast in an oxygen-saturated electrolyte, which is attributed to the formation of an FePc-O2 complex. In situ STM results reveal the sharp contrast change upon shifting the electrode potential to trigger the ORR. Theoretical simulation has supplied further evidence for the contrast difference of the adsorbed FePc species.

  5. 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.

  6. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems.

    PubMed

    Zhang, Wei; Lai, Wenzhen; Cao, Rui

    2017-02-22

    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  7. Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

    PubMed

    Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

    2012-07-25

    A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

  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. Mononuclear copper complex-catalyzed four-electron reduction of oxygen.

    PubMed

    Fukuzumi, Shunichi; Kotani, Hiroaki; Lucas, Heather R; Doi, Kaoru; Suenobu, Tomoyoshi; Peterson, Ryan L; Karlin, Kenneth D

    2010-05-26

    A mononuclear Cu(II) complex acts as an efficient catalyst for four-electron reduction of O(2) to H(2)O. Its reduction by a ferrocene derivative (Fc*) and reaction with O(2) leads to the formation of a peroxodicopper(II) complex; this is subsequently reduced by Fc* in the presence of protons to regenerate the Cu(II) complex.

  10. Oxygen reduction reaction catalyzed by cobalt(III) complexes of macrocyclic ligands supported on multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nasini, Udaya B.; Gartia, Yashraj; Ramidi, Punnamchandar; Kazi, Abul; Shaikh, Ali U.; Ghosh, Anindya

    2013-04-01

    A class of amido-macrocyclic cobalt(III) complexes along with multiwalled carbon nanotubes have been studied for electro-catalytic activity to reduce oxygen. These complexes are efficient for oxygen reduction reaction (ORR) in wide range of pH conditions by following ideal fuel cell reduction mechanism. Depending on the stability of complexes in different pH, electrochemical studies were performed to predict the reduction mechanism. Rotating disk electrode and rotating ring-disk electrode studies show that these complexes reduce oxygen via four electron reduction process in mild acidic pH and two step two electron reduction processes in basic conditions, with negligible amount of hydrogen peroxide generation.

  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. Mechanisms of bacterially catalyzed reductive dehalogenation

    SciTech Connect

    Picardal, Flynn William

    1992-01-01

    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 14C-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.

  13. Oxygen reduction reaction catalyzed by nickel complexes based on thiophosphorylated calix[4]resorcinols and immobilized in the membrane electrode assembly of fuel cells.

    PubMed

    Kadirov, M K; Knyazeva, I R; Nizameev, I R; Safiullin, R A; Matveeva, V I; Kholin, K V; Khrizanforova, V V; Ismaev, T I; Burilov, A R; Budnikova, Yu H; Sinyashin, O G

    2016-10-18

    The catalytic activity of the nickel complexes of thiophosphorylated calix[4]resorcinols for oxygen reduction in a polymer electrolyte membrane fuel cell (PEMFC) has been studied. The conformation of the macrocyclic ligand determines the morphology and catalytic properties of the resulting organometallic species.

  14. 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)

  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

    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

  17. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    SciTech Connect

    Zhao, Y.; Xu, Q.; Cheah, S.

    2013-01-01

    Based on Density Functional Theory (DFT) simulations, we have studied the reduction of nickel oxide and biomass derived oxygenates (catechol, guaiacol, etc.) in hydrogen. Both the kinetic barrier and thermodynamic favorability are calculated with respect to the modeled reaction pathways. In early-stage reduction of the NiO(100) surface by hydrogen, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms coordinately dissociate the hydrogen molecules so that a water molecule can be formed, leaving an oxygen vacancy on the surface. In hydrogen reaction with oxygenates catalyzed by transition metals, hydrogenation of the aromatic carbon ring normally dominates. However, selective deoxygenation is of particular interest for practical application such as biofuel conversion. Our modeling shows that doping of the transition metal catalysts can change the orientation of oxygenates adsorbed on metal surfaces. The correlation between the selectivity of reaction and the orientation of adsorption are discussed.

  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.

  19. 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.

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

    DOE PAGES

    Zhang, Sen; Hao, Yizhou; Su, Dong; ...

    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. 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.

  2. Vanadium-catalyzed chlorination under molecular oxygen.

    PubMed

    Moriuchi, Toshiyuki; Fukui, Yasuhiro; Kato, Satoshi; Kajikawa, Tomomi; Hirao, Toshikazu

    2015-06-01

    A catalytic chlorination of ketones was performed by using a vanadium catalyst in the presence of Bu4NI and AlCl3 under atmospheric molecular oxygen. This catalytic chlorination could be applied to the chlorination of alkenes to give the corresponding vic-dichlorides. AlCl3 was found to serve as both a Lewis acid and a chloride source to induce the facile chlorination. A combination of Bu4NI and AlI3 in the presence of a vanadium catalyst under atmospheric molecular oxygen induced the iodination of ketones.

  3. 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.

  4. 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.

  5. 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.

  6. Copper-catalyzed asymmetric reduction of 3,3-diarylacrylonitriles.

    PubMed

    Lee, Daehyung; Yang, Youngmin; Yun, Jaesook

    2007-07-05

    CuH-catalyzed enantioselective conjugate reduction of 3,3-diaryl-substituted acrylonitriles is described. A range of 3-aryl-3-pyridylacrylonitriles were reduced with high levels of enantioselectivity under optimal conditions employing a copper/Josiphos complex in the presence of polymethylhydrosiloxane (PMHS).

  7. Computational studies of face-to-face porphyrin catalyzed reduction of dioxygen.

    SciTech Connect

    Ingersoll, David T.; Muller, Richard Partain, Dr.

    2004-08-01

    We are investigating the use of face-to-face porphyrin (FTF) materials as potential oxygen reduction catalysts in fuel cells. The FTF materials were popularized by Anson and Collman, and have the interesting property that varying the spacing between the porphyrin rings changes the chemistry they catalyze from a two-electron reduction of oxygen to a four-electron reduction of oxygen. Our goal is to understand how changes in the structure of the FTF materials lead to either two-electron or four-electron reductions. This understand of the FTF catalysis is important because of the potential use of these materials as fuel cell electrocatalysts. Furthermore, the laccase family of enzymes, which has been proposed as an electrocatalytic enzyme in biofuel cell applications, also has family members that display either two-electron or four electron reduction of oxygen, and we believe that an understanding of the structure-function relationships in the FTF materials may lead to an understanding of the behavior of laccase and other enzymes. We will report the results of B3LYP density functional theory studies with implicit solvent models of the reduction of oxygen in several members of the cobalt FTF family.

  8. Aldose Reductase-catalyzed Reduction of Aldehyde Phospholipids

    PubMed Central

    Srivastava, Sanjay; Spite, Matthew; Trent, John O.; West, Matthew B.; Ahmed, Yonis; Bhatnagar, Aruni

    2012-01-01

    SUMMARY Oxidation of unsaturated phospholipids results in the generation of aldehyde side chains that remain esterified to the phospholipid backbone. Such “core” aldehydes elicit immune responses and promote inflammation. However, the biochemical mechanisms by which phospholipid aldehydes are metabolized or detoxified are not well understood. In the studies reported here, we examined whether aldose reductase (AR), which reduces hydrophobic aldehydes, metabolizes phospholipid aldehydes. Incubation with AR led to the reduction of 5-oxovaleroyl, 7-oxo-5-heptenoyl, 5-hydroxy-6-oxo-caproyl, and 5-hydroxy-8-oxo-6-octenoyl phospholipids generated upon oxidation of 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine (PAPC). The enzyme also catalyzed the reduction of phospholipid aldehydes generated from the oxidation of 1-alkyl, and 1-alkenyl analogs of PAPC, and 1-palmitoyl-2-arachidonoyl phosphatidic acid or phosphoglycerol. Aldose reductase catalyzed the reduction of chemically synthesized 1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphatidylcholine (POVPC) with a Km of 10 μM. Addition of POVPC to the culture medium led to incorporation and reduction of the aldehyde in COS-7 and THP-1 cells. Reduction of POVPC in these cells was prevented by the AR inhibitors sorbinil and tolrestat and was increased in COS-7 cells overexpressing AR. Together, these observations suggest that AR may be a significant participant in the metabolism of several structurally diverse phospholipid aldehydes. This metabolism may be a critical regulator of the pro-inflammatory and immunogenic effects of oxidized phospholipids. PMID:15465833

  9. 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.

  10. Iridium-catalyzed reductive nitro-Mannich cyclization.

    PubMed

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

    2015-01-02

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.

    PubMed

    Peljo, Pekka; Murtomäki, Lasse; Kallio, Tanja; Xu, Hai-Jun; Meyer, Michel; Gros, Claude P; Barbe, Jean-Michel; Girault, Hubert H; Laasonen, Kari; Kontturi, Kyösti

    2012-04-04

    Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene-water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyrin, 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene, Co(2)(DPX), actually catalyzes oxygen reduction to hydrogen peroxide when oxygen is bound on the "exo" side ("dock-on") of the catalyst, while four-electron reduction takes place with oxygen bound on the "endo" side ("dock-in") of the molecule. These results can be explained by a "dock-on/dock-in" mechanism. The next step for improving bioinspired oxygen reduction catalysts would be blocking the "dock-on" path to achieve selective four-electron reduction of molecular oxygen.

  12. Human carbonyl reductase catalyzes reduction of 4-oxonon-2-enal.

    PubMed

    Doorn, Jonathan A; Maser, Edmund; Blum, Andreas; Claffey, David J; Petersen, Dennis R

    2004-10-19

    4-Oxonon-2-enal (4ONE) was demonstrated to be a product of lipid peroxidation, and previous studies found that it was highly reactive toward DNA and protein. The present study sought to determine whether carbonyl reductase (CR) catalyzes reduction of 4ONE, representing a potential pathway for metabolism of the lipid peroxidation product. Recombinant CR was cloned from a human liver cDNA library, expressed in Escherichia coli, and purified by metal chelate chromatography. Both 4ONE and its glutathione conjugate were found to be substrates for CR, and kinetic parameters were calculated. TLC analysis of reaction products revealed the presence of three compounds, two of which were identified as 4-hydroxynon-2-enal (4HNE) and 1-hydroxynon-2-en-4-one (1HNO). GC/MS analysis confirmed 4HNE and 1HNO and identified the unknown reaction product as 4-oxononanal (4ONA). Analysis of oxime derivatives of the reaction products via LC/MS confirmed the unknown as 4ONA. The time course for CR-mediated, NADPH-dependent 4ONE reduction and appearance of 4HNE and 1HNO was determined using HPLC, demonstrating 4HNE to be a major product and 1HNO and 4ONA to be minor products. Simulated structures of 4ONE in the active site of CR/NADPH calculated via docking experiments predict the ketone positioned as primary hydride acceptor. Results of the present study demonstrate that 4ONE is a substrate for CR/NADPH and the enzyme may represent a pathway for biotransformation of the lipid. Furthermore, these findings reveal that CR catalyzes hydride transfer selectively to the ketone but also to the aldehyde and C=C of 4ONE, resulting in 4HNE, 1HNO, and 4ONA, respectively.

  13. 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.

  14. Oxygen reduction reaction: A framework for success

    SciTech Connect

    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.

  15. Oxygen reduction reaction: A framework for success

    SciTech Connect

    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.

  16. A highly efficient buckypaper-based electrode material for mediatorless laccase-catalyzed dioxygen reduction.

    PubMed

    Hussein, L; Rubenwolf, S; von Stetten, F; Urban, G; Zengerle, R; Krueger, M; Kerzenmacher, S

    2011-06-15

    The redox enzyme laccase from Trametes versicolor efficiently catalyzes the oxygen reduction reaction (ORR) in mediatorless biofuel cell cathodes when adsorbed onto multi-walled carbon nanotubes (MWCNTs). In this work we demonstrate that the fabrication of MWCNTs in form of buckypaper (BP) results in an excellent electrode material for laccase-catalyzed cathodes. BPs are mechanically stable, self-entangling mats with high dispersion of MWCNTs resulting in easy to handle homogeneous layers with highly mesoporous structures and excellent electrical conductivities. All biocathodes have been electrochemically investigated in oxygen-saturated buffer at pH 5 by galvanostatic polarization and potentiodynamic linear sweep voltammetry. Both methods confirm an efficient direct interaction of laccase with BP with a high open circuit potential of 0.882 V vs. normal hydrogen electrode (NHE). The high oxygen reduction performance leads to high current densities of 422±71 μA cm(-2) at a typical cathode potential of 0.744 V vs. NHE. When the current density is normalized to the mass of the electrode material (mass activity), the BP-based film electrodes exhibit a 68-fold higher current density at 0.744 V vs. NHE than electrodes fabricated from the same MWCNTs in a non-dispersed agglomerated form as packed electrodes. This clearly shows that MWCNTs can act more efficiently as cathode when prepared in form of BP. This can be attributed to reduced diffusional mass transfer limitations and enhanced electrical conductivity. BP is thus a very promising material for the construction of mediatorless laccase cathodes for ORR in biofuel cells. In addition we demonstrated that these electrodes exhibit a high tolerance towards glucose, the most common bioanode fuel. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. 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

  18. Tandem oxidation/rearrangement of beta-ketoesters to tartronic esters with molecular oxygen catalyzed by calcium iodide under visible light irradiation with fluorescent lamp.

    PubMed

    Kanai, Naohiko; Nakayama, Hiroki; Tada, Norihiro; Itoh, Akichika

    2010-05-07

    It was found that beta-ketoesters were directly transformed to the corresponding alpha-hydroxymalonic esters, tartronic esters, with molecular oxygen catalyzed by calcium iodide under visible light irradiation from fluorescent lamp. This reaction includes tandem oxidation/rearrangement and has received much attention from the viewpoint of reduction of energy consumption, labor, and solvents.

  19. Metal fiber - carbon electrodes for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Smith, Robert Fendlay

    An investigation was carried out to determine activities for oxygen reduction and current efficiencies to hydrogen peroxide of commercially available nickel fibers, carbon fibers, and carbon powders. The activities and current efficiencies were determined by conducting Rotating Ring Disk Electrode Experiments (RRDE) on porous electrodes that utilize an interlocking network of metal fibers with carbon fibers and/or powders. Experimentation was also done using PTFE - carbon powder and PTFE - nickel fiber paste electrodes to remove any porosity and symbiotic effects of the nickel - carbon electrodes. Results of the traditional flat plate PTFE electrodes were compared to the porous electrodes to verify the proposed mathematical viability of porous electrode RRDE. RRDE experiments showed that the most active carbons for oxygen reduction have a surface area to volume ratio of 1000 m2/g, and current rent efficiency to hydrogen peroxide was increased as the average pore size increased. A mathematical model and half-cell polarization experiments were used to characterize and optimize oxygen reduction in gas diffusion electrodes consisting of carbon fibers and/or powders entrapped in a sinter-locked network of nickel microfibers. Important electrode physical parameters, such as nickel fiber loading (0.005 to 0.01 g/cm2) , nickel fiber diameter (2 to 12 mum), void volume (73 to 96%), distance of the active layer from the gas supply (0 to 0.005 cm), and addition of a peroxide decomposition catalyst (0 to 0.004 g/cm2) were systematically varied to determine their effects on electrode performance. Experimentally determined total currents and current efficiencies to hydrogen peroxide were compared to calculated values for model verification. Other important parameters, including intra-electrode oxygen and hydrogen peroxide concentrations, overpotentials, and reaction rates, were simulated to help optimize the electrode. Fabricated metal fiber-carbon electrodes were compared to a

  20. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. Analysis of oxygen reduction and microbial community of air-diffusion biocathode in microbial fuel cells.

    PubMed

    Wang, Zejie; Zheng, Yue; Xiao, Yong; Wu, Song; Wu, Yicheng; Yang, Zhaohui; Zhao, Feng

    2013-09-01

    Microbes play irreplaceable role in oxygen reduction reaction of biocathode in microbial fuel cells (MFCs). In this study, air-diffusion biocathode MFCs were set up for accelerating oxygen reduction and microbial community analysis. Linear sweep voltammetry and Tafel curve confirmed the function of cathode biofilm to catalyze oxygen reduction. Microbial community analysis revealed higher diversity and richness of community in plankton than in biofilm. Proteobacteria was the shared predominant phylum in both biofilm and plankton (39.9% and 49.8%) followed by Planctomycetes (29.9%) and Bacteroidetes (13.3%) in biofilm, while Bacteroidetes (28.2%) in plankton. Minor fraction (534, 16.4%) of the total operational taxonomic units (3252) was overlapped demonstrating the disproportionation of bacterial distribution in biofilm and plankton. Pseudomonadales, Rhizobiales and Sphingobacteriales were exoelectrogenic orders in the present study. The research obtained deep insight of microbial community and provided more comprehensive information on uncultured rare bacteria.

  3. Iodide-catalyzed reductions: development of a synthesis of phenylacetic acids.

    PubMed

    Milne, Jacqueline E; Storz, Thomas; Colyer, John T; Thiel, Oliver R; Dilmeghani Seran, Mina; Larsen, Robert D; Murry, Jerry A

    2011-11-18

    A new convenient and scalable synthesis of phenylacetic acids has been developed via the iodide catalyzed reduction of mandelic acids. The procedure relies on in situ generation of hydroiodic acid from catalytic sodium iodide, employing phosphorus acid as the stoichiometric reductant.

  4. 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.

  5. Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions.

    PubMed

    Oderinde, Martins S; Varela-Alvarez, Adrian; Aquila, Brian; Robbins, Daniel W; Johannes, Jeffrey W

    2015-08-07

    In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

  6. 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).

  7. 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.

  8. Enantioselective imine reduction catalyzed by imine reductases and artificial metalloenzymes.

    PubMed

    Gamenara, Daniela; Domínguez de María, Pablo

    2014-05-21

    Adding value to organic synthesis. Novel imine reductases enable the enantioselective reduction of imines to afford optically active amines. Likewise, novel bioinspired artificial metalloenzymes can perform the same reaction as well. Emerging proof-of-concepts are herein discussed.

  9. Selective molecular oxygen oxidation of thioethers to sulfoxides catalyzed by Ce(IV)

    SciTech Connect

    Riley, D.P.; Smith, M.R.; Correa, P.E.

    1988-01-06

    The selective molecular oxygen conversion of thioethers to sulfoxides is catalyzed by ceric ammonium nitrate (CAN) with rate enhancements that are at least three orders of magnitude greater than the uncatalyzed autoxidation of thioethers. Mechanistic studies (including spectroscopic, labeling, uptake, mixed reactant, and autocatalysis studies) of this novel reaction reveal that both atoms of dioxygen are incorporated into product sulfoxide, that a novel oxygen-driven Ce(IV)Ce(III) redox cycle gives rise to the catalysis, and that molecular oxygen efficiently traps a sulfur-centered radial cation of the thioether (produced by Ce(IV) oxidation of thioether) to yield the oxygenated radical cation R/sub 2/S/sup +/OO/sup ./, which, it is proposed, reoxidizes Ce(III) to Ce(IV). The zwitterionic R/sub 2/S/sup +/OO/sup -/ intermediate (persulfoxide) reacts with thioether to yield two sulfoxide product molecules.

  10. 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…

  11. 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…

  12. Reductive dechlorination of tetrachloroethylene (PCE) catalyzed by cyanocobalamin

    SciTech Connect

    Habeck, B.D.; Sublette, K.L.

    1995-12-31

    A biomimetic system has been developed for the reductive dechlorination of tetrachloroethylene (PCE). PCE was dechlorinated to trichloroethylene (TCE) and 1,2-dichloroethylene (DCE) in the presence of dithiothreitol or Ti (III) citrate and catalytic amounts of cyanocobalamin in both homogeneous reaction mixtures and packed bed reactor systems. In packed bed reactors with Ti (III) citrate as the reductant, PCE (0.18 mM) conversion averaged 55% at residence times of 1.75 and 3.5 h. The product distribution was 94% TCE and 6% DCE at the lower residence time. DCE formation increased to 45% at the higher residence time. No reduction of PCE was observed in the absence of cyanocobalamin. This system may be useful as a means of pretreatment of halogenated aliphatic hydrocarbons in advance of biological treatment.

  13. 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.

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

    PubMed

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

    2012-11-27

    A doubly substituted form of the nitrogenase MoFe protein (α-70(Val)(→Ala), α-195(His→Gln)) has the capacity to catalyze the reduction of carbon dioxide (CO(2)) to yield methane (CH(4)). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH(4) within 20 min. The catalytic rate depends on the partial pressure of CO(2) (or concentration of HCO(3)(-)) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H(2)C = CH-CH(3)) through the reductive coupling of CO(2) 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 CO(2) sequestration and formation of olefins.

  15. 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.

  16. Copper-catalyzed extended Pummerer reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides with an accompanying oxygen rearrangement.

    PubMed

    Murakami, Kei; Imoto, Junichi; Matsubara, Hiroshi; Yoshida, Suguru; Yorimitsu, Hideki; Oshima, Koichiro

    2013-04-26

    The first examples of metal-catalyzed extended Pummerer reactions through the activation of sulfoxides are described. The copper-catalyzed reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ-disulfanyl-β,γ-unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4-dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism.

  17. Singlet oxygen in copper-catalyzed lipid peroxidation in erythrocyte membranes

    SciTech Connect

    Ding, A.H.; Chan, P.C.

    1984-04-01

    Lipid hydroperoxide was generated in human erythrocyte membranes by irradiation with near ultraviolet (UV) light in the presence of a photosensitizer, hematoporphyrin, but no production of 2-thiobarbituric acid-reactive materials (malonaldehyde and its precursors) was detected. Incubation of the irradiated membranes with CuSO4 led to increased levels of hydroperoxide and formation of malonaldehyde. Hydroperoxides were essential for initiating the Cu(II)-catalyzed peroxidation as no significant activity was observed with nonirradiated membranes and Cu(II) unless an organic peroxide, either t-butyl hydroperoxide or cumene hydroperoxide, was added. Catalytic activity was also found with Fe(II), but not with other metal ions tested. The peroxidation catalyzed with Cu(II) was partially inhibited by several singlet oxygen quenchers but was not affected by superoxide dismutase, catalase or OH radical scavengers. The possible involvement of singlet oxygen in the Cu(II)-catalyzed peroxidation reaction was further supported by a 3-fold enhancement of malonaldehyde production in D/sub 2/O.

  18. Selective Coke Combustion by Oxygen Pulsing During Mo/ZSM‐5‐Catalyzed Methane Dehydroaromatization

    PubMed Central

    Coumans, Ferdy J. A. G.; Uslamin, Evgeny; Kapteijn, Freek

    2016-01-01

    Abstract Non‐oxidative methane dehydroaromatization is a promising reaction to directly convert natural gas into aromatic hydrocarbons and hydrogen. Commercialization of this technology is hampered by rapid catalyst deactivation because of coking. A novel approach is presented involving selective oxidation of coke during methane dehydroaromatization at 700 °C. Periodic pulsing of oxygen into the methane feed results in substantially higher cumulative product yield with synthesis gas; a H2/CO ratio close to two is the main side‐product of coke combustion. Using 13C isotope labeling of methane it is demonstrated that oxygen predominantly reacts with molybdenum carbide species. The resulting molybdenum oxides catalyze coke oxidation. Less than one‐fifth of the available oxygen reacts with gaseous methane. Combined with periodic regeneration at 550 °C, this strategy is a significant step forward, towards a process for converting methane into liquid hydrocarbons. PMID:27791321

  19. Sodium ascorbate kills Candida albicans in vitro via iron-catalyzed Fenton reaction: importance of oxygenation and metabolism.

    PubMed

    Avci, Pinar; Freire, Fernanda; Banvolgyi, Andras; Mylonakis, Eleftherios; Wikonkal, Norbert M; Hamblin, Michael R

    2016-12-01

    Ascorbate can inhibit growth and even decrease viability of various microbial species including Candida albicans. However the optimum conditions and the mechanism of action are unclear. Materials/methodology: Candida albicans shaken for 90 min in a buffered solution of ascorbate (90 mM) gave a 5-log reduction of cell viability, while there was no killing without shaking, in growth media with different carbon sources or at 4°C. Killing was inhibited by the iron chelator 2,2'-bipyridyl. Hydroxyphenyl fluorescein probe showed the intracellular generation of hydroxyl radicals. Ascorbate-mediated killing of C. albicans depends on oxygenation and metabolism, involves iron-catalyzed generation of hydroxyl radicals via Fenton reaction and depletion of intracellular NADH. Ascorbate could serve as a component of a topical antifungal therapy.

  20. 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.

  1. 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.

  2. 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.

  3. Trends in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium.

    PubMed

    Dathar, Gopi Krishna Phani; Shelton, William A; Xu, Ye

    2012-04-05

    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 O2 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.

  4. 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

    2016-02-07

    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.

  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.

  6. 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

  7. 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.

  8. Enantioselective Brønsted acid catalyzed transfer hydrogenation: organocatalytic reduction of imines.

    PubMed

    Rueping, Magnus; Sugiono, Erli; Azap, Cengiz; Theissmann, Thomas; Bolte, Michael

    2005-08-18

    The first enantioselective Brønsted acid catalyzed reduction of imines has been developed. This new organocatalytic transfer hydrogenation of ketimines with Hantzsch dihydropyridine as the hydrogen source offers a mild method to various chiral amines with high enantioselectivity. The stereochemistry of the chiral amines can be rationalized by a stereochemical model derived from an X-ray crystal structure of a chiral BINOL phosphate catalyst. [reaction: see text

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Ruthenium Catalyzed Reductive Coupling of Paraformaldehyde to Trifluoromethyl Allenes: CF3-Bearing All-Carbon Quaternary Centers

    PubMed Central

    Sam, Brannon; Montgomery, T. Patrick; Krische, Michael J.

    2013-01-01

    Trifluoromethyl substituted allenes engage in ruthenium catalyzed reductive couplings with paraformaldehyde to form products of hydrohydroxymethylation as single regioisomers. This method enables generation of CF3-bearing all-carbon quaternary stereocenters. PMID:23841678

  14. A Biomimetic Mechanism for the Copper-Catalyzed Aerobic Oxygenation of 4-tert-Butylphenol.

    PubMed

    Askari, Mohammad S; Esguerra, Kenneth Virgel N; Lumb, Jean-Philip; Ottenwaelder, Xavier

    2015-09-08

    Controlling product selectivity during the catalytic aerobic oxidation of phenols remains a significant challenge that hinders reaction development. This work provides a mechanistic picture of a Cu-catalyzed, aerobic functionalization of phenols that is selective for phenoxy-coupled ortho-quinones. We show that the immediate product of the reaction is a Cu(II)-semiquinone radical complex and reveal that ortho-oxygenation precedes oxidative coupling. This complex is the resting state of the Cu catalyst during turnover at room temperature. A mechanistic study of the formation of this complex at low temperatures demonstrates that the oxygenation pathway mimics the dinuclear Cu enzyme tyrosinase by involving a dinuclear side-on peroxodicopper(II) oxidant. Unlike the enzyme, however, the rate-limiting step of the ortho-oxygenation reaction is the self-assembly of the oxidant from Cu(I) and O2. We provide details for all steps in the cycle and demonstrate that turnover is contingent upon proton-transfer events that are mediated by a slight excess of ligand. Finally, our knowledge of the reaction mechanism can be leveraged to diversify the reaction outcome. Thus, uncoupled ortho-quinones are favored in polar, coordinating media, highlighting unusually high levels of chemoselectivity for a catalytic aerobic oxidation of a phenol.

  15. Reduction of anoxia through myoglobin-facilitated diffusion of oxygen.

    PubMed Central

    Salathé, E P; Kolkka, R W

    1986-01-01

    At relatively low perfusion rates, anoxic regions may occur in tissue even though oxygen remains in the blood as it leaves the capillary at the venous end. In this paper a mathematical theory of facilitated diffusion is developed and used to determine the extent to which myoglobin increases the removal of oxygen from blood and aids in the reduction or elimination of regions of anoxia. PMID:3790691

  16. 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.

  17. Role of reductants in CuZSM-5 catalyzed NOx reduction

    SciTech Connect

    Bhore, N.A.; Dwyer, F.G.; Marler, D.O.; McWilliams, J.P.

    1993-12-31

    The implementation of clean burn engines is limited by technology to efficiently remove nitrogen oxides from the net oxidizing exhaust composition. High NO{sub x} conversions require the preferential reaction of reductants (hydrogen, carbon monoxide, olefins and paraffins) with nitrogen oxides over that of combustion. This study examines the role of these reactions over CuZM-5 catalyst in a simulated lean burn engine exhaust. By careful addition of a known amount of individual reductant over fresh and aged catalysts, the authors find that propylene is the primary-reductant for NO{sub x} conversion; hydrogen and carbon monoxide are not. For stoichiometric-burn engines, carbon monoxide and hydrogen are known to be primary reductants on three-way catalysts. Other light olefins such as isobutylene and ethylene are also effective in NO{sub x} reduction. Paraffins are much less effective. The efficacy of olefin reductant decreases on aging.

  18. 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

  19. Thermal conductivity reduction in oxygen-deficient strontium titanates

    NASA Astrophysics Data System (ADS)

    Yu, Choongho; Scullin, Matthew L.; Huijben, Mark; Ramesh, Ramamoorthy; Majumdar, Arun

    2008-05-01

    We report significant thermal conductivity reduction in oxygen-deficient lanthanum-doped strontium titanate (Sr1-xLaxTiO3-δ) films as compared to unreduced strontium titanates. Our experimental results suggest that the oxygen vacancies could have played an important role in the reduction. This could be due to the nature of randomly distributed and clustered vacancies, which would be very effective to scatter phonons. Our results could provide a pathway for tailoring the thermal conductivity of complex oxides, which is very beneficial to various applications including thermoelectrics.

  20. Diverse Oxygenations Catalyzed by Carbazole 1,9a-Dioxygenase from Pseudomonas sp. Strain CA10

    PubMed Central

    Nojiri, Hideaki; Nam, Jeong-Won; Kosaka, Mikiko; Morii, Ken-Ichi; Takemura, Tetsuo; Furihata, Kazuo; Yamane, Hisakazu; Omori, Toshio

    1999-01-01

    Carbazole 1,9a-dioxygenase (CARDO) from Pseudomonas sp. strain CA10 is a multicomponent enzyme that catalyzes the angular dioxygenation of carbazole, dibenzofuran, and dibenzo-p-dioxin. It was revealed by gas chromatography-mass spectrometry and 1H and 13C nuclear magnetic resonance analyses that xanthene and phenoxathiin were converted to 2,2′,3-trihydroxydiphenylmethane and 2,2′,3-trihydroxydiphenyl sulfide, respectively. Thus, for xanthene and phenoxathiin, angular dioxygenation by CARDO occurred at the angular position adjacent to the oxygen atom to yield hetero ring-cleaved compounds. In addition to the angular dioxygenation, CARDO catalyzed the cis dihydroxylation of polycyclic aromatic hydrocarbons and biphenyl. Naphthalene and biphenyl were converted by CARDO to cis-1,2-dihydroxy-1,2-dihydronaphthalene and cis-2,3-dihydroxy-2,3-dihydrobiphenyl, respectively. On the other hand, CARDO also catalyzed the monooxygenation of sulfur heteroatoms in dibenzothiophene and of the benzylic methylenic group in fluorene to yield dibenzothiophene-5-oxide and 9-hydroxyfluorene, respectively. These results indicate that CARDO has a broad substrate range and can catalyze diverse oxygenation: angular dioxygenation, cis dihydroxylation, and monooxygenation. The diverse oxygenation catalyzed by CARDO for several aromatic compounds might reflect the differences in the binding of the substrates to the reaction center of CARDO. PMID:10322011

  1. Heme oxygenase reveals its strategy for catalyzing three successive oxygenation reactions.

    PubMed

    Matsui, Toshitaka; Unno, Masaki; Ikeda-Saito, Masao

    2010-02-16

    Heme oxygenase (HO) is an enzyme that catalyzes the regiospecific conversion of heme to biliverdin IXalpha, CO, and free iron. In mammals, HO has a variety of physiological functions, including heme catabolism, iron homeostasis, antioxidant defense, cellular signaling, and O(2) sensing. The enzyme is also found in plants (producing light-harvesting pigments) and in some pathogenic bacteria, where it acquires iron from the host heme. The HO-catalyzed heme conversion proceeds through three successive oxygenations, a process that has attracted considerable attention because of its reaction mechanism and physiological importance. The HO reaction is unique in that all three O(2) activations are affected by the substrate itself. The first step is the regiospecific self-hydroxylation of the porphyrin alpha-meso carbon atom. The resulting alpha-meso-hydroxyheme reacts in the second step with another O(2) to yield verdoheme and CO. The third O(2) activation, by verdoheme, cleaves its porphyrin macrocycle to release biliverdin and free ferrous iron. In this Account, we provide an overview of our current understanding of the structural and biochemical properties of the complex self-oxidation reactions in HO catalysis. The first meso-hydroxylation is of particular interest because of its distinct contrast with O(2) activation by cytochrome P450. Although most heme enzymes oxidize exogenous substrates by high-valent oxo intermediates, HO was proposed to utilize the Fe-OOH intermediate for the self-hydroxylation. We have succeeded in preparing and characterizing the Fe-OOH species of HO at low temperature, and an analysis of its reaction, together with mutational and crystallographic studies, reveals that protonation of Fe-OOH by a distal water molecule is critical in promoting the unique self-hydroxylation. The second oxygenation is a rapid, spontaneous auto-oxidation of the reactive alpha-meso-hydroxyheme; its mechanism remains elusive, but the HO enzyme has been shown not to

  2. 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.

  3. 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

  4. 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

  5. A comparative DFT study of oxygen reduction reaction on mononuclear and binuclear cobalt and iron phthalocyanines

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Li, Mengke; Yu, Zongxue; Ke, Qiang

    2016-12-01

    The oxygen reduction reaction (ORR) catalyzed by mononuclear and planar binuclear cobalt (CoPc) and iron phthalocyanine (FePc) catalysts is investigated in detail by density functional theory (DFT) methods. The calculation results indicate that the ORR activity of Fe-based Pcs is much higher than that of Co-based Pcs, which is due to the fact that the former could catalyze 4e- ORRs, while the latter could catalyze only 2e- ORRs from O2 to H2O2. The original high activities of Fe-based Pcs could be attributed to their high energy level of the highest occupied molecular orbital (HOMO), which could lead to the stronger adsorption energy between catalysts and ORR species. Nevertheless, the HOMO of Co-based Pcs is the ring orbital, not the 3 d Co orbital, thereby inhibiting the electron transfer from metal to adsorbates. Furthermore, compared with mononuclear FePc, the planar binuclear FePc has more stable structure in acidic medium and more suitable adsorption energy of ORR species, making it a promising non-precious electrocatalyst for ORR.

  6. 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

    2013-05-07

    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.

  7. 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

  8. Cytochromes P450 catalyze the reduction of α,β-unsaturated aldehydes.

    PubMed

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

    2011-08-15

    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, O(2), 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 and 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 a 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 the reduction of α,β-unsaturated aldehydes in the liver.

  9. Reduction of nitric oxide catalyzed by hydroxylamine oxidoreductase from an anammox bacterium.

    PubMed

    Irisa, Tatsuya; Hira, Daisuke; Furukawa, Kenji; Fujii, Takao

    2014-12-01

    The hydroxylamine oxidoreductase (HAO) from the anammox bacterium, Candidatus Kuenenia stuttgartiensis has been reported to catalyze the oxidation of hydroxylamine (NH2OH) to nitric oxide (NO) by using bovine cytochrome c as an oxidant. In contrast, we investigated whether the HAO from anammox bacterium strain KSU-1 could catalyze the reduction of NO with reduced benzyl viologen (BVred) and the NO-releasing reagent, NOC 7. The reduction proceeded, resulting in the formation of NH2OH as a product. The oxidation rate of BVred was proportional to the concentration of BVred itself for a short period in each experiment, a situation that was termed quasi-steady state. The analyses of the states at various concentrations of HAO allowed us to determine the rate constant for the catalytic reaction, (2.85 ± 0.19) × 10(5) M(-1) s(-1), governing NO reduction by BVred and HAO, which was comparable to that reported for the HAO from the ammonium oxidizer, Nitrosomonas with reduced methyl viologen. These results suggest that the anammox HAO functions to adjust anammox by inter-conversion of NO and NH2OH depending on the redox potential of the physiological electron transfer protein in anammox bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  10. 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.

  11. Enantioselective Synthesis of β-Arylamines via Chiral Phosphoric Acid-Catalyzed Asymmetric Reductive Amination.

    PubMed

    Kim, Kyung-Hee; Lee, Chun-Young; Cheon, Cheol-Hong

    2015-06-19

    A new method for the synthesis of chiral β-aryl amines via chiral phosphoric acid-catalyzed enantioselective reductive amination of benzyl methyl ketone derivatives with Hantzsch ester was developed. Various chiral β-aryl amines were obtained in high yields and with good to high enantioselectivities. This transformation is applicable to gram-scale reactions, and the catalyst loading can be reduced to 1 mol % without sacrificing any catalytic efficacy. Furthermore, the resulting β-aryl amine was successfully converted into a tetrahydroisoquinoline compound without any loss of enantioselectivity.

  12. Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

    SciTech Connect

    Chlistunoff, Jerzy; Sansinena, Jose -Maria

    2016-11-17

    We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfaces where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.

  13. Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

    DOE PAGES

    Chlistunoff, Jerzy; Sansinena, Jose -Maria

    2016-11-17

    We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

  14. 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

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

    DOE PAGES

    Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; ...

    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

  16. 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.

  17. 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.

  18. Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

    NASA Astrophysics Data System (ADS)

    Oba, Yasuhiro; Poulson, Simon R.

    2009-01-01

    The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO 4 at 10-54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L -1, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10 -6 s -1 under neutral conditions and 2.1 to 37.4 × 10 -7 s -1 under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol -1 and 49.7 ± 13.0 kJ mol -1 under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors ( ɛ) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ɛ values ranging from -4.5‰ to -11.6‰. Under neutral conditions, ɛ does not show any systematic trends vs. temperature or ferrous iron concentration, with ɛ values ranging from -7.3 to -10.3‰. Characterization of the oxygen isotope fractionation factor associated with O 2 reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.

  19. Characteristics of the nitric oxide synthase-catalyzed conversion of arginine to N-hydroxyarginine, the first oxygenation step in the enzymic synthesis of nitric oxide.

    PubMed

    Campos, K L; Giovanelli, J; Kaufman, S

    1995-01-27

    The nitric oxide synthase-catalyzed conversion of L-arginine to L-citrulline and nitric oxide is known to be the sum of two partial reactions: oxygenation of arginine to N-hydroxyarginine, followed by oxygenation of N-hydroxyarginine to citrulline and nitric oxide. Whereas the conversion of N-hydroxyarginine to citrulline and nitric oxide has been the subject of a number of studies, the oxygenation of arginine to N-hydroxyarginine has received little attention. Here we show that substrate amounts of rat cerebellar nitric oxide synthase, in the absence of added NADPH, catalyze the conversion of arginine to N-hydroxyarginine as the dominant product. The product appears not to be tightly bound to the enzyme. A maximum of 0.16 mol of N-hydroxyarginine/mol of nitric oxide synthase subunit was formed. The reaction requires oxygen and the addition of Ca2+/calmodulin and is stimulated 3-fold by tetrahydrobiopterin. Upon addition of NADPH, citrulline is formed exclusively. Conversion of N-hydroxyarginine to citrulline, like the first partial reaction, requires Ca2+/calmodulin and is stimulated by tetrahydrobiopterin but differs from the first partial reaction in being completely dependent upon addition of NADPH. These results indicate that brain nitric oxide synthase contains an endogenous reductant that can support oxygenation of arginine but not of N-hydroxyarginine. The reductant is not NADPH, since the amount of nitric oxide synthase-bound NADPH is appreciably less than the amount required for N-hydroxyarginine synthesis. Possible candidates for this role are discussed in relation to proposed mechanisms of action of nitric oxide synthase.

  20. tert-Butyl hydroperoxide oxygenation of organic sulfides catalyzed by diruthenium(II,III) tetracarboxylates.

    PubMed

    Villalobos, Leslie; Barker Paredes, Julia E; Cao, Zhi; Ren, Tong

    2013-11-04

    Diruthenium(II,III) carboxylates Ru2(esp)2Cl (1a), [Ru2(esp)2(H2O)2]BF4 (1b), and Ru2(OAc)4Cl (2) efficiently catalyze the oxygenation of organic sulfides. As noted in a previous work, 1a is active in oxygenation of organic sulfides with tert-butyl hydroperoxide (TBHP) in CH3CN. Reported herein in detail is the oxygenation activity of 1a, 1b, and 2, with the latter being highly selective in oxo-transfer to organic sulfides using TBHP under ambient conditions. Solvent-free oxidation reactions were achieved through dissolving 1a or 1b directly into the substrate with 2 equiv of TBHP, yielding TOF up to 2056 h(-1) with 1b. Also examined are the rate dependence on both catalyst and oxidant concentration for reactions with catalysts 1a and 2. Ru2(OAc)4Cl may be kinetically saturated with TBHP; however, Ru2(esp)2Cl does not display saturation kinetics. By use of a series of para-substituted thioanisoles, linear free-energy relationships were established for both 1a and 2, where the reactivity constants (ρ) are negative and that of 1a is about half that of 2. Given these reactivity data, two plausible reaction pathways were suggested. Density functional theory (DFT) calculation for the model compound Ru2(OAc)4Cl·TBHP, with TBHP on the open axial site, revealed elongation of the O-O bond of TBHP upon coordination.

  1. Growth and Detachment of Oxygen Bubbles Induced by Gold-Catalyzed Decomposition of Hydrogen Peroxide

    PubMed Central

    2017-01-01

    Whereas bubble growth out of gas-oversatured solutions has been quite well understood, including the formation and stability of surface nanobubbles, this is not the case for bubbles forming on catalytic surfaces due to catalytic reactions, though it has important implications for gas evolution reactions and self-propulsion of micro/nanomotors fueled by bubble release. In this work we have filled this gap by experimentally and theoretically examining the growth and detachment dynamics of oxygen bubbles from hydrogen peroxide decomposition catalyzed by gold. We measured the bubble radius R(t) as a function of time by confocal microscopy and find R(t) ∝ t1/2. This diffusive growth behavior demonstrates that the bubbles grow from an oxygen-oversaturated environment. For several consecutive bubbles detaching from the same position in a short period of time, a well-repeated growing behavior is obtained from which we conclude the absence of noticeable depletion effect of oxygen from previous bubbles or increasing oversaturation from the gas production. In contrast, for two bubbles far apart either in space or in time, substantial discrepancies in their growth rates are observed, which we attribute to the variation in the local gas oversaturation. The current results show that the dynamical evolution of bubbles is influenced by comprehensive effects combining chemical catalysis and physical mass transfer. Finally, we find that the size of the bubbles at the moment of detachment is determined by the balance between buoyancy and surface tension and by the detailed geometry at the bubble’s contact line. PMID:28983387

  2. Growth and Detachment of Oxygen Bubbles Induced by Gold-Catalyzed Decomposition of Hydrogen Peroxide.

    PubMed

    Lv, Pengyu; Le The, Hai; Eijkel, Jan; Van den Berg, Albert; Zhang, Xuehua; Lohse, Detlef

    2017-09-28

    Whereas bubble growth out of gas-oversatured solutions has been quite well understood, including the formation and stability of surface nanobubbles, this is not the case for bubbles forming on catalytic surfaces due to catalytic reactions, though it has important implications for gas evolution reactions and self-propulsion of micro/nanomotors fueled by bubble release. In this work we have filled this gap by experimentally and theoretically examining the growth and detachment dynamics of oxygen bubbles from hydrogen peroxide decomposition catalyzed by gold. We measured the bubble radius R(t) as a function of time by confocal microscopy and find R(t) ∝ t(1/2). This diffusive growth behavior demonstrates that the bubbles grow from an oxygen-oversaturated environment. For several consecutive bubbles detaching from the same position in a short period of time, a well-repeated growing behavior is obtained from which we conclude the absence of noticeable depletion effect of oxygen from previous bubbles or increasing oversaturation from the gas production. In contrast, for two bubbles far apart either in space or in time, substantial discrepancies in their growth rates are observed, which we attribute to the variation in the local gas oversaturation. The current results show that the dynamical evolution of bubbles is influenced by comprehensive effects combining chemical catalysis and physical mass transfer. Finally, we find that the size of the bubbles at the moment of detachment is determined by the balance between buoyancy and surface tension and by the detailed geometry at the bubble's contact line.

  3. Iron(II)-catalyzed intermolecular amino-oxygenation of olefins through the N-O bond cleavage of functionalized hydroxylamines.

    PubMed

    Lu, Deng-Fu; Zhu, Cheng-Liang; Jia, Zhen-Xin; Xu, Hao

    2014-09-24

    An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.

  4. Iron(II)-Catalyzed Intermolecular Amino-Oxygenation of Olefins through the N–O Bond Cleavage of Functionalized Hydroxylamines

    PubMed Central

    2015-01-01

    An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N–O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods. PMID:25166591

  5. Changes in arterial oxygenation and self-reported oxygen use after lung volume reduction surgery.

    PubMed

    Snyder, Margaret L; Goss, Christopher H; Neradilek, Blazej; Polissar, Nayak L; Mosenifar, Zab; Wise, Robert A; Fishman, Alfred P; Benditt, Joshua O

    2008-08-15

    Lung volume reduction surgery (LVRS) is inconsistently reported to improve arterial oxygenation in patients with chronic obstructive pulmonary disease. We studied the effects of surgery on oxygenation in a large cohort and identified predictors of postoperative oxygenation improvement. We evaluated oxygenation in 1,078 subjects with chronic obstructive pulmonary disease enrolled in the National Emphysema Treatment Trial after LVRS compared with medical control subjects, including arterial blood gases, use of supplemental oxygen during treadmill walking, and self-reported use of oxygen during rest, exertion, and sleep. Pa(O(2)) breathing room air was equal in medical and surgical subjects at baseline (64.8 vs. 65.0 mm Hg, P = not significant), but lower in medical subjects at 6 months (63.6 vs. 70.0 mm Hg, P < 0.001), 12 months (63.9 vs. 68.7 mm Hg, P < 0.001), and 24 months (62.4 vs. 68.0 mm Hg, P < 0.001). Fewer medical subjects required oxygen for treadmill walking at baseline compared with surgical subjects (46 vs. 53%, P = 0.02). However, more medical subjects required oxygen for this activity at 6 months (49 vs. 33%, P < 0.001), 12 months (50 vs. 36%, P < 0.001), and 24 months (52 vs. 42%, P = 0.02). Self-reported oxygen use was greater in medical than in surgical subjects at 6, 12, and 24 months. Multivariate modeling of preoperative characteristics showed baseline oxygenation status was the best predictor of postoperative oxygenation. LVRS increases Pa(O(2)), and decreases treadmill and self-reported use of oxygen for up to 24 months post-procedure. Clinical trial registered with www.clinicaltrials.gov (NCT 00000606).

  6. New enzymatic pathways for the reduction of reactive oxygen species in Entamoeba histolytica.

    PubMed

    Cabeza, Matías S; Guerrero, Sergio A; Iglesias, Alberto A; Arias, Diego G

    2015-06-01

    Entamoeba histolytica, an intestinal parasite that is the causative agent of amoebiasis, is exposed to elevated amounts of highly toxic reactive oxygen and nitrogen species during tissue invasion. A flavodiiron protein and a rubrerythrin have been characterized in this human pathogen, although their physiological reductants have not been identified. The present work deals with biochemical studies performed to reach a better understanding of the kinetic and structural properties of rubredoxin reductase and two ferredoxins from E. histolytica. We complemented the characterization of two different metabolic pathways for O2 and H2O2 detoxification in E. histolytica. We characterized a novel amoebic protein with rubredoxin reductase activity that is able to catalyze the NAD(P)H-dependent reduction of heterologous rubredoxins, amoebic rubrerythrin and flavodiiron protein but not ferredoxins. In addition, the protein exhibited an NAD(P)H oxidase activity, which generates hydrogen peroxide from molecular oxygen. We describe how different ferredoxins were also efficient reducing substrates for both flavodiiron protein and rubrerythrin. The enzymatic systems herein characterized could contribute to the in vivo detoxification of O2 and H2O2, playing a key role for the parasite defense against reactive oxidant species. To the best of our knowledge this is the first characterization of a eukaryotic rubredoxin reductase, including a novel kinetic study on ferredoxin-dependent reduction of flavodiiron and rubrerythrin proteins. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. 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.

  8. 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

  9. Bio-inspired nanocatalysts for the oxygen reduction reaction.

    PubMed

    Grumelli, Doris; Wurster, Benjamin; Stepanow, Sebastian; Kern, Klaus

    2013-01-01

    Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.

  10. Bio-inspired nanocatalysts for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Grumelli, Doris; Wurster, Benjamin; Stepanow, Sebastian; Kern, Klaus

    2013-12-01

    Electrochemical conversions at fuel cell electrodes are complex processes. In particular, the oxygen reduction reaction has substantial overpotential limiting the electrical power output efficiency. Effective and inexpensive catalytic interfaces are therefore essential for increased performance. Taking inspiration from enzymes, earth-abundant metal centres embedded in organic environments present remarkable catalytic active sites. Here we show that these enzyme-inspired centres can be effectively mimicked in two-dimensional metal-organic coordination networks self-assembled on electrode surfaces. Networks consisting of trimesic acid and bis-pyridyl-bispyrimidine coordinating to single iron and manganese atoms on Au(111) effectively catalyse the oxygen reduction and reveal distinctive catalytic activity in alkaline media. These results demonstrate the potential of surface-engineered metal-organic networks for electrocatalytic conversions. Specifically designed coordination complexes at surfaces inspired by enzyme cofactors represent a new class of nanocatalysts with promising applications in electrocatalysis.

  11. Highly durable graphene nanoplatelets supported Pt nanocatalysts for oxygen reduction

    SciTech Connect

    Shao, Yuyan; Zhang, Sheng; Wang, Chong M.; Nie, Zimin; Liu, Jun; Wang, Yong; Lin, Yuehe

    2010-06-01

    We report graphene nanoplatelets (GNP), which exhibit the advantages of both single-layer graphene and highly graphitic carbon, as a durable alternative support material for Pt nanoparticles for oxygen reduction in fuel cells. Pt nanoparticles are deposited on poly(diallyldimethylammonium chloride)(PDDA)-coated GNP, and characterized with transmission electron microscopy, X-ray diffraction, Raman spectra, and electrochemical tests. Pt/GNP exhibits greatly enhanced electrochemical durability (2-3 times that of Pt/CNT and commercial Etek Pt/C). These are attributed to the intrinsic high graphitization degree of GNP and the enhanced Pt-carbon interaction in Pt/GNP. If considering that GNP can be easily mass produced from graphite, GNP is a promising, low-cost, and durable electrocatalyst support for oxygen reduction in fuel cells.

  12. Electrochemical reduction of oxygen in the presence of humic acids

    NASA Astrophysics Data System (ADS)

    Mal'Tseva, E. V.; Yudina, N. V.; Lomovskii, O. I.

    2011-07-01

    The effect of the nature of humic acids (HAs), their modification by mechanochemical methods, and the pH of the medium on the electrochemical reduction of oxygen is determined. The mechanical activation of caustobioliths, regardless of their nature, is shown to increase the role of quinone moieties in the composition of HAs, thus promoting the initiation of the electrochemical reduction of O2 in a basic medium. The conclusion is drawn that this changes not only the ratio of redox-active moieties in HAs, which determine the total antioxidant activity, but also their character.

  13. 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

  14. Probing the Viability of Oxo-Coupling Pathways in Iridium-Catalyzed Oxygen Evolution.

    PubMed

    Graeupner, Jonathan; Hintermair, Ulrich; Huang, Daria L; Thomsen, Julianne M; Takase, Mike; Campos, Jesús; Hashmi, Sara M; Elimelech, Menachem; Brudvig, Gary W; Crabtree, Robert H

    2013-10-14

    A series of Cp*Ir(III) dimers have been synthesized to elucidate the mechanistic viability of radical oxo-coupling pathways in iridium-catalyzed O2 evolution. The oxidative stability of the precursors toward nanoparticle formation and their oxygen evolution activity have been investigated and compared to suitable monomeric analogues. We found that precursors bearing monodentate NHC ligands degraded to form nanoparticles (NPs), and accordingly their O2 evolution rates were not significantly influenced by their nuclearity or distance between the two metals in the dimeric precursors. A doubly chelating bis-pyridine-pyrazolide ligand provided an oxidation-resistant ligand framework that allowed a more meaningful comparison of catalytic performance of dimers with their corresponding monomers. With sodium periodate (NaIO4) as the oxidant, the dimers provided significantly lower O2 evolution rates per [Ir] than the monomer, suggesting a negative interaction instead of cooperativity in the catalytic cycle. Electrochemical analysis of the dimers further substantiates the notion that no radical oxyl-coupling pathways are accessible. We thus conclude that the alternative path, nucleophilic attack of water on high-valent Ir-oxo species, may be the preferred mechanistic pathway of water oxidation with these catalysts, and bimolecular oxo-coupling is not a valid mechanistic alternative as in the related ruthenium chemistry, at least in the present system.

  15. Probing the Viability of Oxo-Coupling Pathways in Iridium-Catalyzed Oxygen Evolution

    PubMed Central

    Graeupner, Jonathan; Hintermair, Ulrich; Huang, Daria L.; Thomsen, Julianne M.; Takase, Mike; Campos, Jesús; Hashmi, Sara M.; Elimelech, Menachem; Brudvig, Gary W.; Crabtree, Robert H.

    2013-01-01

    A series of Cp*IrIII dimers have been synthesized to elucidate the mechanistic viability of radical oxo-coupling pathways in iridium-catalyzed O2 evolution. The oxidative stability of the precursors toward nanoparticle formation and their oxygen evolution activity have been investigated and compared to suitable monomeric analogues. We found that precursors bearing monodentate NHC ligands degraded to form nanoparticles (NPs), and accordingly their O2 evolution rates were not significantly influenced by their nuclearity or distance between the two metals in the dimeric precursors. A doubly chelating bis-pyridine–pyrazolide ligand provided an oxidation-resistant ligand framework that allowed a more meaningful comparison of catalytic performance of dimers with their corresponding monomers. With sodium periodate (NaIO4) as the oxidant, the dimers provided significantly lower O2 evolution rates per [Ir] than the monomer, suggesting a negative interaction instead of cooperativity in the catalytic cycle. Electrochemical analysis of the dimers further substantiates the notion that no radical oxyl-coupling pathways are accessible. We thus conclude that the alternative path, nucleophilic attack of water on high-valent Ir-oxo species, may be the preferred mechanistic pathway of water oxidation with these catalysts, and bimolecular oxo-coupling is not a valid mechanistic alternative as in the related ruthenium chemistry, at least in the present system. PMID:24474842

  16. 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

  17. Oxygen reduction activity of carbon nitride supported on carbon nanotubes.

    PubMed

    Lyth, S M; Nabae, Y; Islam, N M; Kuroki, S; Kakimoto, M; Miyata, S

    2012-06-01

    Fuel cells offer an alternative to burning fossil fuels, but use platinum as a catalyst which is expensive and scarce. Cheap, alternative catalysts could enable fuel cells to become serious contenders in the green energy sector. One promising class of catalyst for electrochemical oxygen reduction is iron-containing, nanostructured, nitrogen-doped carbon. The catalytic activity of such N-doped carbons has improved vastly over the years bringing industrial applications ever closer. Stoichiometric carbon nitride powder has only been observed in recent years. It has nitrogen content up to 57% and as such is an extremely interesting material to work with. The electrochemical activity of carbon nitride has already been explored, confirming that iron is not a necessary ingredient for 4-electron oxygen reduction. Here, we synthesize carbon nitride on a carbon nanotube support and subject it to high temperature treatment in an effort to increase the surface area and conductivity. The results lend insight into the mechanism of oxygen reduction and show the potential for carbon nanotube-supported carbon nitride to be used as a catalyst to replace platinum in fuel cells.

  18. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    PubMed Central

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-01-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm−2 at 80 °C with a low platinum loading of 0.09 mgPt cm−2, corresponding to a platinum utilization of 0.13 gPt kW−1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction. PMID:28737170

  19. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  20. High performance platinum single atom electrocatalyst for oxygen reduction reaction.

    PubMed

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-24

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm(-2) at 80 °C with a low platinum loading of 0.09 mgPt cm(-2), corresponding to a platinum utilization of 0.13 gPt kW(-1) in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  1. 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.

  2. A facile synthesis of highly stable modified carbon nanotubes as efficient oxygen reduction reaction catalysts

    NASA Astrophysics Data System (ADS)

    Stenmark, Theodore Axel

    Proton Exchange Membrane Fuel Cell (PEMFC) technology is an exciting alternative energy prospect, especially in the field of transportation. PEMFCs are three times as efficient as internal combustion (IC) engines and emit only water as a byproduct. The latter point is especially important in a day and age when climate change is upon us. However, platinum required to catalyze the sluggish oxygen reduction reaction (ORR) which takes place on the cathode of the PEMFC has rendered fuel cell automobiles economically unviable. Therefore, the pursuit of an inexpensive replacement for platinum has become an active research area. Herein, a facile synthetic process for modified carbon nanotubes for ORR catalysis is described. These nanotubes display catalytic activity via rotating disc electrode (RDE) analysis which, in some cases, equals that of a Pt/C standard.

  3. Sewage sludge biochar as an efficient catalyst for oxygen reduction reaction in an microbial fuel cell.

    PubMed

    Yuan, Yong; Yuan, Tian; Wang, Dingmei; Tang, Jiahuan; Zhou, Shungui

    2013-09-01

    Sewage sludge (SS) biochars have been prepared under an inert atmosphere at different temperatures. Morphologic and chemical analyses reveal that the surface of the biochar carbonized at 900°C (SS900) has more abundant micropores, and higher nitrogen and iron contents as compared to those carbonized at 500 (SS500) and 700°C (SS700). The electrochemical analyses display that the prepared biochars are active for catalyzing oxygen reduction reaction (ORR). However, more positive peak potential and larger peak current of ORR are found using the SS900 as compared to the SS500 and SS700. In MFCs, the maximum power density of 500±17 mW m(-2) was obtained from the SS900 cathode, which is comparable to the Pt cathode. The proposed cathode exhibited good stability and great tolerance to methanol. Given these results, it is expected that the SS-derived biochar cathode can find application in fuel cell systems.

  4. Oxygen electro-reduction catalysts for self-assembly on supports

    NASA Astrophysics Data System (ADS)

    Dougan, Jennifer; Panton, Raquel; Cheng, Qiling; Gervasio, Don F.

    2005-01-01

    A new strategy for making low cost, catalytic electrodes is being developed for fuel-cells and electrochemical sensors. The strategy is to synthesize a macrocyclic catalyst derivatized with a functional group (like phosphate or carboxylate), which has affinity for a metal-oxide/metal surface. The purpose of the functional group is to anchor the modified catalyst to the metal surface, thereby promoting the formation of a self-assembled monolayer (SAM) of catalyst on a metal support. Syntheses are given for new ferrocene compounds and metallo porphyrins with anchor groups. The ferrocenes, which are relatively easy to synthesize, were made to learn how to form a stable SAM on a metal-oxide/metal surface. The metallo porphyrins were made for catalyzing oxygen electro-reduction with no platinum. Strategies for attaining an ideal catalytic electrode are discussed.

  5. Reduction of xylose to xylitol catalyzed by glucose-fructose oxidoreductase from Zymomonas mobilis.

    PubMed

    Zhang, Xiaomei; Chen, Guanjun; Liu, Weifeng

    2009-04-01

    Genetic improvements of Zymomonas mobilis for pentose utilization have a huge potential in fuel ethanol production. The production of xylitol and the resulting growth inhibition by xylitol phosphate have been considered to be one of the important factors affecting the rates and yields from xylose metabolism by the recombinant Z. mobilis, but the mechanism of xylitol formation is largely unknown. Here, we reported that glucose-fructose oxidoreductase (GFOR), a periplasmic enzyme responsible for sorbitol production, catalyzed the reduction of xylose to xylitol in vitro, operating via a ping-pong mechanism similar to that in the formation of sorbitol. However, the specific activity of GFOR for sorbitol was higher than that for xylitol (68.39 vs. 1.102 micromol min(-1) mg(-1)), and an apparent substrate-induced positive cooperativity occurred during the catalyzed formation of xylitol, with the Hill coefficient being about 2. While a change of the potential acid-base catalyst Tyr269 to Phe almost completely abolished the activity toward xylose as well as fructose, mutant S116D, which has been shown to lose tight cofactor binding, displayed an even slower catalytic process against xylose.

  6. 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.

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

    DOE PAGES

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

    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

  8. 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)

  9. The mechanisms of oxygen reduction and evolution reactions in nonaqueous lithium-oxygen batteries.

    PubMed

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

    2014-09-01

    A fundamental understanding of the mechanisms of both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in nonaqueous lithium-oxygen (Li-O2) batteries is essential for the further development of these batteries. In this work, we systematically investigate the mechanisms of the ORR/OER reactions in nonaqueous Li-O2 batteries by using electron paramagnetic resonance (EPR) spectroscopy, using 5,5-dimethyl-pyrroline N-oxide as a spin trap. The study provides direct verification of the formation of the superoxide radical anion (O2(˙-)) as an intermediate in the ORR during the discharge process, while no O2(˙-) was detected in the OER during the charge process. These findings provide insight into, and an understanding of, the fundamental reaction mechanisms involving oxygen and guide the further development of this field. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ni-catalyzed reductive homocoupling of unactivated alkyl bromides at room temperature and its synthetic application.

    PubMed

    Peng, Yu; Luo, Long; Yan, Chang-Song; Zhang, Jian-Jian; Wang, Ya-Wen

    2013-11-01

    A room-temperature Ni-catalyzed reductive approach to homocoupling of unactivated primary, secondary, and tertiary alkyl bromides is described. The catalytic system can be easily generated from air-stable and cheap materials and demonstrates broad functional group tolerance, thus allowing facile access to useful dimeric triterpene and lignan-like molecules. Moreover, the dimerization of tertiary bromide 6 efficiently establishes sterically hindered vicinal quaternary carbons (C3a and C3a'), which is a key linkage of intriguing bispyrrolo[2,3-b]indoline alkaloids, thereby enabling us to complete the total syntheses of racemic chimonanthine (9) and folicanthine (10). In addition, this dimerization method can be expanded to the highly stereoselective synthesis of bisperhydrofuro[2,3-b]furan (5a) and the dimeric spiroketal 5b, signifying the involvement of possible radical species.

  11. Ability of different biomaterials to enantioselectively catalyze oxidation and reduction reactions.

    PubMed

    Nagaoka, Hiroyuki

    2004-01-01

    We studied the ability of different biomaterials to enantioselectively catalyze oxidation or reduction reactions with the help of substrate rac-1-m or p-ArCH(OH)Me and the 1-o-ArC(O)Me derivatives. Apoenzyme (NAD(P)(+)-dependent secondary alcohol dehydrogenase(NAD(P)-E)) and cofactor (NAD(P)(+)) were activated by preincubating immobilized aqueous plant leaf (e.g., young wheat leaves), cereal tissue (wheat bran), vegetable (e.g., carrot), and seaweed (e.g., wakame seaweed) solutions, and the NAD(P)-E oxidized only (R)-isomers highly enantioselectively. Thus, greater than 99% ee(s) of (S)-isomers (1m-5m and 1p-5p) can be obtained from corresponding rac-1-m or p-ArCH(OH)Me. Further, immobilized chlorella cells and immobilized baker's yeast can reduce highly stereoselectively; greater than 99% ee(s) of (S)-isomers (1o-5o) can be obtained from corresponding 1-o-ArC(O)Me. Specific use of each isomer ((S)-6 and (R)-6) with greater than 99% ee(s) of racemic-1-2-NpCH(OH)Me becomes possible through selective use of NAD(P)-E eluted from artemisia vulgaris indica leaves and young wheat leaves. We suggest that the pH of the reaction media can determine not only the direction of NAD(P)-E, toward enantioselectively catalyzed oxidation (pH > 7.0) or reduction reaction (pH < 7.0), but also the regioselective reactivity of NAD(P)-E to the substrate o- (pH < 7.0), m-, and p-substituted groups (pH > 7.0). Thus, in comparison to current biocatalysts, several biomaterials can serve as asymmetric reagent bases, providing easily obtained, low-cost natural catalysts with stereoselectivity, regioselectivity, and substrate specificity that work under mild conditions for asymmetric synthesis of organic compounds.

  12. Chemically Driven Enhancement of Oxygen Reduction Electrocatalysis in Supported Perovskite Oxides.

    PubMed

    Lee, Daehee; Tan, Jeiwan; Chae, Keun Hwa; Jeong, Beomgyun; Soon, Aloysius; Ahn, Sung-Jin; Kim, Joosun; Moon, Jooho

    2017-01-05

    Perovskite oxides have the capacity to efficiently catalyze the oxygen reduction reaction (ORR), which is of fundamental importance for electrochemical energy conversion. While the perovskite catalysts have been generally utilized with a support, the role of the supports, regarded as inert toward the ORR, has been emphasized mostly in terms of the thermal stability of the catalyst system and as an ancillary transport channel for oxygen ions during the ORR. We demonstrate a novel approach to improving the catalytic activity of perovskite oxides for solid oxide fuel cells by controlling the oxygen-ion conducting oxide supports. Catalytic activities of (La0.8Sr0.2)0.95MnO3 perovskite thin-film placed on different oxide supports are characterized by electrochemical impedance spectroscopy and X-ray absorption spectroscopy. These analyses confirm that the strong atomic orbital interactions between the support and the perovskite catalyst enhance the surface exchange kinetics by ∼2.4 times, in turn, improving the overall ORR activity.

  13. Copper-catalyzed activation of molecular oxygen for oxidative destruction of acetaminophen: The mechanism and superoxide-mediated cycling of copper species.

    PubMed

    Zhang, Yunfei; Fan, Jinhong; Yang, Bo; Huang, Wutao; Ma, Luming

    2017-01-01

    In this study, the commercial zero-valent copper (ZVC) was investigated to activate the molecular oxygen (O2) for the degradation of acetaminophen (ACT). 50 mg/L ACT could be completely decomposed within 4 h in the ZVC/air system at initial pH 3.0. The H2O2, hydroxyl radical (OH) and superoxide anion radical (O2(-)) were identified as the main reactive oxygen species (ROSs) generated in the above reaction; however, only OH caused the decomposition and mineralization of ACT in the copper-catalyzed O2 activation process. In addition, the in-situ generated Cu(+) from ZVC dissolution not only activated O2 to produce H2O2, but also initiated the decomposition of H2O2 to generate OH. Meanwhile, the H2O2 could also be partly decomposed into O2(-), which served as a mediator for copper cycling by reduction of Cu(2+) to Cu(+) in the ZVC/air system. Therefore, OH could be continuously generated; and then ACT was effectively degraded. Additionally, the effect of solution pH and the dosage of ZVC were also investigated. As a result, this study indicated the key behavior of the O2(-) during Cu-catalyzed activation of O2, which further improved the understanding of O2 activation mechanism by zero-valent metals.

  14. 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.

  15. Photosynthetic water oxidation vs. mitochondrial oxygen reduction: distinct mechanistic parallels.

    PubMed

    Silverstein, Todd P

    2011-08-01

    The photosynthetic oxygen evolving complex (PSII-OEC) and the mitochondrial cytochrome c oxidase (CcO) not only catalyze anti-parallel reactions (the OEC oxidizes water to dioxygen, whereas CcO reduces dioxygen to water), they also share a number of uncanny molecular and mechanistic similarities. Both feature a redox-active polymetallic cluster that includes a key tyrosine, and both utilize a two-phase mechanism. In one phase the polymetallic cluster undergoes four sequential one-electron transfers: In the PSII-OEC, four successive photooxidations of the photosystem II reaction center P680 (to P680(+)) allows acceptance of 4 × 1e- from the Mn(4)Ca cluster; in CcO, four reduced cytochrome c Fe(2+) cations donate 4 × 1e- to the bimetallic center. In the second phase for each enzyme, the polymetallic cluster undergoes a single four-electron transfer with the O(2)/2 H(2)O redox couple. Intriguing mechanistic similarities between these two complex redox enzymes first delineated over a decade ago by Hoganson/Proshlyakov/Babcock et al. are updated and expanded in this article.

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

    PubMed

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

    2015-09-09

    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%.

  17. Superoxide production during reduction of molecular oxygen by assimilatory nitrate reductase.

    PubMed

    Barber, M J; Kay, C J

    1996-02-15

    Assimilatory NADH:nitrate reductase catalyzes the transfer of reducing equivalents from NADH to molecular oxygen. Initial rate studies performed under conditions of optimal pH (8.0) and constant ionic strength (mu = 0.2) revealed that the maximal rate of activity with molecular oxygen was 0.5% (0.44 mumol NADH consumed/min/nmol heme) with a Km for O2 of 586 microM. NADH:molecular oxygen reductase activity exhibited a pH optimum of 9.2, was inhibited by cyanide, and was unaffected by changes in ionic strength or the presence of phosphate ions. Spectroscopic studies indicated NADH:molecular oxygen reductase activity resulted in the production of the superoxide radical, detected as the formation of adrenochrome from epinephrine and by the formation of adrenochrome from epinephrine and by the reduction of nitroblue tetrazolium, both of which could be inhibited by the addition of superoxide dismutase and were unaffected by the addition of catalase. Direct observation of superoxide production using spin-trapping in combination with EPR spectroscopy resulted in the detection of the spin adduct 5.5-dimethyl-5-hydroxy-1-pyrrolidinyloxy (DMPO-OH). The formation of this spin adduct was abolished either in the absence of nitrate reductase, NADH, or DMPO or the the addition of superoxide dismutase or nitrate and was greatly reduced by the presence of cyanide. Inclusion of catalase or ethanol had no effect on the formation of the spin adduct. These results indicate that nitrate reductase can utilize molecular oxygen as an electron acceptor and that the product, O2.(-), is primarily generated via the Mopterin center.

  18. Oxygen and nitrate reduction kinetics of a nonflocculating strain of Zoogloea ramigera.

    PubMed

    Strand, S E; McDonnell, A J; Unz, R F

    1988-01-01

    The oxygen and nitrate reduction kinetics of a nonflocculating strain of Zoogloea ramigera were determined. Axenic, nitrate-reducing bacterial suspensions were acclimated to various oxygen levels in a chemostat while measuring nitrate reduction in the presence of high ammonium nitrogen concentrations. Significant nitrate reduction was observed at oxygen concentrations up to 8 mg L-1. Oxygen consumption was inhibited by oxygen concentrations in excess of 2 mg L-1.

  19. Capacity of reductants and chelators to prevent lipid oxidation catalyzed by fish hemoglobin.

    PubMed

    Maestre, Rodrigo; Pazos, Manuel; Iglesias, Jacobo; Medina, Isabel

    2009-10-14

    The efficiency of different reductants (reduced glutathione, ascorbic acid, and catalase) and metal chelators [ethylenediaminetetraacetic acid (EDTA), citric acid, sodium tripolyphosphate (STPP), and adenosine-5'-triphosphate (ATP)] to inhibit lipid oxidation promoted by fish hemoglobin was investigated. The inhibitory activity on hemoglobin-catalyzed lipid oxidation was also evaluated for grape oligomeric catechins (proanthocyanidins), which have both reducing and chelating properties. The antioxidant activity was studied in two different lipid oxidation models, liposomes and washed minced fish muscle. Grape proanthocyanidins were found to be significantly more effective than other reductants to prevent hemoglobin-mediated lipid oxidation in both liposomes and washed fish muscle. Reduced glutathione was also efficient to retard lipid oxidation at the same molarity in washed fish muscle, whereas catalase and ascorbic acid showed a lower antioxidant activity. Metal chelators were less active than reductants, and consequently, the former were necessarily evaluated at much higher concentration than grape proanthocyanidins and reducing compounds. STPP was found to be the iron chelator with the strongest efficiency to delay hemoglobin-mediated lipid oxidation followed by EDTA. Citric acid and ATP were ineffective in retarding lipid oxidation in both systems. Grape proanthocyanidins provided the most extensive protection to preserve hemoglobin at ferrous state in washed fish muscle. Our results draw attention to the greater capacity of reducing compounds to prevent fish hemoglobin-mediated lipid oxidation in comparison with iron chelators, suggesting that the free radical scavenging and/or reduction of ferrylHb species are crucial actions to avoid the pro-oxidant capacity of fish hemoglobin.

  20. 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.

  1. Charge transfer mediator based systems for electrocatalytic oxygen reduction

    DOEpatents

    Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

    2017-07-18

    Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

  2. 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.

  3. Asymmetric reduction of α-amino ketones with a KBH4 solution catalyzed by chiral Lewis acids.

    PubMed

    He, Peng; Zheng, Haifeng; Liu, Xiaohua; Lian, Xiangjin; Lin, Lili; Feng, Xiaoming

    2014-10-13

    An efficient enantioselective reduction of α-amino ketones with potassium borohydride solution catalyzed by chiral N,N'-dioxide-metal complex catalysts was accomplished under mild reaction conditions for the first time. It provided a simple, convenient, and practical approaches for obtaining synthetically important chiral β-amino alcohols in good to excellent yields (up to 98%) and enantioselectivities (up to 97% ee).

  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. Vitamin A as an enzyme that catalyzes the reduction of MTT to formazan by vitamin C.

    PubMed

    Chakrabarti, R; Kundu, S; Kumar, S; Chakrabarti, R

    2000-09-18

    The tetrazolium salt 3(4,5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is reduced to formazan by the succinate dehydrogenase system of active mitochondria, and hence, specifically used to assay for the viable cells, such as measurement of cell proliferation, cytotoxicity, and cell number. However, in the present study we have shown that some component specifically present in M199 but not in RPMI 1640 media can reduce MTT to formazan in the absence of a living system. Further study revealed that ascorbic acid reduced MTT to formazan, which was profoundly increased by a very small amount of retinol, whereas retinol alone had no effect. Oxidation of ascorbic acid by H(2)O(2) destroyed its ability to reduce MTT. The rate of MTT reduction was directly proportional to the concentration of MTT in the absence of retinol, but approached a zero-order state beyond a certain concentration of MTT in the presence of retinol. Furthermore, retinol remained unchanged after the completion of the reaction. Taken together, these results showed that retinol acts as a reductase that catalyzes the reduction of MTT to formazan using ascorbic acid as the cosubstrate (electron donor).

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

    SciTech Connect

    Holby, Edward F.; Zelenay, Piotr

    2016-05-17

    Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by these materials.

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

    SciTech Connect

    Holby, Edward F.; Zelenay, Piotr

    2016-05-17

    Atomic-scale structures of oxygen reduction reaction (ORR) active sites in non-platinum group metal (non-PGM) catalysts, made from pyrolysis of carbon, nitrogen, and transition-metal (TM) precursors have been the subject of continuing discussion in the fuel cell electrocatalysis research community. We found that quantum chemical modeling is a path forward for understanding of these materials and how they catalyze the ORR. Here, we demonstrate through literature examples of how such modeling can be used to better understand non-PGM ORR active site relative stability and activity and how such efforts can also aid in the interpretation of experimental signatures produced by these materials.

  8. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters.

    PubMed

    Zhang, J; Sasaki, K; Sutter, E; Adzic, R R

    2007-01-12

    We demonstrated that platinum (Pt) oxygen-reduction fuel-cell electrocatalysts can be stabilized against dissolution under potential cycling regimes (a continuing problem in vehicle applications) by modifying Pt nanoparticles with gold (Au) clusters. This behavior was observed under the oxidizing conditions of the O2 reduction reaction and potential cycling between 0.6 and 1.1 volts in over 30,000 cycles. There were insignificant changes in the activity and surface area of Au-modified Pt over the course of cycling, in contrast to sizable losses observed with the pure Pt catalyst under the same conditions. In situ x-ray absorption near-edge spectroscopy and voltammetry data suggest that the Au clusters confer stability by raising the Pt oxidation potential.

  9. Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters

    SciTech Connect

    Zhang,J.; Sasaki, K.; Sutter, E.; Adzic, R.

    2007-01-01

    We demonstrated that platinum (Pt) oxygen-reduction fuel-cell electrocatalysts can be stabilized against dissolution under potential cycling regimes (a continuing problem in vehicle applications) by modifying Pt nanoparticles with gold (Au) clusters. This behavior was observed under the oxidizing conditions of the O{sub 2} reduction reaction and potential cycling between 0.6 and 1.1 volts in over 30,000 cycles. There were insignificant changes in the activity and surface area of Au-modified Pt over the course of cycling, in contrast to sizable losses observed with the pure Pt catalyst under the same conditions. In situ x-ray absorption near-edge spectroscopy and voltammetry data suggest that the Au clusters confer stability by raising the Pt oxidation potential.

  10. Frontispiece: asymmetric reduction of α-amino ketones with a KBH4 solution catalyzed by Chiral Lewis acids.

    PubMed

    He, Peng; Zheng, Haifeng; Liu, Xiaohua; Lian, Xiangjin; Lin, Lili; Feng, Xiaoming

    2014-10-13

    Asymmetric Alkali Metal Borohydride Reduction Alkali metal borohydrides are mild, inexpensive, highly selective, and environmentally friendly reducing agents in organic chemistry. In their Communication on page 13482 ff., X. Feng et al. demonstrate an efficient enantioselective reduction of both secondary and primary α-amino ketones with potassium borohydride solution catalyzed by chiral N,N'-dioxide-metal complex catalysts. The catalytic system features a convenient operation and tolerance to water, without the need for basic additives.

  11. 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

  12. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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.

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

    PubMed

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

    2013-10-07

    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.

  15. Nanostructured MnxOy for oxygen reduction reaction (ORR) catalysts

    NASA Astrophysics Data System (ADS)

    Delmondo, Luisa; Salvador, Gian Paolo; Muñoz-Tabares, José Alejandro; Sacco, Adriano; Garino, Nadia; Castellino, Micaela; Gerosa, Matteo; Massaglia, Giulia; Chiodoni, Angelica; Quaglio, Marzia

    2016-12-01

    In the field of fuel cells, oxygen plays a key role as the final electron acceptor. To facilitate its reduction (Oxygen Reduction Reaction-ORR), a proper catalyst is needed and platinum is considered the best one due to its low overpotential for this reaction. By considering the high price of platinum, alternative catalysts are needed and manganese oxides (MnxOy) can be considered promising substitutes. They are inexpensive, environmental friendly and can be obtained into several forms; most of them show significant electro-catalytic performance, even if strategies are needed to increase their efficiency. In particular, by developing light and high-surface area materials and by optimizing the presence of catalytic sites, we can obtain a cathode with improved electro-catalytic performance. In this case, nanofibers and xerogels are two of the most promising nanostructures that can be used in the field of catalysis. In this work, a study of the morphological and catalytic behavior of MnxOy nanofibers and xerogels is proposed. Nanofibers were obtained by electrospinning, while xerogels were prepared by sol-gel and freeze drying techniques. Despite of the different preparation approaches, the obtained nanostructured manganese oxides exhibited similar catalytic performance for the ORR, comparable to those obtained from Pt catalysts.

  16. Single Platinum Atoms Electrocatalysts: Oxygen Reduction and Hydrogen Oxidation Reactions

    DOE PAGES

    Vukmirovic, Miomir B.; Teeluck, Krishani M.; Liu, Ping; ...

    2017-08-08

    We prepared atomically dispersed catalyst consisting of Pt atoms arranged in a c(2 × 2) array on RuO2(110) substrate. A large interatomic distance of Pt atoms in a c(2 × 2) phase precludes the reactants to interact with more than one Pt atoms. A strong bond of Pt atoms with RuO2 prevents agglomeration of Pt atoms to form 2D-islands or 3D-clusters. The activities of single Pt atom catalyst for the oxygen reduction and hydrogen oxidation reactions were determined and compared with those of bulk Pt. It has lower catalytic activity for the oxygen reduction reaction and similar activity for hydrogenmore » oxidation reaction compared to Pt(111). This was explained by a large calculated up-shift of the dband center of Pt atoms and larger Pt-Pt interatomic distance than that of Pt(111). Our information is of considerable interest for further development of electrocatalysis.« less

  17. Carbon Reduction of Lunar Regolith for Oxygen Production

    NASA Astrophysics Data System (ADS)

    Gustafson, Robert J.; Rice, Eric E.; White, Brant C.

    2005-02-01

    The utilization of extraterrestrial resources will become a key element in the exploration of the Moon and Mars. The ability to locally make propellants, life support consumables, and fuel cell reagents will significantly reduce mission cost by reducing launch mass, and reduce risk through reduced dependence on Earth-supplied materials. The presence of water/hydrogen on the Moon will significantly impact the design of space exploration hardware and systems, but the form and concentration of these resources are unknown. The goal of the first robotic lunar lander mission in 2009/2010 will likely be to determine what is in the permanently shadowed craters of the lunar poles. To meet this goal, the NASA/JSC-led RESOLVE project will develop and integrate an experiment package that can perform the following objectives: (1) obtain ``ground truth'' data for resources at lunar pole; (2) obtain bulk and fine-grained regolith characteristic and environment data; (3) extract and collect volatiles from regolith; (4) produce oxygen from regolith; and (5) perform a hydrogen/water resource processing demonstration after it has been evolved and collected. ORBITEC, an industry partner in the RESOLVE project, is developing a small chemical reactor that will produce oxygen from the lunar regolith using the carbothermal reduction process. The carbothermal reduction process uses a carbonaceous source (such as methane gas) at high temperatures (~1625 °C) to reduce ilmenite and silicates present in the lunar regolith.

  18. 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.

  19. Fractionation of Nitrogen and Oxygen Isotopes During Microbial Nitrate Reduction

    NASA Astrophysics Data System (ADS)

    Lehmann, M. F.; Bernasconi, S. M.; Reichert, P.; Barbieri, A.; McKenzie, J. A.

    2001-12-01

    Lakes represent an important continental sink of fixed nitrogen. Besides the burial of particulate nitrogen, fixed nitrogen is eliminated from lakes by emission of N2 and N2O to the atmosphere during dissimilative nitrate reduction within suboxic and anoxic waters or sediments. The understanding and quantification of this efficient nitrogen removal process in eutrophic lakes is crucial for nitrogen budget modelling and the application and evaluation of lake restoration measures. In order to use natural abundance N and O isotope ratios as tracers for microbial nitrate reduction and to obtain quantitative estimates on its intensity, it is crucial to constrain the associated isotope fractionation. This is the first report of nitrogen and oxygen isotope effects associated with microbial nitrate reduction in lacustrine environments. Nitrate reduction in suboxic and anoxic waters of the southern basin of Lake Lugano (Switzerland) is demonstrated by a progressive nitrate depletion coupled to increasing δ 15N and δ 18O values for residual nitrate. 15N and 18O enrichment factors (ɛ ) were estimated using a closed-system (Rayleigh-distillation) model and a dynamic reaction-diffusion model. Calculated enrichment factors ɛ ranged between -11.2 and -22‰ for 15N and between -6.6 and -11.3‰ for 18O with both nitrogen and oxygen isotope fractionation being greatest during times with the highest nitrate reduction rates. The closed-system model neglects vertical diffusive mixing and does not distinguish between sedimentary and water-column nitrate reduction. Therefore, it tends to underestimate the intrinsic isotope effect of microbial nitrate reduction. Based upon results from earlier studies that indicate that nitrate reduction in sediments displays a highly reduced N-isotope effect (Brandes and Devol, 1997), model-derived enrichment factors could be used to discern the relative importance of nitrate reduction in the water column and in the sediment. Sedimentary nitrate

  20. The Pyruvate and α-Ketoglutarate Dehydrogenase Complexes of Pseudomonas aeruginosa Catalyze Pyocyanin and Phenazine-1-carboxylic Acid Reduction via the Subunit Dihydrolipoamide Dehydrogenase.

    PubMed

    Glasser, Nathaniel R; Wang, Benjamin X; Hoy, Julie A; Newman, Dianne K

    2017-03-31

    Phenazines are a class of redox-active molecules produced by diverse bacteria and archaea. Many of the biological functions of phenazines, such as mediating signaling, iron acquisition, and redox homeostasis, derive from their redox activity. Although prior studies have focused on extracellular phenazine oxidation by oxygen and iron, here we report a search for reductants and catalysts of intracellular phenazine reduction in Pseudomonas aeruginosa Enzymatic assays in cell-free lysate, together with crude fractionation and chemical inhibition, indicate that P. aeruginosa contains multiple enzymes that catalyze the reduction of the endogenous phenazines pyocyanin and phenazine-1-carboxylic acid in both cytosolic and membrane fractions. We used chemical inhibitors to target general enzyme classes and found that an inhibitor of flavoproteins and heme-containing proteins, diphenyleneiodonium, effectively inhibited phenazine reduction in vitro, suggesting that most phenazine reduction derives from these enzymes. Using natively purified proteins, we demonstrate that the pyruvate and α-ketoglutarate dehydrogenase complexes directly catalyze phenazine reduction with pyruvate or α-ketoglutarate as electron donors. Both complexes transfer electrons to phenazines through the common subunit dihydrolipoamide dehydrogenase, a flavoprotein encoded by the gene lpdG Although we were unable to co-crystallize LpdG with an endogenous phenazine, we report its X-ray crystal structure in the apo-form (refined to 1.35 Å), bound to NAD(+) (1.45 Å), and bound to NADH (1.79 Å). In contrast to the notion that phenazines support intracellular redox homeostasis by oxidizing NADH, our work suggests that phenazines may substitute for NAD(+) in LpdG and other enzymes, achieving the same end by a different mechanism. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  1. Reduction of CO2 to methanol catalyzed by a biomimetic organo-hydride produced from pyridine.

    PubMed

    Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

    2014-11-12

    We use quantum chemical calculations to elucidate a viable mechanism for pyridine-catalyzed reduction of CO2 to methanol involving homogeneous catalytic steps. The first phase of the catalytic cycle involves generation of the key catalytic agent, 1,2-dihydropyridine (PyH2). First, pyridine (Py) undergoes a H(+) transfer (PT) to form pyridinium (PyH(+)), followed by an e(-) transfer (ET) to produce pyridinium radical (PyH(0)). Examples of systems to effect this ET to populate PyH(+)'s LUMO (E(0)(calc) ∼ -1.3 V vs SCE) to form the solution phase PyH(0) via highly reducing electrons include the photoelectrochemical p-GaP system (E(CBM) ∼ -1.5 V vs SCE at pH 5) and the photochemical [Ru(phen)3](2+)/ascorbate system. We predict that PyH(0) undergoes further PT-ET steps to form the key closed-shell, dearomatized (PyH2) species (with the PT capable of being assisted by a negatively biased cathode). Our proposed sequential PT-ET-PT-ET mechanism for transforming Py into PyH2 is analogous to that described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics important aspects of the role of NADPH in the formation of C-H bonds in the photosynthetic CO2 reduction process. In particular, in the second phase of the catalytic cycle, which involves three separate reduction steps, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely, formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first of these reduction steps, the homogeneous reduction of CO2, are sequential in nature (in which the formate to formic acid protonation can be assisted by a negatively biased cathode). In contrast, these transfers are coupled in each of the two

  2. Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe-N(x)/C groups.

    PubMed

    Rincón, Rosalba A; Masa, Justus; Mehrpour, Sara; Tietz, Frank; Schuhmann, Wolfgang

    2014-12-07

    The incorporation of Fe-Nx/C moieties into perovskites remarkably activates them for the oxygen reduction reaction (ORR) and also leads to notable improvement of their activity towards the oxygen evolution reaction (OER) thus presenting a new route for realizing high performance, low cost bifunctional catalysts for reversible oxygen electrodes.

  3. 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

  4. 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.

  5. 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

  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. Nanocarbon for Oxygen Reduction Electrocatalysis: Dopants, Edges, and Defects.

    PubMed

    Tang, Cheng; Zhang, Qiang

    2017-01-09

    The oxygen reduction reaction (ORR) is the cornerstone of various sustainable energy-conversion technologies. Metal-free nanocarbon electrocatalysts with competitive activity, enhanced durability, and satisfactory cost, have been proposed as the most promising substitute for precious-metal catalysts. However, their further development is still primarily based on trial-and-error approaches due to the controversial knowledge of critical active sites and mechanisms. Herein, the activity origins of nanocarbon-based ORR electro-catalysts are comprehensively reviewed and correlated, considering the dopants, edges, and defects. Analogously, they can effectively modify the charge/spin distribution on the sp(2) -conjugated carbon matrix, leading to optimized intermediate chemisorption and facilitated electron transfer. Specific doping at defective edges is expected to render practical applications for metal-free nanocarbon electrocatalysts.

  8. 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.

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

    DOE PAGES

    Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; ...

    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

  10. 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.

  11. Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

    DOE PAGES

    Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

    2017-05-11

    Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

  12. Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution.

    PubMed

    Lu, Fang; Zhang, Yu; Liu, Shizhong; Lu, Deyu; Su, Dong; Liu, Mingzhao; Zhang, Yugang; Liu, Ping; Wang, Jia X; Adzic, Radoslav R; Gang, Oleg

    2017-05-31

    Four-electron oxygen reduction reaction (4e-ORR), a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. A long-standing puzzle remains unsolved: why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways on single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nanocubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H2O molecules in activating the facet- and potential-dependent 4e-ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.

  13. Brønsted Acid Catalyzed Oxygenative Bimolecular Friedel-Crafts-type Coupling of Ynamides.

    PubMed

    Patil, Dilip V; Kim, Seung Woo; Nguyen, Quynh H; Kim, Hanbyul; Wang, Shan; Hoang, Tuan; Shin, Seunghoon

    2017-03-20

    A non-metal approach for accessing α-oxo carbene surrogates for a C-C bond-forming bimolecular coupling between ynamides and nucleophilic arenes was developed. This acid-catalyzed coupling features mild temperature, which is critical for the required temporal chemoselectivity among nucleophiles. The scope of nucleophiles includes indoles, pyrroles, anilines, phenols and silyl enolethers. Furthermore, a direct test of SN 2' mechanism has been provided by employing chiral N,N'-dioxides which also enlightens the nature of the intermediates in related metal-catalyzed processes.

  14. Theoretical investigations of the oxygen reduction reaction on Pt(111).

    PubMed

    Keith, John A; Jerkiewicz, Gregory; Jacob, Timo

    2010-09-10

    Computational modeling can provide important insights into chemical reactions in both applied and fundamental fields of research. One of the most critical processes needed in practical renewable energy sources is the oxygen reduction reaction (ORR). Besides being the key process in combustion and corrosion, the ORR has an elusive mechanism that may proceed in a number of complicated reaction steps in electrochemical fuel cells. Indeed, the mechanism of the ORR on highly studied Pt(111) electrodes has been the subject of interest and debate for decades. Herein, we first outline the theory behind these types of simulations and then show how to use these quantum mechanical approaches and approximations to create a realistic model. After reviewing the performance of these methods in studying the binding of molecular oxygen to Pt(111), we then outline our own results in elucidating the ORR and its dependence on environmental parameters, such as solvent, thermodynamic energies, and the presence of an external electrode potential. This approach can, in principle, be applied to other equally complicated investigations of other surfaces or electrochemical reactions.

  15. 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.

  16. Understanding and Controlling Cu-Catalyzed Graphene Nucleation: The Role of Impurities, Roughness, and Oxygen Scavenging

    PubMed Central

    2016-01-01

    The mechanism by which Cu catalyst pretreatments control graphene nucleation density in scalable chemical vapor deposition (CVD) is systematically explored. The intrinsic and extrinsic carbon contamination in the Cu foil is identified by time-of-flight secondary ion mass spectrometry as a major factor influencing graphene nucleation and growth. By selectively oxidizing the backside of the Cu foil prior to graphene growth, a drastic reduction of the graphene nucleation density by 6 orders of magnitude can be obtained. This approach decouples surface roughness effects and at the same time allows us to trace the scavenging effect of oxygen on deleterious carbon impurities as it permeates through the Cu bulk. Parallels to well-known processes in Cu metallurgy are discussed. We also put into context the relative effectiveness and underlying mechanisms of the most widely used Cu pretreatments, including wet etching and electropolishing, allowing a rationalization of current literature and determination of the relevant parameter space for graphene growth. Taking into account the wider CVD growth parameter space, guidelines are discussed for high-throughput manufacturing of “electronic-quality” monolayer graphene films with domain size exceeding 1 mm, suitable for emerging industrial applications, such as electronics and photonics. PMID:28133416

  17. 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

  18. Iron-catalyzed, hydrogen-mediated reductive cyclization of 1,6-enynes and diynes: evidence for bis(imino)pyridine ligand participation.

    PubMed

    Sylvester, Kevin T; Chirik, Paul J

    2009-07-01

    The bis(imino)pyridine iron dinitrogen complex (((i)Pr)PDI)Fe(N(2))(2) catalyzes the hydrogen-mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of established precious metal catalysts. Amino, oxygenated, and carbon-based substrates are readily cyclized to the corresponding hetero- and carbocycles with 5 mol % iron and 4 atm H(2) at 23 degrees C. Stoichiometric reactions between selected substrates and the iron compound under a N(2) atmosphere established transfer dehydrogenation from an isopropyl aryl substituent to either the enyne or diyne substrate. In situ monitoring of the catalytic reaction by (1)H NMR spectroscopy coupled with deuterium labeling experiments established rapid cyclization followed by turnover-limiting hydrogenation.

  19. 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.

  20. 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.

  1. Chiral Phosphoric Acid-Catalyzed Enantioselective Reductive Amination of 2-Pyridyl Ketones: Construction of Structurally Chiral Pyridine-Based Ligands.

    PubMed

    Abudu Rexit, Abulikemu; Luo, Shiwei; Mailikezati, Maihemuti

    2016-11-18

    A chiral phosphoric acid-catalyzed one-pot enantioselective reductive amination of 2-pyridyl ketones was realized to provide chiral pyridine-based ligands in excellent yields with high enantioselectivities (up to 98% yield, 94% ee). Computational studies on the key intermediate imine and transition state of the hydride transfer process revealed that the nitrogen atom of the pyridyl ring might be an important factor to significantly promote both the reaction activity and enantioselectivity.

  2. Contribution of oxygen reduction to charge injection on platinum and sputtered iridium oxide neural stimulation electrodes.

    PubMed

    Cogan, Stuart F; Ehrlich, Julia; Plante, Timothy D; Gingerich, Marcus D; Shire, Douglas B

    2010-09-01

    The extent to which oxygen reduction occurs on sputtered iridium oxide (SIROF) and platinum neural stimulation electrodes was quantified by cyclic voltammetry and voltage-transient measurements in oxygen-saturated physiological saline. Oxygen reduction was the dominant charge-admittance reaction on platinum electrodes during slow-sweep-rate cyclic voltammetry, contributing approximately 12 mC/cm(2) (88% of total charge) to overall cathodal charge capacity. For a 300-nm-thick SIROF electrode, oxygen reduction was a minor reaction contributing 1.3 mC/cm(2), approximately 3% of total charge. During current pulsing with platinum electrodes, oxygen reduction was observed at a level of 7% of the total injected charge. There was no indication of oxygen reduction on pulsed SIROF electrodes. A sweep-rate-dependent contribution of oxygen reduction was observed on penetrating SIROF microelectrodes (nominal surface area 2000 microm(2)) and is interpreted in terms of rate-limited diffusion of oxygen in electrolyte that penetrates the junction between the insulation and electrode shaft. For typical neural stimulation pulses, no oxygen reduction could be observed on penetrating SIROF microelectrodes. Based on the in vivo concentration of dissolved oxygen, it is estimated that oxygen reduction on platinum microelectrodes will contribute less than 0.5% of the total injected charge and considerably less on SIROF electrodes.

  3. 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

  4. 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.

  5. Copper(I)-catalyzed aryl bromides to form intermolecular and intramolecular carbon-oxygen bonds.

    PubMed

    Niu, Jiajia; Guo, Pengran; Kang, Juntao; Li, Zhigang; Xu, Jingwei; Hu, Shaojing

    2009-07-17

    A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K(3)PO(4) as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

  6. Molybdenum-Catalyzed Synthesis of Nitrogenated Polyheterocycles from Nitroarenes and Glycols with Reuse of Waste Reduction Byproduct.

    PubMed

    Rubio-Presa, Rubén; Pedrosa, Marı A R; Fernández-Rodríguez, Manuel A; Arnáiz, Francisco J; Sanz, Roberto

    2017-10-06

    A novel domino reduction/imine formation/intramolecular cyclization/oxidation for the efficient synthesis of pyrrolo(indolo)[1,2-a]quinoxalines and pyrrolo(indolo)[3,2-c]-quinolines from readily available nitrobenzenes and glycols is reported. The process utilizes the carbonyl byproduct of the initial dioxomolybdenum(VI)-catalyzed reduction of nitroaromatics with glycols as a reagent for the imine generation. This method represents the first sustainable domino reaction for the preparation of biologically relevant heterocycles that internally incorporates the waste formed in the first step to the final product.

  7. 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

  8. Z-Selective Olefin Synthesis via Iron-Catalyzed Reductive Coupling of Alkyl Halides with Terminal Arylalkynes

    PubMed Central

    2015-01-01

    Selective catalytic synthesis of Z-olefins has been challenging. Here we describe a method to produce 1,2-disubstituted olefins in high Z selectivity via reductive cross-coupling of alkyl halides with terminal arylalkynes. The method employs inexpensive and nontoxic catalyst (iron(II) bromide) and reductant (zinc). The substrate scope encompasses primary, secondary, and tertiary alkyl halides, and the reaction tolerates a large number of functional groups. The utility of the method is demonstrated in the synthesis of several pharmaceutically relevant molecules. Mechanistic study suggests that the reaction proceeds through an iron-catalyzed anti-selective carbozincation pathway. PMID:25831473

  9. Effects of ionomer morphology on oxygen reduction on Pt

    DOE PAGES

    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. 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.

  12. Efficient oxygen reduction catalysis by subnanometer Pt alloy nanowires.

    PubMed

    Jiang, Kezhu; Zhao, Dandan; Guo, Shaojun; Zhang, Xu; Zhu, Xing; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2017-02-01

    The common knowledge is that Pt and Pt alloy nanoparticles (NPs) less than 2 nm are not desirable for oxygen reduction reaction (ORR). However, whether the same trend is expected in Pt-based nanowires (NWs) and nanoplates remains questionable because there is no scalable approach to make such Pt nanostructures. We report a general approach for preparing subnanometer Pt alloy NWs with a diameter of only 4 to 5 atomic layer thickness, ranging from monometallic Pt NWs to bimetallic PtNi and PtCo NWs and to trimetallic PtNiCo NWs. In a sharp contrast to Pt alloy NPs, the subnanometer Pt alloy NWs demonstrate exceptional mass and specific activities of 4.20 A/mg and 5.11 mA/cm(2) at 0.9 V versus reversible hydrogen electrode (RHE), respectively, 32.3 and 26.9 times higher than those of the commercial Pt/C. Density functional theory simulations reveal that the enhanced ORR activities are attributed to the catalytically active sites on high-density (111) facets in the subnanometer Pt alloy NWs. They are also very stable under the ORR condition with negligible activity decay over the course of 30,000 cycles. Our work presents a new approach to maximize Pt catalytic efficiency with atomic level utilization for efficient heterogeneous catalysis and beyond.

  13. Efficient oxygen reduction catalysis by subnanometer Pt alloy nanowires

    PubMed Central

    Jiang, Kezhu; Zhao, Dandan; Guo, Shaojun; Zhang, Xu; Zhu, Xing; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2017-01-01

    The common knowledge is that Pt and Pt alloy nanoparticles (NPs) less than 2 nm are not desirable for oxygen reduction reaction (ORR). However, whether the same trend is expected in Pt-based nanowires (NWs) and nanoplates remains questionable because there is no scalable approach to make such Pt nanostructures. We report a general approach for preparing subnanometer Pt alloy NWs with a diameter of only 4 to 5 atomic layer thickness, ranging from monometallic Pt NWs to bimetallic PtNi and PtCo NWs and to trimetallic PtNiCo NWs. In a sharp contrast to Pt alloy NPs, the subnanometer Pt alloy NWs demonstrate exceptional mass and specific activities of 4.20 A/mg and 5.11 mA/cm2 at 0.9 V versus reversible hydrogen electrode (RHE), respectively, 32.3 and 26.9 times higher than those of the commercial Pt/C. Density functional theory simulations reveal that the enhanced ORR activities are attributed to the catalytically active sites on high-density (111) facets in the subnanometer Pt alloy NWs. They are also very stable under the ORR condition with negligible activity decay over the course of 30,000 cycles. Our work presents a new approach to maximize Pt catalytic efficiency with atomic level utilization for efficient heterogeneous catalysis and beyond. PMID:28275723

  14. 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.

  15. 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.

  16. Designed protein aggregates entrapping carbon nanotubes for bioelectrochemical oxygen reduction.

    PubMed

    Garcia, Kristen E; Babanova, Sofia; Scheffler, William; Hans, Mansij; Baker, David; Atanassov, Plamen; Banta, Scott

    2016-11-01

    The engineering of robust protein/nanomaterial interfaces is critical in the development of bioelectrocatalytic systems. We have used computational protein design to identify two amino acid mutations in the small laccase protein (SLAC) from Streptomyces coelicolor to introduce new inter-protein disulfide bonds. The new dimeric interface introduced by these disulfide bonds in combination with the natural trimeric structure drive the self-assembly of SLAC into functional aggregates. The mutations had a minimal effect on kinetic parameters, and the enzymatic assemblies exhibited an increased resistance to irreversible thermal denaturation. The SLAC assemblies were combined with single-walled carbon nanotubes (SWNTs), and explored for use in oxygen reduction electrodes. The incorporation of SWNTs into the SLAC aggregates enabled operation at an elevated temperature and reduced the reaction overpotential. A current density of 1.1 mA/cm(2) at 0 V versus Ag/AgCl was achieved in an air-breathing cathode system. Biotechnol. Bioeng. 2016;113: 2321-2327. © 2016 Wiley Periodicals, Inc.

  17. Tuning nanoparticle catalysis for the oxygen reduction reaction.

    PubMed

    Guo, Shaojun; Zhang, Sen; Sun, Shouheng

    2013-08-12

    Advances in chemical syntheses have led to the formation of various kinds of nanoparticles (NPs) with more rational control of size, shape, composition, structure and catalysis. This review highlights recent efforts in the development of Pt and non-Pt based NPs into advanced nanocatalysts for efficient oxygen reduction reaction (ORR) under fuel-cell reaction conditions. It first outlines the shape controlled synthesis of Pt NPs and their shape-dependent ORR. Then it summarizes the studies of alloy and core-shell NPs with controlled electronic (alloying) and strain (geometric) effects for tuning ORR catalysis. It further provides a brief overview of ORR catalytic enhancement with Pt-based NPs supported on graphene and coated with an ionic liquid. The review finally introduces some non-Pt NPs as a new generation of catalysts for ORR. The reported new syntheses with NP parameter-tuning capability should pave the way for future development of highly efficient catalysts for applications in fuel cells, metal-air batteries, and even in other important chemical reactions.

  18. Effect of microstructure of nitrogen-doped graphene on oxygen reduction activity in fuel cells.

    PubMed

    Zhang, Lipeng; Niu, Jianbing; Dai, Liming; Xia, Zhenhai

    2012-05-15

    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 nonmetal catalysts to replace platinum. Here, we present a first-principles study of ORR on nitrogen-doped graphene in acidic environment. We demonstrate that the ORR activity primarily correlates to charge and spin densities of the graphene. The nitrogen doping and defects introduce high positive spin and/or charge densities that facilitate the ORR on graphene surface. The identified active sites are closely related to doping cluster size and dopant-defect interactions. Generally speaking, a large doping cluster size (number of N atoms >2) reduces the number of catalytic active sites per N atom. In combination with N clustering, Stone-Wales defects can strongly promote ORR. For four-electron transfer, the effective reversible potential ranges from 1.04 to 1.15 V/SHE, depending on the defects and cluster size. The catalytic properties of graphene could be optimized by introducing small N clusters in combination with material defects.

  19. 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.

  20. 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

  1. 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.

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

    SciTech Connect

    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 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.

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

    DOE PAGES

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; ...

    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

  4. Metal Nanoparticle-Catalyzed Reduction Using Borohydride in Aqueous Media: A Kinetic Analysis of the Surface Reaction by Microfluidic SERS.

    PubMed

    Xie, Wei; Grzeschik, Roland; Schlücker, Sebastian

    2016-10-24

    Hydrides are widely used in reduction reactions. In protic solvents, their hydrolysis generates molecular hydrogen as a second reducing agent. The competition between these two parallel reduction pathways has been overlooked so far since both typically yield the same product. We investigated the platinum-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol in aqueous sodium borohydride solution as a prominent model reaction, by using label-free SERS monitoring in a microfluidic reactor. Kinetic analysis revealed a strong pH dependence. Surprisingly, only at pH>13 the reduction is driven exclusively by sodium borohydride. This study demonstrates the potential of microfluidics-based kinetic SERS monitoring of heterogeneous catalysis in colloidal suspension. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Enantiotopos-selective C-H oxygenation catalyzed by a supramolecular ruthenium complex.

    PubMed

    Frost, James R; Huber, Stefan M; Breitenlechner, Stefan; Bannwarth, Christoph; Bach, Thorsten

    2015-01-07

    Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive C-H bond and suggest--in line with the kinetic isotope effect--an oxygen rebound mechanism for the reaction.

  6. 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.

  7. Platinum monolayer electrocatalysts for oxygen reduction in fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Junliang

    Fuel cells are expected to be one of the major clean energy sources in the near future. However, the slow kinetics of electrocatalytic oxygen reduction reaction (ORR) and the high loading of Pt for the cathode material are the urgent issues to be addressed since they determine the efficiency and the cost of this energy source. In this study, a new approach was developed for designing electrocatalysts for the ORR in fuel cells. These electrocatalysts consist of only one Pt monolayer, or mixed transition metal-Pt monolayer, on suitable carbon-supported metal, or alloy nanoparticles. The synthesis involved depositing a monolayer of Cu on a suitable transition metal or metal alloy surface at underpotentials, followed by galvanic displacement of the Cu monolayer with Pt or mixed metal-Pt. It was found that the electronic properties of Pt monolayer could be fine-tuned by the electronic and geometric effects introduced by the substrate metal (or alloy) and the lateral effects of the neighboring metal atoms. The role of substrates was found reflected in a "volcano" plot of the monolayer activity for the ORR as a function of their calculated d-band centers. The Pt mass-specific activity of the new Pt monolayer electrocatalysts was up to twenty times higher than the state-of-the-art commercial Pt/C catalysts. The enhancement of the activity is caused mainly by decreased formation of PtOH (the blocking species for ORR), and to a lesser degree by the electronic effects. Fuel cell tests showed a very good long term stability of the new electrocatalysts. Our results demonstrated a viable way to designing the electrocatalysts which could successfully alleviate two issues facing the commercialization of fuel cells---the costs of electrocatalysts and their efficiency.

  8. Rhodium-catalyzed oxygenative [2 + 2] cycloaddition of terminal alkynes and imines for the synthesis of β-lactams.

    PubMed

    Kim, Insu; Roh, Sang Weon; Lee, Dong Gil; Lee, Chulbom

    2014-05-02

    A rhodium-catalyzed oxygenative [2 + 2] cycloaddition of terminal alkynes and imines has been developed, which gives β-lactams as products with high trans diastereoselectivity. In the presence of a Rh(I) catalyst and 4-picoline N-oxide, a terminal alkyne is converted to a rhodium ketene species via oxidation of a vinylidene complex and subsequently undergoes a [2 + 2] cycloaddition with an imine to give rise to the 2-azetidinone ring system. Mechanistic studies suggest that the reaction proceeds through a metalloketene rather than free ketene intermediate. The new method taking advantage of catalytic generation of a ketene species directly from a terminal alkyne provides a novel and efficient entry to the Staudinger synthesis of β-lactams under mild conditions.

  9. Structural study of the X-ray-induced enzymatic reduction of molecular oxygen to water by Steccherinum murashkinskyi laccase: insights into the reaction mechanism.

    PubMed

    Polyakov, K M; Gavryushov, S; Ivanova, S; Fedorova, T V; Glazunova, O A; Popov, A N; Koroleva, O V

    2017-05-01

    The laccase from Steccherinum murashkinskyi is a member of the large family of multicopper oxidases that catalyze the oxidation of a wide range of organic and inorganic substrates, accompanied by the reduction of dioxygen to water. The reducing properties of X-ray radiation and the high quality of the laccase crystals allow the study of the catalytic reduction of dioxygen to water directly in a crystal. A series of diffraction data sets with increasing absorbed radiation dose were collected from a single crystal of Steccherinum murashkinskyi laccase at 1.35 Å resolution. Changes in the active-site structure associated with the reduction of molecular oxygen to water on increasing the absorbed dose of ionizing radiation were detected. The structures in the series are mixtures of different states of the enzyme-substrate complex. Nevertheless, it was possible to interpret these structures as complexes of various oxygen ligands with copper ions in different oxidation states. The results allowed the mechanism of oxygen reduction catalyzed by laccases to be refined.

  10. Lipoxygenase-catalyzed oxygenation of storage lipids is implicated in lipid mobilization during germination.

    PubMed Central

    Feussner, I; Wasternack, C; Kindl, H; Kühn, H

    1995-01-01

    The etiolated germination process of oilseed plants is characterized by the mobilization of storage lipids, which serve as a major carbon source for the seedling. We found that during early stages of germination in cucumber, a lipoxygenase (linoleate: oxygen oxidoreductase, EC 1.13.11.12) form is induced that is capable of oxygenating the esterified fatty acids located in the lipid-storage organelles, the so-called lipid bodies. Large amounts of esterified (13S)-hydroxy-(9Z,11E)-octadecadienoic acid were detected in the lipid bodies, whereas only traces of other oxygenated fatty acid isomers were found. This specific product pattern confirms the in vivo action of this lipoxygenase form during germination. Lipid fractionation studies of lipid bodies indicated the presence of lipoxygenase products both in the storage triacylglycerols and, to a higher extent, in the phospholipids surrounding the lipid stores as a monolayer. The degree of oxygenation of the storage lipids increased drastically during the time course of germination. We show that oxygenated fatty acids are preferentially cleaved from the lipid bodies and are subsequently released into the cytoplasm. We suggest that they may serve as substrate for beta-oxidation. These data suggest that during the etiolated germination, a lipoxygenase initiates the mobilization of storage lipids. The possible mechanisms of this implication are discussed. PMID:11607617

  11. 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.

  12. A new method to prevent degradation of lithium-oxygen batteries: reduction of superoxide by viologen.

    PubMed

    Yang, L; Frith, J T; Garcia-Araez, N; Owen, J R

    2015-01-31

    Lithium-oxygen battery development is hampered by degradation reactions initiated by superoxide, which is formed in the pathway of oxygen reduction to peroxide. This work demonstrates that the superoxide lifetime is drastically decreased upon addition of ethyl viologen, which catalyses the reduction of superoxide to peroxide.

  13. 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.

  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. 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.

  16. Effects of Ca2+ and sulfhydryl reductant on the polymerization of soybean glycinin catalyzed by mammalian and microbial transglutaminases.

    PubMed

    Zhang, Guoyan; Matsumura, Yasuki; Matsumoto, Shinya; Hayashi, Yukako; Mori, Tomohiko

    2003-01-01

    Two types of transglutaminases (TGases), Ca(2+)-dependent TGase derived from guinea pig liver (GTGase) and Ca(2+)-independent TGase derived from a variant of Streptoverticillium mobaraense (MTGase), were used to study the cross-linking of soybean 11S globulin (glycinin). The effects of sulfhydryl reductant (dithiothreitol, DTT) and Ca(2+) on the conformation and TGase-catalyzed polymerization of glycinin were investigated. The conformational change of glycinin was probed by spectral methods. The degree of cross-linking and the polymer (aggregate) formation were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and dynamic light scattering, respectively. Addition of DTT stimulated the TGase-catalyzed cross-linking reactions without destroying the secondary and tertiary structure of glycinin but did not influence the polymer or aggregate formation. It was found that Ca(2+) caused the formation of larger size polymers at lower concentrations, while it suppressed the polymerization at higher concentrations. In addition, the cross-linking behaviors of glycinin were shown to be different between MTGase- and GTGase-catalyzed systems.

  17. Synthesis of trans-disubstituted alkenes by cobalt-catalyzed reductive coupling of terminal alkynes with activated alkenes.

    PubMed

    Mannathan, Subramaniyan; Cheng, Chien-Hong

    2012-09-10

    A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. 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).

  19. 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

  20. 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

    2014-05-27

    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.

  1. Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols.

    PubMed

    Riduan, Siti Nurhanna; Ying, Jackie Y; Zhang, Yugen

    2012-04-06

    A simple protocol for the stereoselective copper-catalyzed hydrothiolation of alkynes under a CO(2) atmosphere has been developed. The stereoselectivity is determined by the presence/absence of a CO(2) atmosphere. The reaction system is robust and utilizes inexpensive, readily available substrates. A cyclic alkene/carboxylate copper complex intermediate is proposed as the key step in determining the stereoselectivity, and an equivalent amount of water is found to play an active role as a proton donor.

  2. Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of Unsaturated Carbohydrates.

    PubMed

    Bender, Trandon A; Dabrowski, Jennifer A; Zhong, Hongyu; Gagné, Michel R

    2016-08-19

    A B(C6F5)3-catalyzed method for the selective conversion of unsaturated carbohydrates to cyclopentanes and cyclopropanes is disclosed. Catalyst activation of tertiary silanes generates the ion pair [(C6F5)3B-H][ROSi2] whose components synergistically activate C-O bonds for diastereoselective C-C bond formation. Sila-THF cations are invoked as key intermediates facilitating carbocyclizations. Complex chiral synthons are thereby obtained in a single pot.

  3. Facile synthesis of fluoroalkenes by palladium-catalyzed reductive defluorination of allylic gem-difluorides.

    PubMed

    Narumi, Tetsuo; Tomita, Kenji; Inokuchi, Eriko; Kobayashi, Kazuya; Oishi, Shinya; Ohno, Hiroaki; Fujii, Nobutaka

    2007-08-16

    Chemo- and stereoselective synthesis of fluoroalkenes was achieved in excellent yields via Pd-catalyzed C-F bond activation. In this transformation, Et3N plays a crucial role to produce reactive hydride species such as Ph(EtO)SiH2 and Ph(EtO)2SiH by promoting dehydrogenative coupling. The reaction proceeds efficiently at 50 degrees C with a variety of substrates and is also useful for the synthesis of fluoroalkene peptidomimetics.

  4. 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

  5. Glucose as a clean and renewable reductant in the Pd-nanoparticle-catalyzed reductive homocoupling of bromo- and chloroarenes in water.

    PubMed

    Monopoli, Antonio; Calò, Vincenzo; Ciminale, Francesco; Cotugno, Pietro; Angelici, Carlo; Cioffi, Nicola; Nacci, Angelo

    2010-06-04

    An efficient and highly sustainable Ullmann-type homocoupling of bromo- and chloroarenes, including the more challenging electron-rich chloroarenes (e.g., 4-chloroanisole), catalyzed by in situ generated Pd colloids, is carried out in aqueous medium under relatively mild conditions (temperatures ranging from 40 to 90 degrees C). Glucose is used as a clean and renewable reductant, while tetrabutylammonium hydroxide (TBAOH) acts as base, surfactant, and phase-transfer agent, creating a favorable environment for the catalyst. Pd nanoparticle sizes, morphology, and chemical composition are ascertained by TEM and XPS analyses.

  6. 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.

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

    DOE PAGES

    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

  8. 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

  9. Boron-Catalyzed Silylative Reduction of Nitriles in Accessing Primary Amines and Imines.

    PubMed

    Gandhamsetty, Narasimhulu; Jeong, Jinseong; Park, Juhyeon; Park, Sehoon; Chang, Sukbok

    2015-07-17

    Silylative reduction of nitriles was studied under transition metal-free conditions by using B(C6F5)3 as a catalyst with hydrosilanes as a reductant. Alkyl and (hetero)aryl nitriles were efficiently converted to primary amines or imines under mild conditions. The choice of silanes was found to determine the selectivity: while a full reduction of nitriles was highly facile, the use of sterically bulky silanes allowed for the partial reduction leading to N-silylimines.

  10. 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

  11. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    PubMed

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  12. Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: development of the method and mechanistic investigations.

    PubMed

    Harris, Jason R; Haynes, M Taylor; Thomas, Andrew M; Woerpel, K A

    2010-08-06

    A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with (17)O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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.

  15. 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.

  16. Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

    SciTech Connect

    Gao, Yongjun; Tang, Pei; Zhou, Hu; Zhang, Wei; Yang, Hanjun; Yan, Ning; Hu, Gang; Mei, Donghai; Wang, Jianguo; Ma, Ding

    2016-02-24

    A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giant π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.

  17. Ultraviolet irradiation-dependent fluorescence enhancement of hemoglobin catalyzed by reactive oxygen species.

    PubMed

    Pan, Leiting; Wang, Xiaoxu; Yang, Shuying; Wu, Xian; Lee, Imshik; Zhang, Xinzheng; Rupp, Romano A; Xu, Jingjun

    2012-01-01

    Ultraviolet (UV) light has a potent effect on biological organisms. Hemoglobin, an oxygen-transport protein, plays an irreplaceable role in sustaining life of all vertebrates. In this study we scrutinize the effects of ultraviolet irradiation (UVI) as well as visible irradiation on the fluorescence characteristics of bovine hemoglobin (BHb) in vitro. Data show that UVI results in fluorescence enhancement of BHb in a dose-dependent manner. Furthermore, UVI-induced fluorescence enhancement is significantly increased when BHb is pretreated with hydrogen peroxide (H(2)O(2)), a type of reactive oxygen species (ROS). Meanwhile, The water-soluble antioxidant vitamin C suppresses this UVI-induced fluorescence enhancement. In contrast, green light irradiation does not lead to fluorescence enhancement of BHb no matter whether H(2)O(2) is acting on the BHb solution or not. Taken together, these results indicate that catalysis of ROS and UVI-dependent irradiation play two key roles in the process of UVI-induced fluorescence enhancement of BHb.

  18. A Peroxygenase from Chaetomium globosum Catalyzes the Selective Oxygenation of Testosterone

    PubMed Central

    Schmidtke, Kai‐Uwe; Zimmermann, Jörg; Kellner, Harald; Jehmlich, Nico; Ullrich, René; Zänder, Daniel; Hofrichter, Martin; Scheibner, Katrin

    2017-01-01

    Abstract Unspecific peroxygenases (UPO, EC 1.11.2.1) secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less‐activated hydrocarbons, by transferring peroxide‐borne oxygen. We investigated a cell‐free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg−1. Although the well‐known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5‐epoxide of testosterone in β‐configuration and 16α‐hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules. PMID:28103392

  19. Reduction Kinetics of a CasO4 Based Oxygen Carrier for Chemical-Looping Combustion

    NASA Astrophysics Data System (ADS)

    Xiao, R.; Song, Q. L.; Zheng, W. G.; Deng, Z. Y.; Shen, L. H.; Zhang, M. Y.

    The CaSO4 based oxygen carrier has been proposed as an alternative low cost oxygen carrier for Chemical-looping combustion (CLC) of coal. The reduction of CaSO4 to CaS is an important step for the cyclic process of reduction/oxidation in CLC of coal with CaSO4 based oxygen carrier. Thermodynamic analysis of CaSO4 oxygen carrier with CO based on the principle of Gibbs free energy minimization show that the essentially high purity of CO2 can be obtained, while the solid product is CaS instead of CaO. The intrinsic reduction kinetics of a CaSO4 based oxygen carrier with CO was investigated in a differential fixed bed reactor. The effects of gas partial pressure (20%-70%) and temperature (880-950°C) on the reduction were investigated. The reduction was described with shrinking unreacted core model. Experimental results of CO partial pressure on the solid conversion show that the reduction of fresh oxygen carriers is of first order with respect to the CO partial pressure. Both chemical reaction control and product layer diffusion control determine the reduction rate. The dependences of reaction rate constant and effective diffusivity with temperature were both obtained. The kinetic equation well predicted the experimental data.

  20. Lisicon Glass-Ceramics Mediated Catalysis of Oxygen Reduction

    DTIC Science & Technology

    2011-06-01

    oxygen. In this context, the Lisicon structure resembles the structure of well-known zeolites . It is conceivable that in addi- tion to an ability to...process followed by a nucleation and crystallization thermal treatments. Fu (Refs. 3 and 4) reported processing and characterization of lithium ion...CV measurements. Thermal characterization was conducted on approximately 10 mg of LAGP specimen using TGA (TA Instruments, model 2050). The specimens

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Cobalt-porphine catalyzed CO2 electro-reduction: a novel protonation mechanism.

    PubMed

    Yao, Cang Lang; Li, Jian Chen; Gao, Wang; Jiang, Qing

    2017-06-14

    The urgent need for artificially fixing CO2 calls for catalysts of high efficiency. The transition metal functionalized porphyrin (TMP) is one of the most important types of organic catalysts for CO2 reduction. However, the catalytic mechanisms of TMP in CO2 reduction still remain controversial. Starting from the previously neglected catalyst self-protonation model, we uncover a new CO2 reduction mechanism on cobalt-porphine, which involves an indirect proton transfer step occurring at the beginning of the reduction cycle. Based on this protonation mechanism, we demonstrate the different correlations between producing rate and pH for the formation of CO and methane, in good agreement with available experimental observations. Our results reveal how pH and potential affect the CO2 reduction process, providing important clues and insights for further optimization of TMP catalysts.

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

    PubMed

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

    2015-11-18

    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 β,β'-enones and substituted β,β'-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 Δ(5)-unsaturation are key controlling 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.

  8. 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

  9. Rhodium(II)-Catalyzed Asymmetric Sulfur(VI) Reduction of Diazo Sulfonylamidines

    PubMed Central

    Selander, Nicklas; Fokin, Valery V.

    2013-01-01

    Diazo sulfonylamidines readily undergo enantioselective oxygen transfer from sulfur to carbon atom in the presence of chiral rhodium(II) carboxylates resulting in chiral sulfinylamidines. This unusual asymmetric atom transfer “reduction” occurs rapidly under mild conditions, and sulfinylamidines are obtained in excellent yield. PMID:22233190

  10. Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

    PubMed Central

    Rainka, Matthew P.; Aye, Yimon; Buchwald, Stephen L.

    2004-01-01

    A chiral copper-hydride catalyst for the asymmetric conjugate reduction of α,β-unsaturated carbonyl compounds has been used for the reduction of substrates containing β-nitrogen substituents. A new set of reaction conditions has allowed for a variety of β-azaheterocyclic acid derivatives to be synthesized in excellent yields and with high degrees of enantioselectivity. In addition, the effect that the nature of the nitrogen substituent has on the rate of the conjugate reduction reaction has been explored. PMID:15067136

  11. Pd(0)-Catalyzed PMHS reductions of aromatic acid chlorides to aldehydes.

    PubMed

    Lee, Kyoungsoo; Maleczka, Robert E

    2006-04-27

    [reaction: see text] Contrary to previous reports, polymethylhydrosiloxane (PMHS) under Pd(0) catalysis can efficiently reduce aryl acid chlorides to their corresponding aldehydes without requiring an additional reductant, provided the reactions are run in the presence of fluoride.

  12. 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.

  13. Oxygen dependence of the reduction of nitroimidazoles in a radiolytic model system

    SciTech Connect

    Rauth, A.M.; McClelland, R.A.; Michaels, H.B.; Battistella, R.

    1984-08-01

    Radiation chemical reductions using e/sub aq//sup -/ and CO/sub 2//sup -/ have been carried out in the presence of oxygen with metronidazole, p-nitroacetophenone, misonidazole and three other 2-nitroimidazoles. Low concentrations of oxygen were found to effectively inhibit the reduction of the first two compounds while much higher concentrations of oxygen were required for all of the 2-nitroimidazoles. Kinetic modelling of the radiochemical system suggests that the explanation for the differences lies in different reactions of the nitro radical anions; it appears that the anion derived from metronidazole undergoes disproportionation while that derived from misonidazole undergoes a unimolecular decay.

  14. Nitrogen Doping in Oxygen-Deficient Ca2Fe2O5: A Strategy for Efficient Oxygen Reduction Oxide Catalysts.

    PubMed

    Jijil, Chamundi P; Lokanathan, Moorthi; Chithiravel, Sundaresan; Nayak, Chandrani; Bhattacharyya, Dibyendu; Jha, Shambhu Nath; Babu, P D; Kakade, Bhalchandra; Devi, R Nandini

    2016-12-21

    Oxygen reduction reaction (ORR) is increasingly being studied in oxide systems due to advantages ranging from cost effectiveness to desirable kinetics. Oxygen-deficient oxides like brownmillerites are known to enhance ORR activity by providing oxygen adsorption sites. In parallel, nitrogen and iron doping in carbon materials, and consequent presence of catalytically active complex species like C-Fe-N, is also suggested to be good strategies for designing ORR-active catalysts. A combination of these features in N-doped Fe containing brownmillerite can be envisaged to present synergistic effects to improve the activity. This is conceptualized in this report through enhanced activity of N-doped Ca2Fe2O5 brownmillerite when compared to its oxide parents. N doping is demonstrated by neutron diffraction, UV-vis spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Electrical conductivity is also found to be enhanced by N doping, which influences the activity. Electrochemical characterization by cyclic voltammetry, rotating disc electrode, and rotating ring disk electrode (RRDE) indicates an improved oxygen reduction activity in N-doped brownmillerite, with a 10 mV positive shift in the onset potential. RRDE measurements show that the compound exhibits 4-electron reduction pathways with lower H2O2 production in the N-doped system; also, the N-doped sample exhibited better stability. The observations will enable better design of ORR catalysts that are stable and cost-effective.

  15. Oxygen reduction reaction on anisotropic silver nanoparticles in alkaline media

    NASA Astrophysics Data System (ADS)

    Gupta, Rajeev Kumar; Verma, A. D.; Sinha, I.; Malviya, Manisha

    2017-07-01

    The effect of anisotropy of Ag nanoparticles on their electrocatalytic activity was investigated. By using increasing amounts of Cu salt etchant, we could obtain two AgNPs samples (S1 and S2) with different percentages of anisotropic nanoparticles. The third AgNPs sample was synthesized in the absence of any etchant and therefore resulted in the formation of only spherical nanoparticles. Investigation of ORR activity in an alkaline solution of these AgNPs samples showed that the S1/GC electrode gives rise to better reduction peak current, more positive reduction peak potential and stable electrocatalytic performance. Better results for the S1/GC electrode as compared to S2/GC electrode & S3/GC electrode can be owed to a higher percentage of anisotropic nanoparticles in S1 sample.

  16. Leg oxygen uptake in the initial phase of intense exercise is slowed by a marked reduction in oxygen delivery.

    PubMed

    Christensen, Peter M; Nyberg, Michael; Mortensen, Stefan P; Nielsen, Jens Jung; Secher, Niels H; Damsgaard, Rasmus; Hellsten, Ylva; Bangsbo, Jens

    2013-08-01

    The present study examined whether a marked reduction in oxygen delivery, unlike findings in moderate-intensity exercise, would slow leg oxygen uptake (Vo2) kinetics during intense exercise (86 ± 3% of incremental test peak power). Seven healthy males (26 ± 1 years, means ± SE) performed one-legged knee-extensor exercise (60 ± 3 W) for 4 min in a control setting (CON) and with arterial infusion of N(G)-monomethyl-l-arginine and indomethacin in the working leg to reduce blood flow by inhibiting formation of nitric oxide and prostanoids (double blockade; DB). In DB leg blood flow (LBF) and oxygen delivery during the first minute of exercise were 25-50% lower (P < 0.01) compared with CON (LBF after 10 s: 1.1 ± 0.2 vs. 2.5 ± 0.3 l/min and 45 s: 2.7 ± 0.2 vs. 3.8 ± 0.4 l/min) and 15% lower (P < 0.05) after 2 min of exercise. Leg Vo2 in DB was attenuated (P < 0.05) during the first 2 min of exercise (10 s: 161 ± 26 vs. 288 ± 34 ml/min and 45 s: 459 ± 48 vs. 566 ± 81 ml/min) despite a higher (P < 0.01) oxygen extraction in DB. Net leg lactate release was the same in DB and CON. The present study shows that a marked reduction in oxygen delivery can limit the rise in Vo2 during the initial part of intense exercise. This is in contrast to previous observations during moderate-intensity exercise using the same DB procedure, which suggests that fast-twitch muscle fibers are more sensitive to a reduction in oxygen delivery than slow-twitch fibers.

  17. Direct, Electrocatalytic Oxygen Reduction by Laccase on Anthracene-2-methanethiol Modified Gold.

    PubMed

    Thorum, Matthew S; Anderson, Cyrus A; Hatch, Jeremy J; Campbell, Andrew S; Marshall, Nicholas M; Zimmerman, Steven C; Lu, Yi; Gewirth, Andrew A

    2010-08-01

    Laccase, a multicopper oxidase, catalyses the four electron reduction of oxygen to water. Upon adsorption to an electrode surface, laccase is known to reduce oxygen at overpotentials lower than the best noble metal electrocatalysts usually employed. While the electrocatalytic activity of laccase is well established on carbon electrodes, laccase does not typically adsorb to better defined noble metal surfaces in an orientation that allows for efficient electrocatalysis. In this work, we utilized anthracene-2-methanethiol (AMT) to modify the surface of Au electrodes and examined the electrocatalytic activity of adsorbed laccase. AMT facilitated the adsorption of laccase, and the onset of electrocatalytic oxygen reduction was observed as high as 1.13 V(RHE). We observed linear Tafel behavior with a 144 mV/dec slope, consistent with an outer sphere single electron transfer from the electrode to a Cu site in the enzyme as the rate determining step of the oxygen reduction mechanism.

  18. 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.

  19. Participation of oxygen-free radicals in the oxido-reduction of proteins.

    PubMed

    Vilar-Rojas, C; Guzman-Grenfell, A M; Hicks, J J

    1996-01-01

    Recent studies have focused attention on the possible role of active oxygen species on protein damage and degradation. The reactions of free radicals on biomolecules are important in physiology and pathology. A number of systems that generate free radicals catalyze the oxidative modification of proteins in two species: protein peroxides, which can consume important antioxidants; and protein-bound reducing moieties, which can reduce transition metals, and may enhance their activity in radical reactions. Protein oxidation also contributes to the pool of damaged enzymes and accumulation of abnormal and damaged proteins, which increases during aging and in various pathological states, such as atherosclerosis, cancer, etc.

  20. Fluoride-Catalyzed Methylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes.

    PubMed

    Liu, Xiao-Fang; Ma, Ran; Qiao, Chang; Cao, Han; He, Liang-Nian

    2016-11-07

    An effective and inexpensive organocatalyst tetrabutylammonium fluoride (TBAF) was developed for the reductive functionalization of CO2 with amines to selectively afford formamides or methylamines by employing hydrosilanes. Hydrosilanes with different substituents show discriminatory reducing activity. Thus, the formation of formamides and further reduction products, that is, methylamines could be controlled by elegantly tuning hydrosilane types. Formamides were obtained exclusively under an atmospheric pressure of CO2 with triethoxysilane. Using phenylsilane as a reductant, methylamines were attained with up to 99 % yield at 50 °C coupled to a complete deoxygenation of CO2 . The crucial intermediate silyl formate in the formylation step was identified and thereby a tentative mechanism involving the fluoride-promoted hydride transfer from the hydrosilane to CO2 /formamide was proposed. Striking features of this metal-free protocol are formylation and methylation of amines by reductive functionalization of CO2 with hydrosilanes and mild reaction conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

    DOE PAGES

    Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.; ...

    2017-03-09

    In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO2 reduction ability. We reported complexes are of the type Re(N-N)(CO)3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO2 reduction by 1 in acetonitrile using density functional theory (DFT) supportsmore » the C–O bond cleavage step being the rate-determining step (RDS) (ΔG‡ = 27.2 kcal mol–1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO)3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (icat/ip)2, up to 7 times larger than that of I.« less

  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. Palladium-indium catalyzed reduction of N-nitrosodimethylamine: indium as a promoter metal.

    PubMed

    Davie, Matthew G; Shih, Kaimin; Pacheco, Federico A; Leckie, James O; Reinhard, Martin

    2008-04-15

    An emerging technology for the removal of N-nitrosodimethylamine (NDMA) from drinking and groundwater is reductive destruction using noble metal catalysts and hydrogen gas as a reducing agent. Bimetallic palladium-indium (Pd-In) supported on alumina combines the ability of Into activate NDMA with the hydrogen activating properties of Pd. This study examined the effect of In addition to a commercial 5% Pd by weight on gamma-Al2O3 catalyst on the efficacy of NDMA reduction. The pseudo-first-order rate constant increased proportionately to In loading from 0.057 h(-1) for 0% In to a maximum of 0.25 h(-1) for 1% In and then decreased with additional in loading. Data suggest that hydrogen activation occurred only on Pd surfaces and In activated NDMA 20 times more effectively than Pd on a mass basis. The rate-limiting factor was NDMA activation for In loadings below 1%. The decrease at higher loadings is interpreted as In blocking pore spaces and limiting access to Pd sites, suggesting monatomic hydrogen limitation. The only products detected were dimethylamine and ammonium with carbon and nitrogen balances in excess of 92%, consistent with a mechanism involving reductive N-N bond cleavage. Results from this study serve as a basis for optimizing bimetallic catalysts for treating NDMA contaminated waters.

  4. Asymmetric synthesis of tetrahydroquinolin-3-ols via CoCl2-catalyzed reductive cyclization of nitro cyclic sulfites with NaBH4.

    PubMed

    Jagdale, Arun R; Reddy, R Santhosh; Sudalai, Arumugam

    2009-02-19

    A new method for the construction of chiral 3-substituted tetrahydroquinoline derivatives based on asymmetric dihydroxylation and CoCl(2)-catalyzed reductive cyclization of nitro cyclic sulfites with NaBH(4) has been described with high optical purities. This method has been successfully applied in the formal synthesis of PNU 95666E and anachelin H chromophore.

  5. 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.

  6. 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

  7. Pyrolyzed cobalt phthalocyanine as electrocatalyst for oxygen reduction

    SciTech Connect

    Ladouceur, M.; Lalande, G.; Guay, D.; Dodelet, J.P. ); Dignard-Bailey, L. . Lab. de Recherche en Diversification Energetique); Trudeau, M.L.; Schulz, R. . Technologie des Materiaux)

    1993-07-01

    Cobalt phthalocyanine (CoPc) adsorbed on carbon black (XC-72) and heat-treated at temperature ranging from 300 to 1,150 C display catalytic activity toward the electroreduction of oxygen in acidic medium (H[sub 2]SO[sub 4],pH 0.5). The best catalysts are obtained for pyrolysis temperatures ranging from 700 to 950 C. X-ray diffraction performed on CoPc/XC-72 pyrolyzed between 700 and 1,150 C reveals the presence of [beta]-Co particles whose average size varies from 9 nm at 700 C to 44 nm at 1,150 C. Co and N bulk elemental analyses have been performed on CoPc/XC-72 heat-treated from 20 to 1,150 C. These show that: (1) there is no loss of Co even after pyrolysis at 1,150 C when the loading is at 2 weight percent (w/o) Co; (2) the bulk N content decreases as the pyrolysis temperatures are increased and the N content reaches the detection limit (0.5 w/o) at pyrolysis temperatures [>=] 1000 C. X-ray photoelectron spectroscopy (XPS) study shows that at 600 C there is a sudden three-fold increase in the surface concentration of Co and N at the surface of the carbon black support. A sublimation-redistribution of the CoPc is proposed. The effect appears to limit the Co loading to approximately 2 w/o (At loadings of 4 and 8 w/o Co, most of the Co is lost due to the sublimation.) The XPS study also shows that metallic Co particles begin to be formed at 600 C, and that the formation and growth of Co particles occurs as the pyrolysis temperature increases to 1,050 C. The chemical stability of the pyrolyzed catalysts was evaluated in concentrated H[sub 2]SO[sub 4],HCl, and HNO[sub 3] for time periods ranging from 1 to 30 min. Bulk Co analysis, after immersion in acid, indicate that up to 40% of the Co can be lost in the process, and that this induces a decrease in the catalyst activity.

  8. Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.

    PubMed

    Nguyen, Khoa D; Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Garza, Victoria J; Krische, Michael J

    2016-10-21

    α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond-forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition. Copyright © 2016, American Association for the Advancement of Science.

  9. Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Zeller, Robert August

    Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set

  10. Size-dependent production of radicals in catalyzed reduction of Eosin Y using gold nanorods

    NASA Astrophysics Data System (ADS)

    Weng, Guojun; Qi, Ying; Li, Jianjun; Zhao, Junwu

    2015-09-01

    Gold nanostructures have been widely used as catalysts for chemical processes, energy conversion, and pollution control. The size of gold nanocatalysts is thus paramount for their catalytic activity. In this paper, gold nanorods with different sizes were prepared by means of the improved seeding growth approach by adding aromatic additive. The sizes and aspect ratios of the obtained gold nanorods were calculated according to the TEM characterization. Then, we studied the catalytic activities of gold nanorods using a model reaction based on the reduction of Eosin Y by NaBH4. By monitoring the absorption intensities of the radicals induced by gold nanorods in real time, we observed the clear size-dependent activity in the conversion of EY2- to EY3-. The conversion efficiency indicated that the gold nanorods with the smallest size were catalytically the most active probably due to their high number of coordinatively unsaturated surface atoms. In addition, a compensation effect dominated by the surface area of nanorods was observed in this catalytic reduction, which could be primarily attributed to the configuration of Eosin Y absorbed onto the surfaces of gold nanorods.

  11. 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.

  12. An innovative method for oxidative degradation of chitosan with molecular oxygen catalyzed by metal phthalocyanine in neutral ionic liquid.

    PubMed

    Zhao, Xinhua; Kong, Aiguo; Hou, Yawei; Shan, Chongchong; Ding, Hanming; Shan, Yongkui

    2009-10-12

    A novel aqueous solution-ionic liquid biphasic catalytic system was established for the oxidative degradation of chitosan under mild conditions. In this process, the environmentally acceptable and inexpensive molecular oxygen was first used as oxidant, the metal phthalocyanine was immobilized in ionic liquid as catalyst, and the aqueous solution as medium carried the reactants and the products. Under vigorous stirring and heating, the reactants fully contacted the catalysts in the emulsion and chitosan efficiently degraded into water-soluble materials. At the end of the reaction, the catalytic system could be easily separated by simple decantation and could also be reused in subsequent runs without apparent change in activity. These characters are in favor of the elimination of pollution and the reduction of the economic cost in the large-scale production of the water-soluble chitosan derivatives in chemical industry.

  13. 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

  14. Effect of hydrogen peroxide and camellia sinensis extract on reduction of oxygen level in graphene oxide

    NASA Astrophysics Data System (ADS)

    Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.

    2016-10-01

    The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV-vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.

  15. Electrochemistry-mass spectrometry for mechanism study of oxygen reduction at water/oil interface

    NASA Astrophysics Data System (ADS)

    Liu, Shu-Juan; Yu, Zheng-Wei; Qiao, Liang; Liu, Bao-Hong

    2017-04-01

    Electrochemistry methods have been widely employed in the development of renewable energy, and involved in various processes, e.g. water splitting and oxygen reduction. Remarkable progress notwithstanding, there are still many challenges in further optimization of catalysts to achieve high performance. For this purpose, an in-depth understanding of reaction mechanism is needed. In this study, an electrochemistry-mass spectrometry method based on a Y-shaped dual-channel microchip as electrochemical cell and ionization device was demonstrated. Combined solutions of aqueous phase and oil phase were introduced into mass spectrometer directly when electrochemical reactions were happening to study the reduction of oxygen by decamethylferrocene or tetrathiafulvalene under the catalysis of a metal-free porphyrin, tetraphenylporphyrin, at water/1,2-dichloroethane interfaces. Monoprotonated and diprotonated tetraphenylporphyrin were detected by mass spectrometer, confirming the previously proposed mechanism of the oxygen reduction reaction. This work offers a new approach to study electrochemical reactions at liquid-liquid interface.

  16. 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

  17. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells.

    PubMed

    Qu, Liangti; Liu, Yong; Baek, Jong-Beom; Dai, Liming

    2010-03-23

    Nitrogen-doped graphene (N-graphene) was synthesized by chemical vapor deposition of methane in the presence of ammonia. The resultant N-graphene was demonstrated to act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction via a four-electron pathway in alkaline fuel cells. To the best of our knowledge, this is the first report on the use of graphene and its derivatives as metal-free catalysts for oxygen reduction. The important role of N-doping to oxygen reduction reaction (ORR) can be applied to various carbon materials for the development of other metal-free efficient ORR catalysts for fuel cell applications, even new catalytic materials for applications beyond fuel cells.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. Replacing conventional carbon nucleophiles with electrophiles: nickel-catalyzed reductive alkylation of aryl bromides and chlorides.

    PubMed

    Everson, Daniel A; Jones, Brittany A; Weix, Daniel J

    2012-04-11

    A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO(2)Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe(3)), and organosilicon (-SiMe(2)OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents. © 2012 American Chemical Society

  3. Replacing Conventional Carbon Nucleophiles with Electrophiles: Nickel-Catalyzed Reductive Alkylation of Aryl Bromides and Chlorides

    PubMed Central

    2012-01-01

    A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (−OH, −NHTs, −OAc, −OTs, −OTf, −COMe, −NHBoc, −NHCbz, −CN, −SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki–Miyaura, Stille, and Hiyama–Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R–X) and no reaction at the nucleophilic carbon (R–[M]) for organoboron (−Bpin), organotin (−SnMe3), and organosilicon (−SiMe2OH) containing organic halides (X–R–[M]). A Hammett study showed a linear correlation of σ and σ(−) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2–1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents. PMID:22463689

  4. Catalytic characteristics of AgCu bimetallic nanoparticles in the oxygen reduction reaction.

    PubMed

    Shin, Kihyun; Kim, Da Hye; Lee, Hyuck Mo

    2013-06-01

    Intensive research on oxygen reduction reaction (ORR) catalysts has been undertaken to find a Pt substitute or reduce the amount of Pt. Ag nanoparticles are potential Pt substitutes; however, the weak oxygen adsorption energy of Ag prompted investigation of other catalysts. Herein, we prepared AgCu bimetallic nanoparticle (NP) systems to improve the catalytic performance and compared the catalytic performance of Ag, Cu, AgCu (core-shell), and AgCu (alloy) NP systems as new catalyst by investigating the adsorption energy of oxygen and the activation energy of oxygen dissociation, which is known to be the rate-determining step of ORR. By analyzing HOMO-level isosurfaces of metal NPs and oxygen, we found that the adsorption sites and the oxygen adsorption energies varied with different configurations of NPs. We then plotted the oxygen adsorption energies against the energy barrier of oxygen dissociation to determine the catalytic performance. AgCu (alloy) and Cu NPs exhibited strong adsorption energies and low activation-energy barriers. However, the overly strong oxygen adsorption energy of Cu NPs hindered the ORR. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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

  6. 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.

  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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. Enhanced Activity and Stability of Pt catalysts on Functionalized Graphene Sheets for Electrocatalytic Oxygen Reduction

    SciTech Connect

    Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chong M.; Lin, Yuehe; Wang, Yong; Aksay, Ilhan A.; Liu, Jun

    2009-04-30

    Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets.

  13. Pd-Pt Alloy with Coral-Like Nanostructures Showing High Performance for Oxygen Electrocatalytic Reduction.

    PubMed

    Liu, Xing-Quan; Chen, Xue-Song; Wu, Jian; Yao, Lei

    2016-03-01

    Three-dimensional (3D) Pd-Pt alloy with coral-like nanostructures were synthesized via bubble dynamic templated electrodeposition method at room temperature. The morphology of the as-prepared nanostructures was characterized using scanning electron microscopy (SEM), EDS, high-resolution transmission electron microscopy (HRTEM), respectively. Cyclic voltammetry method was adopted to evaluate the electrocatalytic activities of the synthesized electrodes toward oxygen reduction in KCl solution. The electrochemical results indicated that the Pd-Pt alloy with coral-like nanostructures hold the high performance for oxygen reduction.

  14. 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

  15. Gold-catalyzed hydrative carbocyclization of 1,5- and 1,6-diyn-3-ones via an oxygen transfer process.

    PubMed

    Tang, Jhih-Meng; Liu, Ting-An; Liu, Rai-Shung

    2008-11-07

    This study reports new hydrative carbocyclizations of 1,5- and 1,6-diyn-3-ones catalyzed by PPh3AuOTf, involving a pi-alkyne-assisted oxygen transfer in the reaction mechanisms. Treatment of 2-(alk-2-yn-1-onyl)-1-alkynylbenzenes with PPh3AuOTf (5 mol %) in wet 1,4-dioxane (23 degrees C, 10 min) led to hydrative aromatization to give 4-hydroxyl-1-naphthyl ketones efficiently. This approach is also extendible to the hydrative cyclization of acyclic 1,5-diyn-3-ones, which afforded 4-cyclopentenonyl ketones in reasonable yields. On the basis of this oxygen-labeling study, we propose a plausible mechanism involving an alkyne-assisted oxygen transfer to generate key oxonium and gold-enolate intermediates.

  16. 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.

  17. Enzyme-catalyzed modification of PES surfaces: reduction in adsorption of BSA, dextrin and tannin.

    PubMed

    Nady, Norhan; Schroën, Karin; Franssen, Maurice C R; Fokkink, Remco; Mohy Eldin, Mohamed S; Zuilhof, Han; Boom, Remko M

    2012-07-15

    Poly(ethersulfone) (PES) can be modified in a flexible manner using mild, environmentally benign components such as 4-hydroxybenzoic acid and gallic acid, which can be attached to the surface via catalysis by the enzyme laccase. This leads to grafting of mostly linear polymeric chains (for 4-hydroxybenzoic acid, and for gallic acid at low concentration and short modification time) and of networks (for gallic acid at high concentration and long exposure time). The reaction is stopped at a specific time, and the modified surfaces are tested for adsorption of BSA, dextrin and tannin using in-situ reflectometry and AFM imaging. At short modification times, the adsorption of BSA, dextrin and tannin is significantly reduced. However, at longer modification times, the adsorption increases again for both substrates. As the contact angle on modified surfaces at short modification times is reduced (indicative of more hydrophilic surfaces), and keeps the same low values at longer modification times, hydrophilicity is not the only determining factor for the measured differences. At longer modification times, intra-layer reactivity will increase the amount of cross-linking (especially for gallic acid), branching (for 4-hydroxybenzoic acid) and/or collapse of the polymer chains. This leads to more compact layers, which leads to increased protein adsorption. The modifications were shown to have clear potential for reduction of fouling by proteins, polysaccharides, and polyphenols, which could be related to the surface morphology.

  18. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates.

    PubMed

    Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N; Vajtai, Robert; Yu, Aaron Z; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J A; Ajayan, Pulickel M

    2016-12-13

    Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

  19. 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.

  20. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

    NASA Astrophysics Data System (ADS)

    Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, Chandrasekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

    2016-12-01

    Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

  1. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

    PubMed Central

    Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

    2016-01-01

    Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts. PMID:27958290

  2. Phosphate Shifted Oxygen Reduction Pathway on Fe@Fe2O3 Core-Shell Nanowires for Enhanced Reactive Oxygen Species Generation and Aerobic 4-Chlorophenol Degradation.

    PubMed

    Mu, Yi; Ai, Zhihui; Zhang, Lizhi

    2017-07-18

    Phosphate ions widely exist in the environment. Previous studies revealed that the adsorption of phosphate ions on nanoscale zerovalent iron would generate a passivating oxide shell to block reactive sites and thus decrease the direct pollutant reduction reactivity of zerovalent iron. Given that molecular oxygen activation process is different from direct pollutant reduction with nanoscale zerovalent iron, it is still unclear how phosphate ions will affect molecular oxygen activation and reactive oxygen species generation with nanoscale zerovalent iron. In this study, we systematically studied the effect of phosphate ions on molecular oxygen activation with Fe@Fe2O3 nanowires, a special nanoscale zerovalent iron, taking advantages of rotating ring disk electrochemical analysis. It was interesting to find that the oxygen reduction pathway on Fe@Fe2O3 nanowires was gradually shifted from a four-electron reduction pathway to a sequential one-electron reduction one, along with increasing the phosphate ions concentration from 0 to 10 mmol·L(-1). This oxygen reduction pathway change greatly enhanced the molecular oxygen activation and reactive oxygen species generation performances of Fe@Fe2O3 nanowires, and thus increased their aerobic 4-chlorophenol degradation rate by 10 times. These findings shed insight into the possible roles of widely existed phosphate ions in molecular oxygen activation and organic pollutants degradation with nanoscale zerovalent iron.

  3. 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.

  4. Electrochemical Investigations on Graphene and Lithium Phthalocyanine as Catalysts for Reversible Oxygen Reduction Reaction in Li-O2 Cells

    DTIC Science & Technology

    2015-05-11

    phthalocyanine as catalysts for reversible oxygen reduction reaction in Li-O2 cells 5a. CONTRACT NUMBER FA2386-13-1-4006 5b. GRANT NUMBER Grant...Electrochemical investigations on graphene and lithium phthalocyanine as catalysts for reversible oxygen reduction reaction in Li-O2 cells 5a...catalysts for reversible oxygen reduction reaction in Li-O2 cells (FA2386-13-1-4006) Final Report Submitted to: Asian Office of Aerospace

  5. 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

  6. In vacuo reduction of silver orthophosphate with graphite for high-precision oxygen isotope analysis.

    PubMed

    Pelc, Andrzej; Halas, Stanislaw

    2010-10-15

    The reduction of silver phosphate with graphite under vacuum conditions was studied at final reaction temperatures varying from 430 to 915°C to determine: (i) the CO(2) extraction yield, and (ii) the oxygen isotopic composition of CO(2). The CO(2) yield and oxygen isotopic composition were determined on a calibrated dual inlet and triple collector isotope ratio mass spectrometer. We observed the following three stages of the reduction process. (1) At temperatures below 590°C only CO(2) is formed, while silver orthophosphate decays to pyrophosphate. (2) At higher temperatures, 590-830°C, predominantly CO is formed from silver pyrophosphate which decays to metaphosphate; this CO was always converted into CO(2) by the glow discharge method. (3) At temperatures above 830°C the noticeable sublimation of silver orthophosphate occurs. This observation was accompanied by the oxygen isotope analysis of the obtained CO(2). The measured δ(18)O value varied from -11.93‰ (at the lowest temperature) to -20.32‰ (at the highest temperature). The optimum reduction temperature range was found to be 780-830°C. In this temperature range the oxygen isotopic composition of CO(2) is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ(18)O value of oxygen in silver phosphate and that in CO(2) extracted from this phosphate is +0.70‰. Copyright © 2010 John Wiley & Sons, Ltd.

  7. Compositional engineering of perovskite oxides for highly efficient oxygen reduction reactions.

    PubMed

    Chen, Dengjie; Chen, Chi; Zhang, Zhenbao; Baiyee, Zarah Medina; Ciucci, Francesco; Shao, Zongping

    2015-04-29

    Mixed conducting perovskite oxides are promising catalysts for high-temperature oxygen reduction reaction. Pristine SrCoO(3-δ) is a widely used parent oxide for the development of highly active mixed conductors. Doping a small amount of redox-inactive cation into the B site (Co site) of SrCoO(3-δ) has been applied as an effective way to improve physicochemical properties and electrochemical performance. Most findings however are obtained only from experimental observations, and no universal guidelines have been proposed. In this article, combined experimental and theoretical studies are conducted to obtain fundamental understanding of the effect of B-site doping concentration with redox-inactive cation (Sc) on the properties and performance of the perovskite oxides. The phase structure, electronic conductivity, defect chemistry, oxygen reduction kinetics, oxygen ion transport, and electrochemical reactivity are experimentally characterized. In-depth analysis of doping level effect is also undertaken by first-principles calculations. Among the compositions, SrCo0.95Sc0.05O(3-δ) shows the best oxygen kinetics and corresponds to the minimum fraction of Sc for stabilization of the oxygen-vacancy-disordered structure. The results strongly support that B-site doping of SrCoO(3-δ) with a small amount of redox-inactive cation is an effective strategy toward the development of highly active mixed conducting perovskites for efficient solid oxide fuel cells and oxygen transport membranes.

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

    SciTech Connect

    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. 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.

  9. Synthesis and oxygen reduction properties of three-dimensional sulfur-doped graphene networks.

    PubMed

    Zhang, Yijia; Chu, Mi; Yang, Lu; Deng, Wenfang; Tan, Yueming; Ma, Ming; Xie, Qingji

    2014-06-18

    Novel three-dimensional sulfur-doped graphene networks were synthesized using an ion-exchange/activation combination method using a 732-type sulfonic acid ion exchange resin as the carbon precursor, which showed high electrocatalytic activity, good stability and excellent methanol tolerance for four-electron oxygen reduction in alkaline solution.

  10. A universal method to synthesize nanoscale carbides as electrocatalyst supports towards oxygen reduction reaction.

    PubMed

    He, Guoqiang; Yan, Zaoxue; Ma, Xueming; Meng, Hui; Shen, Pei Kang; Wang, Chengxin

    2011-09-01

    We have developed a general ion-exchange method of preparing a composite of low nanometre size carbide particles with controllable size less than 10 nm on carbon foams. The nanoarchitectures of the carbide nanoparticles on carbon foam are used to load Pt nanoparticles as electrocatalysts which show enhanced activity for the oxygen reduction reaction.

  11. Efficient oxygen reduction catalysts formed of cobalt phosphide nanoparticle decorated heteroatom-doped mesoporous carbon nanotubes.

    PubMed

    Chen, Kuiyong; Huang, Xiaobin; Wan, Chaoying; Liu, Hong

    2015-05-07

    Oxygen reduction catalysts based on heteroatom-doped mesoporous carbon nanotubes loaded with Co2P nanoparticles were skilfully fabricated. The electronic interaction between the embedded Co2P nanoparticles and the heteroatom-doped carbon structures could strongly promote the ORR catalytic performance of the heteroatom-doped carbon nanotubes.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Elevated Pb(II) release from the reduction of Pb(IV) corrosion product PbO2 induced by bromide-catalyzed monochloramine decomposition.

    PubMed

    Zhang, Yuanyuan; Lin, Yi-Pin

    2013-10-01

    The stability of Pb(IV) corrosion product PbO2 has been linked to lead contamination in chloraminated drinking water. Recent studies have shown that autodecomposition of monochloramine (NH2Cl) can cause lead release from PbO2 via reductive dissolution. Bromide (Br(-)) is a known catalyst for NH2Cl decomposition. In this study, we investigated whether Br(-)-catalyzed NH2Cl decomposition could further enhance lead release from PbO2. Our results showed that Br(-_)catalyzed NH2Cl decomposition did accelerate the reduction of PbO2, and the rate was enhanced by the lower pH value, higher Br(-), and NH2Cl concentrations. A single linear correlation was found between the amount of NH2Cl decomposed and the amount of total Pb(II) released either in the absence or presence of Br(-), suggesting that Br(-)-catalyzed NH2Cl decomposition and NH2Cl autodecomposition may generate the same intermediate toward PbO2 reduction. The kinetics of total Pb(II) release can be successfully modeled by considering the overall rate of NH2Cl decomposition with NOH as the reactive intermediate responsible for PbO2 reduction. Our findings suggested that special attentions on lead contamination should be paid to systems with PbO2 scales and high Br(-)-containing source waters when switching disinfectant from free chlorine to monochloramine.

  17. 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.

  18. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    PubMed Central

    Hassan, Diab; El-safty, Sherif; Khalil, Khalil Abdelrazek; Dewidar, Montasser; Abu El-magd, Gamal

    2016-01-01

    The design of cheap and efficient oxygen reduction reaction (ORR) electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies. PMID:28773878

  19. 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

  20. 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.

  1. Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway.

    PubMed

    Poux, Tiphaine; Bonnefont, Antoine; Kéranguéven, Gwénaëlle; Tsirlina, Galina A; Savinova, Elena R

    2014-07-21

    The mechanism of the oxygen reduction reaction (ORR) on LaCoO(3) and La(0.8)Sr(0.2)MnO(3) perovskite oxides is studied in 1 M NaOH by using the rotating ring disc electrode (RRDE) method. By combining experimental studies with kinetic modeling, it was demonstrated that on perovskite, as well as on perovskite/carbon electrodes, the ORR follows a series pathway through the intermediate formation of hydrogen peroxide. The escape of this intermediate from the electrode strongly depends on: 1) The loading of perovskite; high loadings lead to an overall 4 e(-) oxygen reduction due to efficient hydrogen peroxide re-adsorption on the active sites and its further reduction. 2) The addition of carbon to the catalytic layer, which affects both the utilization of the perovskite surface and the production of hydrogen peroxide. 3) The type of oxide; La(0.8)Sr(0.2)MnO(3) displays higher (compared to LaCoO(3)) activity in the reduction of oxygen to hydrogen peroxide and in the reduction/oxidation of the latter.

  2. 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.

  3. 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

  4. Diastereoselective Synthesis of syn-β-Lactams Using Rh-Catalyzed Reductive Mannich-Type Reaction of α,β-Unsaturated Esters.

    PubMed

    Isoda, Motoyuki; Sato, Kazuyuki; Funakoshi, Masato; Omura, Keiko; Tarui, Atsushi; Omote, Masaaki; Ando, Akira

    2015-08-21

    The combination of Et2Zn and RhCl(PPh3)3 led to the facile generation of a rhodium-hydride complex (Rh-H) that catalyzed the 1,4-reduction of α,β-unsaturated esters. The resulting rhodium enolate performed as a Reformatsky-type reagent and reacted with various imines to give syn-β-lactams in good to excellent yields with high diastereoselectivity.

  5. 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

    2015-10-12

    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.

  6. 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

  7. Provocative intraocular pressure challenge preferentially decreases venous oxygen saturation despite no reduction in blood flow.

    PubMed

    O'Connell, Rachael A; Anderson, Andrew J; Hosking, Sarah L; Bui, Bang V

    2015-03-01

    Ocular disease can both alter the retina's oxygen requirements, and decrease its ability to cope with changes in metabolic demand. We examined the influence of a moderate intraocular pressure (IOP) elevation on three outcome measures: arterial and venous oxygen saturation, blood flow, and the pattern electroretinogram (PERG). We increased IOP to ˜30 mmHg in 23 healthy participants (22-39 years) using a mechanical probe applied to the eyelid, thereby lowering ocular perfusion pressure (OPP) by ~30%. The Oxymap retinal oximeter was used to measure oxygen saturation for arteries and veins. Blood flow, volume and velocity were measured using the Heidelberg retinal flowmeter and steady-state PERG waveforms (8.34 Hz) were recorded bilaterally (200 sweeps). For each outcome measure, data was obtained three times: at baseline, 1 min into sustained IOP elevation, and 1 min after the probe was removed. During IOP elevation, changes in oxygen saturation of retinal arteries failed to reach statistical significance [F(1,30) = 3.69, p = 0.05], whereas venous oxygen saturation was significantly reduced [F(1,21) = 27.43, p < 0.01]. Blood flow increased slightly [F(2,40) = 6.28, p < 0.0001], PERG amplitude significantly reduced [F(2,44) = 24.24, p < 0.0001] and PERG phase was significantly delayed [F(2,44) = 17.00, p < 0.0001]. Contralateral eyes were unchanged. OPP reduction correlated little with PERG amplitude, PERG phase or venous oxygen saturation. Mild, acute IOP elevation increases arterio-venous oxygen saturation differences primarily through lowering venous oxygen saturation, suggesting increased oxygen consumption by healthy neurons when physiologically stressed. © 2014 The Authors Ophthalmic & Physiological Optics © 2014 The College of Optometrists.

  8. 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

  9. Oxygen and sulfur isotope fractionation during methane dependent sulfate reduction in high pressure continuous incubation studies

    NASA Astrophysics Data System (ADS)

    Deusner, C.; Brunner, B.; Holler, T.; Widdel, F.; Ferdelman, T. G.

    2009-12-01

    The anaerobic oxidation of methane (AOM) coupled to sulfate reduction in marine sediments is an important sink in the global methane budget. However, many aspects of methane dependent sulfate reduction are not fully understood. We developed a novel high pressure biotechnical system to simulate marine conditions with high concentrations of dissolved gases, e.g. at gas seeps and gas hydrate systems. The system allows for batch, fed-batch and continuous gas-phase free incubation. We employ this system to study the kinetics and isotope fractionation during AOM at varying methane partial pressures up to 10 MPa. We present the results of long-term continuous and fed-batch incubations with highly active naturally enriched biomass from microbial mats from the Black Sea. During these experiments the methane partial pressure was increased stepwise from 0.1 to 10 MPa. The methane dependent sulfate reduction rate increased from 0.1 mmol/l/d to 3.5 mmol/l/d resulting from the increase in methane concentration and microbial growth. Sulfate reduction was negligible in the absence of methane. The sulfur and oxygen isotope fractionation during sulfate reduction was strongly influenced by the concentration of dissolved methane. Sulfur isotope fractionation was highest at low methane concentrations, and lowest at high methane concentrations. Relative to sulfate reduction rates, oxygen isotope exchange between sulfate and water was highest at low methane concentrations, and lowest at high methane concentrations.

  10. 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.

  11. Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes.

    PubMed

    Maldonado, Stephen; Stevenson, Keith J

    2005-03-17

    Nondoped and nitrogen-doped (N-doped) carbon nanofiber (CNF) electrodes were prepared via a floating catalyst chemical vapor deposition (CVD) method using precursors consisting of ferrocene and either xylene or pyridine to control the nitrogen content. Structural and compositional differences between the nondoped and N-doped varieties were assessed using TEM, BET, Raman, TGA, and XPS. Electrochemical methods were used to study the influence of nitrogen doping on the oxygen reduction reaction (ORR). The N-doped CNF electrodes demonstrate significant catalytic activity toward oxygen reduction in aqueous KNO(3) solutions at neutral to basic pH. Electrochemical data are presented which indicate that the ORR proceeds by the peroxide pathway via two successive two-electron reductions. However, for N-doped CNF electrodes, the reduction process can be treated as a catalytic regenerative process where the intermediate hydroperoxide (HO(2)(-)) is chemically decomposed to regenerate oxygen, 2HO(2)(-) <==> O(2) + 2OH(-). The proposed electrocatalysis mechanisms for ORR at both nondoped and N-doped varieties are supported by electrochemical simulations and by measured difference in hydroperoxide decomposition rate constants. Remarkably, approximately 100 fold enhancement for hydroperoxide decomposition is observed for N-doped CNFs, with rates comparable to the best known peroxide decomposition catalysts. Collectively the data indicate that exposed edge plane defects and nitrogen doping are important factors for influencing adsorption of reactive intermediates (i.e., superoxide, hydroperoxide) and for enhancing electrocatalysis for the ORR at nanostructured carbon electrodes.

  12. 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.

  13. Self-assembly of Spinel Nano-crystals into Mesoporous Spheres as Bi-functionally Active Oxygen Reduction and Evolution Electrocatalysts.

    PubMed

    Lee, Dong Un; Li, Jingde; Park, Moon Gyu; Seo, Min Ho; Ahn, Wook; Stadelmann, Ian; Ricardez-Sandoval, Luis; Chen, Zhongwei

    2017-03-29

    The present work introduces spinel oxide nano-crystals self-assembled into mesoporous spheres that are bi-functionally active towards catalyzing both oxygen reduction reaction (ORR), and oxygen evolution reaction (OER). The electrochemical evaluation reveals that (Ni,Co)3O4 demonstrates significantly positive shifted ORR on-set and half-wave potentials (-0.127 and -0.292 V vs. SCE, respectively), while Co3O4 results in a negative shifted OER potential (0.65 V vs. SCE) measured at 10 mA cm-2. Based on the DFT analysis, the potential at which all oxygen intermediate reactions proceed spontaneously is the highest for (Ni,Co)3O4 (U = 0.66 eV) during ORR, while it is the lowest for Co3O4 (U = 2.09 eV) during OER. The high ORR activity of (Ni,Co)3O4 is attributed to the enhanced electrical conductivity of the spinel lattice, while the high OER activity of Co3O4 is attributed to relatively weak adsorption energy promoting rapid release of evolved oxygen.

  14. Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials

    NASA Astrophysics Data System (ADS)

    Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

    2017-09-01

    It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

  15. Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials.

    PubMed

    Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

    2017-09-08

    It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

  16. Roles of Fe-Nx and Fe-Fe3C@C Species in Fe-N/C Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Kim, Jae Hyung; Sa, Young Jin; Jeong, Hu Young; Joo, Sang Hoon

    2017-03-22

    Iron and nitrogen codoped carbons (Fe-N/C) have emerged as promising nonprecious metal catalysts for the oxygen reduction reaction (ORR). While Fe-Nx sites have been widely considered as active species for Fe-N/C catalysts, very recently, iron and/or iron carbide encased with carbon shells (Fe-Fe3C@C) has been suggested as a new active site for the ORR. However, most of synthetic routes to Fe-N/C catalysts involve high-temperature pyrolysis, which unavoidably yield both Fe-Nx and Fe-Fe3C@C species, hampering the identification of exclusive role of each species. Herein, in order to establish the respective roles of Fe-Nx and Fe-Fe3C@C sites we rationally designed model catalysts via the phase conversion reactions of Fe3O4 nanoparticles supported on carbon nanotubes. The resulting catalysts selectively contained Fe-Nx, Fe-Fe3C@C, and N-doped carbon (C-Nx) sites. It was revealed that Fe-Nx sites dominantly catalyze ORR via 4-electron (4 e(-)) pathway, exerting a major role for high ORR activity, whereas Fe-Fe3C@C sites mainly promote 2 e(-) reduction of oxygen followed by 2 e(-) peroxide reduction, playing an auxiliary role.

  17. High Rate Oxygen Reduction in Non-aqueous Electrolytes with the Addition of Perfluorinated Additives

    SciTech Connect

    Wang, Y.; Yang, X.; Zheng, D.; Qu, D.

    2011-08-04

    The discharge rate capability of Li-air batteries is substantially increased by using perfluorinated compounds as oxygen carriers. The solubility of oxygen in a non-aqueous electrolyte can be significantly increased by the introduction of such compounds, which leads to the increase in the diffusion-limited current of oxygen reduction on the gas diffusion electrode in a Li-air battery. The perfluorinated compound is found to be stable within the electrochemical window of the electrolyte. A powder microelectrode and a rotating disk electrode were used to study the gas diffusion-limited current together with a rotating disk electrode. A 5 mA cm{sup -2} discharge rate is demonstrated in a lab Li-O{sub 2} cell.

  18. Using ordered carbon nanomaterials for shedding light on the mechanism of the cathodic oxygen reduction reaction.

    PubMed

    Ruvinskiy, Pavel S; Bonnefont, Antoine; Pham-Huu, Cuong; Savinova, Elena R

    2011-07-19

    Insufficient understanding of the mechanism of the cathodic oxygen reduction reaction puts constraints on the improvement of the efficiency of polymer electrolyte fuel cells (PEMFCs). We apply ordered catalytic layers based on vertically aligned carbon nanofilaments and combine experimental rotating ring-disk studies with mathematical modeling for shedding light on the mechanism of the oxygen reduction reaction on Pt nanoparticles. Based on the experimental and simulation evidence we propose a dual path ORR mechanism which comprises a "direct 4e(-)" and a "series 2e(-) + 2e(-)" pathway and explains switching between the two. For the first time we show that below 0.8 V the "direct" path may be discarded and the ORR predominantly occurs via H(2)O(2) mediated pathway, while in the potential interval between ca. 0.8 V and the onset of the ORR the "direct" path is dominating.

  19. 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

  20. Nanocrystaline tungsten carbide supported Au-Pd electrocatalyst for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Nie, Ming; Shen, Pei Kang; Wei, Zidong

    Au-Pd nanobimetallic particles supported on nanocrystaline tungsten carbide as electrocatalysts for oxygen reduction were prepared by an intermittent microwave heating (IMH) method. XRD measurement revealed that AuPd alloy formed during the IMH process. We showed these novel electrocatalysts could offer the activities that surpass that of the state-of-the-art Pt-based electrocatalysts for oxygen reduction reaction. The AuPd-WC/C electrode showed an over 70 mV shift towards more positive potentials compared to Pt/C electrode for ORR. The advantage seemed to come from the novel support of tungsten carbide which itself has the catalytic activity to enhance the catalytic activity of the metal electrocatalysts.

  1. 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.

  2. Electronic metal-support interaction enhanced oxygen reduction activity and stability of boron carbide supported platinum

    NASA Astrophysics Data System (ADS)

    Jackson, Colleen; Smith, Graham T.; Inwood, David W.; Leach, Andrew S.; Whalley, Penny S.; Callisti, Mauro; Polcar, Tomas; Russell, Andrea E.; Levecque, Pieter; Kramer, Denis

    2017-06-01

    Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50-100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

  3. 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

  4. Recent advances in the design of tailored nanomaterials for efficient oxygen reduction reaction

    DOE PAGES

    Lv, Haifeng; Li, Dongguo; Strmcnik, Dusan; ...

    2016-04-11

    In the past decade, polymer electrolyte membrane fuels (PEMFCs) have been evaluated for both automotive and stationary applications. One of the main obstacles for large scale commercialization of this technology is related to the sluggish oxygen reduction reaction that takes place on the cathode side of fuel cell. Consequently, ongoing research efforts are focused on the design of cathode materials that could improve the kinetics and durability. Majority of these efforts rely on novel synthetic approaches that provide control over the structure, size, shape and composition of catalytically active materials. This article highlights the most recent advances that have beenmore » made to tailor critical parameters of the nanoscale materials in order to achieve more efficient performance of the oxygen reduction reaction (ORR).« less

  5. 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.

  6. Synergy among manganese, nitrogen and carbon to improve the catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Kang, Jian; Wang, Hui; Ji, Shan; Key, Julian; Wang, Rongfang

    2014-04-01

    A highly active electrocatalyst for oxygen reduction reaction, manganese modified glycine derivative-carbon (Mn-CNx), is synthesized by a two-step carbonizing process. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy are used to characterize structure and morphology of the catalysts. Electrochemical tests show that Mn-CNx has higher catalytic activity for oxygen reduction reaction than CNx derived glycine and Mn modified Vulcan carbon. Moreover, the half-wave potential of Mn-CNx is only 12 mV lower than that of commercial Pt/C. Mn-CNx also has excellent durability to methanol crossover in alkaline solution, and thus provides a promising low cost, non-precious metal cathode catalyst for fuel cells.

  7. 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.

  8. Mechanism of Oxygen Reduction in Cytochrome c Oxidase and the Role of the Active Site Tyrosine.

    PubMed

    Blomberg, Margareta R A

    2016-01-26

    Cytochrome c oxidase, the terminal enzyme in the respiratory chain, reduces molecular oxygen to water and stores the released energy through electrogenic chemistry and proton pumping across the membrane. Apart from the heme-copper binuclear center, there is a conserved tyrosine residue in the active site (BNC). The tyrosine delivers both an electron and a proton during the O-O bond cleavage step, forming a tyrosyl radical. The catalytic cycle then occurs in four reduction steps, each taking up one proton for the chemistry (water formation) and one proton to be pumped. It is here suggested that in three of the reduction steps the chemical proton enters the center of the BNC, leaving the tyrosine unprotonated with radical character. The reproprotonation of the tyrosine occurs first in the final reduction step before binding the next oxygen molecule. It is also suggested that this reduction mechanism and the presence of the tyrosine are essential for the proton pumping. Density functional theory calculations on large cluster models of the active site show that only the intermediates with the proton in the center of the BNC and with an unprotonated tyrosyl radical have a high electron affinity of similar size as the electron donor, which is essential for the ability to take up two protons per electron and thus for the proton pumping. This type of reduction mechanism is also the only one that gives a free energy profile in accordance with experimental observations for the amount of proton pumping in the working enzyme.

  9. Electrochemical oxygen reduction reaction by Pt nanoparticles on carbon support stabilized by polyoxometalates.

    PubMed

    Kishore, Pilli Satyananda; Viswanathan, Balasubramanian; Varadarajan, Thirukkallam Kanthadai

    2009-09-01

    The abilities of Keggin type polyoxometalate, silicotungstic acid (STA) to reduce metal ions by electron transfer and to modify carbon surface by strong adsorption have been explored for the preparation of Pt nanoparticles supported on carbon composites (20% Pt/STA-C). The prepared composites were characterized by Transmission electron microscopy (TEM and HRTEM)), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The electrocatalytic activities of the prepared nanocomposites were examined by using Cyclic voltammetry (CV) for oxygen reduction reaction which takes place at cathode in fuel cells. The prepared composite (20% Pt/STA-C) proved efficient compared to STA free 20% Pt/C, prepared by hydrogen reduction method. H2O2 intermediate formation is a serious concern as it reduces the activity of Pt sites during oxygen reduction. The composites prepared by polyoxometalate reduction method (20% Pt/STA-C) showed better reduction ability towards H2O2 compared to STA free 20% Pt/C composite and thus showed better performance as cathode electrocatalyst for fuel cells.

  10. 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.

  11. Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Kong, Jiangrong; Liu, Yaru; Liu, Qicheng; Zhu, Hongze

    2015-03-01

    Mesoporous carbon is constructed by monolithic polyaromatic mesophase deriving from the hexane insoluble of coal-tar pitch. This carbon material exhibits spherical morphology and layered crystallite, and thereby can be graphitized at 900 °C without destroying the mesoporous structure. Electrochemical measurements indicate that graphitic mesoporous carbon (GMC) support not only improves the activity of Pt electrocatalyst to oxygen reduction reaction (ORR), but also shows higher corrosion resistance than commercial XC-72 carbon black in the acid cathode environment.

  12. Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

    DOE PAGES

    Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

    2016-12-28

    Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

  13. 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.

  14. CYP450 Enzymes Effect Oxygen-Dependent Reduction of Azide-Based Fluorogenic Dyes

    PubMed Central

    2016-01-01

    Azide-containing compounds have broad utility in organic synthesis and chemical biology. Their use as powerful tools for the labeling of biological systems in vitro has enabled insights into complex cellular functions. To date, fluorogenic azide-containing compounds have primarily been employed in the context of click chemistry and as sensitive functionalities for hydrogen sulfide detection. Here, we report an alternative use of this functionality: as fluorogenic probes for the detection of depleted oxygen levels (hypoxia). Oxygen is imperative to all life forms, and probes that enable quantification of oxygen tension are of high utility in many areas of biology. Here we demonstrate the ability of an azide-based dye to image hypoxia in a range of human cancer cell lines. We have found that cytochrome P450 enzymes are able to reduce these probes in an oxygen-dependent manner, while hydrogen sulfide does not play an important role in their reduction. These data indicate that the azide group is a new bioreductive functionality that can be employed in prodrugs and dyes. We have uncovered a novel mechanism for the cellular reduction of azides, which has implications for the use of click chemistry in hypoxia. PMID:28149949

  15. Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

    SciTech Connect

    Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

    2016-12-28

    Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specific and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.

  16. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

    DOE PAGES

    To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira; ...

    2016-11-30

    The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O2-H2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell.more » The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.« less

  17. High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

    SciTech Connect

    To, John W. F.; Ng, Jia Wei Desmond; Siahrostami, Samira; Koh, Ai Leen; Lee, Yangjin; Chen, Zhihua; Fong, Kara D.; Chen, Shucheng; He, Jiajun; Bae, Won -Gyu; Wilcox, Jennifer; Jeong, Hu Young; Kim, Kwanpyo; Studt, Felix; Nørskov, Jens K.; Jaramillo, Thomas F.; Bao, Zhenan

    2016-11-30

    The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O2-H2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. As a result, this work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.

  18. Oxygen reduction in the strict anaerobe Desulfovibrio vulgaris Hildenborough: characterization of two membrane-bound oxygen reductases.

    PubMed

    Lamrabet, O; Pieulle, L; Aubert, C; Mouhamar, F; Stocker, P; Dolla, A; Brasseur, G

    2011-09-01

    Although Desulfovibrio vulgaris Hildenborough (DvH) is a strictly anaerobic bacterium, it is able to consume oxygen in different cellular compartments, including extensive periplasmic O₂ reduction with hydrogen as electron donor. The genome of DvH revealed the presence of cydAB and cox genes, encoding a quinol oxidase bd and a cytochrome c oxidase, respectively. In the membranes of DvH, we detected both quinol oxygen reductase [inhibited by heptyl-hydroxyquinoline-N-oxide (HQNO)] and cytochrome c oxidase activities. Spectral and HPLC data for the membrane fraction revealed the presence of o-, b- and d-type haems, in addition to a majority of c-type haems, but no a-type haem, in agreement with carbon monoxide-binding analysis. The cytochrome c oxidase is thus of the cc(o/b)o₃ type, a type not previously described. The monohaem cytochrome c₅₅₃ is an electron donor to the cytochrome c oxidase; its encoding gene is located upstream of the cox operon and is 50-fold more transcribed than coxI encoding the cytochrome c oxidase subunit I. Even when DvH is grown under anaerobic conditions in lactate/sulfate medium, the two terminal oxidase-encoding genes are expressed. Furthermore, the quinol oxidase bd-encoding genes are more highly expressed than the cox genes. The cox operon exhibits an atypical genomic organization, with the gene coxII located downstream of coxIV. The occurrence of these membrane-bound oxygen reductases in other strictly anaerobic Deltaproteobacteria is discussed.

  19. Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Zhuang; Li, Mian; Fan, Liquan; Han, Jianan; Xiong, Yueping

    2017-04-01

    The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-Nx and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

  20. Carbon Nanotube/Boron Nitride Nanocomposite as a Significant Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.

    PubMed

    Patil, Indrajit M; Lokanathan, Moorthi; Ganesan, Balakrishnan; Swami, Anita; Kakade, Bhalchandra

    2017-01-12

    It is an immense challenge to develop bifunctional electrocatalysts for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in low temperature fuel cells and rechargeable metal-air batteries. Herein, a simple and cost-effective approach is developed to prepare novel materials based on carbon nanotubes (CNTs) and a hexagonal boron nitride (h-BN) nanocomposite (CNT/BN) through a one-step hydrothermal method. The structural analysis and morphology study confirms the formation of a homogeneous composite and merging of few exfoliated graphene layers of CNTs on the graphitic planes of h-BN, respectively. Moreover, the electrochemical study implies that CNT/BN nanocomposite shows a significantly higher ORR activity with a single step 4-electron transfer pathway and an improved onset potential of +0.86 V versus RHE and a current density of 5.78 mA cm(-2) in alkaline conditions. Interestingly, it exhibits appreciably better catalytic activity towards OER at low overpotential (η=0.38 V) under similar conditions. Moreover, this bifunctional catalyst shows substantially higher stability than a commercial Pt/C catalyst even after 5000 cycles. Additionally, this composite catalyst does not show any methanol oxidation reactions that nullify the issues due to fuel cross-over effects in direct methanol fuel cell applications.

  1. Factors that Affect Oxygen Activation and Coupling of the Two Redox Cycles in the Aromatization Reaction Catalyzed by NikD, an Unusual Amino Acid Oxidase†‡

    PubMed Central

    Kommoju, Phaneeswara-Rao; Bruckner, Robert C.; Ferreira, Patricia; Carrell, Christopher J.; Mathews, F. Scott; Jorns, Marilyn Schuman

    2009-01-01

    NikD is a flavoprotein oxidase that catalyzes the oxidation of piperideine-2-carboxylate (P2C) to picolinate in a remarkable aromatization reaction comprising two redox cycles and at least one isomerization step. Tyr258 forms part of an "aromatic cage" that surrounds the ring in picolinate and its precursors. Mutation of Tyr258 to Phe does not perturb the structure of nikD but does affect the coupling of the two redox cycles and causes a 10-fold decrease in turnover rate. Tyr258Phe catalyzes a quantitative 2-electron oxidation of P2C but only 60% of the resulting dihydropicolinate intermediate undergoes a second redox cycle to produce picolinate. The mutation does not affect product yield with an alternate substrate (3,4-dehydro-L-proline) that is aromatized in a single 2-electron oxidation step. Wild-type and mutant enzyme exhibit identical rate constants for P2C oxidation to dihydropicolinate and isomerization of a reduced enzyme•dihydropicolinate complex. The observed rates are 200- and 10-fold faster, respectively, than the mutant turnover rate. Picolinate release from Tyr258Phe is 100-fold faster than turnover. The presence of bound substrate or product is a key factor in oxygen activation by wild-type nikD, as judged by the 10- to 75-fold faster rates observed for complexes of the reduced enzyme with picolinate, benzoate or 1-cyclohexenoate, a 1-deaza P2C analog. The reduced Tyr258Phe•1-cyclohexenoate complex is 25-fold less reactive with oxygen than the wild-type complex. We postulate that mutation of Tyr258 causes subtle changes in active site dynamics that promote release of the reactive dihydropicolinate intermediate and disrupt the efficient synchronization of oxygen activation observed with wild-type nikD. PMID:19702312

  2. Enhanced Photoelectrocatalytic Reduction of Oxygen Using Au@TiO2 Plasmonic Film.

    PubMed

    Guo, Limin; Liang, Kun; Marcus, Kyle; Li, Zhao; Zhou, Le; Mani, Prabhu Doss; Chen, Hao; Shen, Chen; Dong, Yajie; Zhai, Lei; Coffey, Kevin R; Orlovskaya, Nina; Sohn, Yong-Ho; Yang, Yang

    2016-12-28

    Novel Au@TiO2 plasmonic films were fabricated by individually placing Au nanoparticles into TiO2 nanocavity arrays through a sputtering and dewetting process. These discrete Au nanoparticles in TiO2 nanocavities showed strong visible-light absorption due to the plasmonic resonance. Photoelectrochemical studies demonstrated that the developed Au@TiO2 plasmonic films exhibited significantly enhanced catalytic activities toward oxygen reduction reactions with an onset potential of 0.92 V (vs reversible hydrogen electrode), electron transfer number of 3.94, and limiting current density of 5.2 mA cm(-2). A superior ORR activity of 310 mA mg(-1) is achieved using low Au loading mass. The isolated Au nanoparticle size remarkably affected the catalytic activities of Au@TiO2, and TiO2 coated with 5 nm Au (Au5@TiO2) exhibited the best catalytic function to reduce oxygen. The plasmon-enhanced reductive activity is attributed to the surface plasmonic resonance of isolated Au nanoparticles in TiO2 nanocavities and suppressed electron recombination. This work provides comprehensive understanding of a novel plasmonic system using isolated noble metals into nanostructured semiconductor films as a potential alternative catalyst for oxygen reduction reaction.

  3. 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

    2014-09-17

    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.

  4. 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.

  5. 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.

  6. A Class of High Performance Metal-Free Oxygen Reduction Electrocatalysts based on Cheap Carbon Blacks

    PubMed Central

    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/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. PMID:23974295

  7. 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.

  8. 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

  9. 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

  10. Stable platinum nanoclusters on genomic DNA-graphene oxide with a high oxygen reduction reaction activity.

    PubMed

    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.

  11. 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.

  12. The Mechanisms of Oxygen Reduction in the Terminal Reducing Segment of the Chloroplast Photosynthetic Electron Transport Chain.

    PubMed

    Kozuleva, Marina A; Ivanov, Boris N

    2016-07-01

    The review is dedicated to ascertainment of the roles of the electron transfer cofactors of the pigment-protein complex of PSI, ferredoxin (Fd) and ferredoxin-NADP reductase in oxygen reduction in the photosynthetic electron transport chain (PETC) in the light. The data regarding oxygen reduction in other segments of the PETC are briefly analyzed, and it is concluded that their participation in the overall process in the PETC under unstressful conditions should be insignificant. Data concerning the contribution of Fd to the oxygen reduction in the PETC are examined. A set of collateral evidence as well as results of direct measurements of the involvement of Fd in this process in the presence of isolated thylakoids led to the inference that this contribution in vivo is negligible. The increase in oxygen reduction rate in the isolated thylakoids in the presence of either Fd or Fd plus NADP(+) under increasing light intensity was attributed to the increase in oxygen reduction executed by the membrane-bound oxygen reductants. Data are presented which imply that a main reductant of the O2 molecule in the terminal reducing segment of the PETC is the electron transfer cofactor of PSI, phylloquinone. The physiological significance of characteristic properties of oxygen reductants in this segment of the PETC is discussed. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  13. 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

  14. 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.

  15. Nitrogen-modified carbon-based catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Subramanian, Nalini P.; Li, Xuguang; Nallathambi, Vijayadurda; Kumaraguru, Swaminatha P.; Colon-Mercado, Hector; Wu, Gang; Lee, Jong-Won; Popov, Branko N.

    Nitrogen-modified carbon-based catalysts for oxygen reduction were synthesized by modifying carbon black with nitrogen-containing organic precursors. The electrocatalytic properties of catalysts were studied as a function of surface pre-treatments, nitrogen and oxygen concentrations, and heat-treatment temperatures. On the optimum catalyst, the onset potential for oxygen reduction is approximately 0.76 V (NHE) and the amount of hydrogen peroxide produced at 0.5 V (NHE) is approximately 3% under our experimental conditions. The characterization studies indicated that pyridinic and graphitic (quaternary) nitrogens may act as active sites of catalysts for oxygen reduction reaction. In particular, pyridinic nitrogen, which possesses one lone pair of electrons in addition to the one electron donated to the conjugated π bond, facilitates the reductive oxygen adsorption.

  16. Structural Basis of the Divergent Oxygenation Reactions Catalyzed by the Rieske Nonheme Iron Oxygenase Carbazole 1,9a-Dioxygenase

    PubMed Central

    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

    2014-01-01

    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

  17. Effect of Oxygen Tension, Mn(II) Concentration, and Temperature on the Microbially Catalyzed Mn(II) Oxidation Rate in a Marine Fjord †

    PubMed Central

    Tebo, Bradley M.; Emerson, Steven

    1985-01-01

    We present evidence that the oxidation of Mn(II) in a zone above the O2/H2S interface in the water column of Saanich Inlet, British Columbia, Canada, is microbially catalyzed. We measured the uptake of 54Mn(II) in water samples under in situ conditions of pH and temperature and in the presence and absence of oxygen. Experiments in the absence of oxygen provided a measure of the exchange of the tracer between the dissolved and solid pools of Mn(II); we interpret the difference between experiments in the presence and absence of oxygen to be a measure of Mn(II) oxidation. Using this method we examined the effect of oxygen tension, Mn(II) concentration, and temperature on the initial in situ Mn(II) oxidation rate (V0). Mn(II) oxidation was almost twice as fast under conditions of 67% air saturation (V0=5.5 nM h−1) as with the in situ concentration of 15 μM (5% air saturation; V0=3.1 nM h−1). Additions of ca. 18 μM Mn(II) completely inhibited all Mn(II) oxidation at three different depths in the oxidizing zone, and there was a temperature optimum for Mn(II) oxidation of around 20°C. These results are consistent with biologically mediated Mn(II) oxidation and indicate that the rate is limited by both oxygen and the concentration of microbial binding sites in this environment. PMID:16346931

  18. Mechanistic Investigation into Olefin Epoxidation with H2O2 Catalyzed by Aqua‐Coordinated Sandwich‐Type Polyoxometalates: Role of the Noble Metal and Active Oxygen Position

    PubMed Central

    Ci, Chenggang; Liu, Hongsheng

    2016-01-01

    Abstract Aqua‐coordinated sandwich‐type polyoxometalates (POMs), {[WZnTM2(H2O)2](ZnW9O34)2}n− (TM=RhIII, PdII, and PtII), catalyze olefin epoxidation with hydrogen peroxide and have been well established, and they present an advance toward the utilization of olefins. To elucidate the epoxidation mechanism, we systematically performed density functional calculations. The reaction proceeds through a two‐step mechanism: activation of H2O2 and oxygen transfer. The aqua‐coordinated complexes show two distinct H2O2 activation pathways: “two‐step” and “concerted”. The concerted processes are more facile and proceed with similar and rate‐determining energy barriers at the Rh‐, Pd‐, and Pt‐containing transition states, which agrees well with the experimental results. Next, the resulting TM−OH−(μ‐OOH) intermediate transfers an O atom to olefin to form an epoxide. The higher reactivity of the Rh‐containing POM is attributed to more interactions between the Rh and hydroperoxo unit. We also calculated all active oxygen positions to locate the most favorable pathway. The higher reactivity of the two‐metal‐bonded oxygen position is predominantly ascribed to its lower stereoscopic hindrance. Furthermore, the presence of one and two explicit water solvent molecules significantly reduces the energy barriers, making these sandwich POMs very efficient for the olefin epoxidation with H2O2. PMID:27777840

  19. Graphene supported Co-g-C3N4 as a novel metal-macrocyclic electrocatalyst for the oxygen reduction reaction in fuel cells.

    PubMed

    Liu, Qiao; Zhang, Junyan

    2013-03-19

    Graphitic carbon nitride (g-C3N4) polymer was doped with cobalt species and supported on a similar sp(2) structure graphene, to form a novel nitrogen-metal macrocyclic catalyst for the oxygen reduction reaction (ORR) in alkaline fuel cells. The structural characterizations confirmed the formation of Co-N bonds and the close electron coupling between Co-g-C3N4 and graphene sheets. The electrocatalytic measurements demonstrated Co-g-C3N4-catalyzed reduction of oxygen mainly in a four electron pathway. The improvement of ORR activity is closely related to the abundant accessible Co-Nx active sites and fast charge transfer at the interfaces of Co-g-C3N4/graphene. Also, Co-g-C3N4@graphene exhibited comparable ORR activity, better durability, and methanol tolerance ability in comparison to Pt/C, and bodes well for a promising non-noble cathode catalyst for the application of direct methanol fuel cells. The chemical doping strategy in this work would be helpful to improve other present catalysts for fuel cell applications.

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

    PubMed

    Cheng, Daojian; Qiu, Xiangguo; Yu, Haiyan

    2014-10-14

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

  1. Ti(3+)-Promoted High Oxygen-Reduction Activity of Pd Nanodots Supported by Black Titania Nanobelts.

    PubMed

    Yuan, Xiaotao; Wang, Xin; Liu, Xiangye; Ge, Hongxin; Yin, Guoheng; Dong, Chenlong; Huang, Fuqiang

    2016-10-04

    One-dimensional nanocrystals favoring efficient charge transfer have attracted enormous attentions, and conductive nanobelts of black titania with a unique band structure and high electrical conductivity would be interestingly used in electrocatalysis. Here, Pd nanodots supported by two kinds of black titania, the oxygen-deficient titania (TiO2-x) and nitrogen-doped titania (TiO2-x:N), were synthesized as efficient composite catalysts for oxygen-reduction reaction (ORR). These composite catalysts show improved catalytic activity with lower overpotential and higher limited current, compared to the Pd nanodots supported on the white titania (Pd/TiO2). The improved activity is attributed to the relatively high conductivity of black titania nanobelts for efficient charge transfer (CT) between Ti(3+) species and Pd nanodots. The CT process enhances the strong metal-support interaction (SMSI) between Pd and TiO2, which lowers the absorption energy of O2 on Pd and makes it more suitable for oxygen reduction. Because of the stronger interaction between Pd and support, the Pd/TiO2-x:N also shows excellent durability and immunity to methanol poisoning.

  2. Reduction of calcium channel antagonist binding sites by oxygen free radicals in rat heart.

    PubMed

    Kaneko, M; Lee, S L; Wolf, C M; Dhalla, N S

    1989-09-01

    In view of the importance of Ca2+-channels in controlling the entry of Ca2+ into the myocardium, this study was undertaken to examine the effects of oxygen free radicals on the binding of Ca2+-channel antagonists in rat heart by employing [3H]-nitrendipine as a ligand. Isolated heart membranes were incubated with xanthine + xanthine oxidase (a superoxide anion radicals generating system), hydrogen peroxide (an activated species of oxygen), or hydrogen peroxide + Fe2+ (a hydroxyl radicals generating system). The assay of the [3H]-nitrendipine binding activity revealed that the maximal number of binding sites (Bmax) were reduced in a time-dependent manner by superoxide radicals without any changes in the binding constant (Kd); a significant reduction of Bmax was seen after incubating membranes with xanthine + xanthine oxidase for a 10-min-period. Superoxide dismutase showed a protective effect on the superoxide radicals induced reduction in Bmax. Both hydrogen peroxide and hydroxyl radicals also depressed the Bmax for [3H]-nitrendipine binding without any significant change in Kd; catalase and mannitol showed protective effects on hydrogen peroxide or hydroxyl radicals induced depression in Bmax, respectively. These results indicate that oxygen free radicals may reduce the number of Ca2+-channels in the cell membrane and this change may contribute towards decreasing the voltage-dependent Ca2+ influx in the cardiac cell.

  3. Effects of phosphoric acid concentration on oxygen reduction kinetics at platinum

    SciTech Connect

    Hsueh, K.L.; Chin, D.T.; Gonzalez, E.R.; Srinivasan, S.

    1984-04-01

    The oxygen reduction reaction was investigated at platinum electrodes in phosphoric acid in the concentration range 0.7M(6.6%) to 17.5M(95%) at 25/sup 0/C using the rotating ring-disk electrode technique. As a complement, cyclic voltammograms on platinum and potentials of zero charge of mercury were obtained as a function of phosphoric aci concentration. The mechanism of the oxygen electrode reaction is discussed in terms of the direct four-electron transfer reduction to water and the formation of hydrogen peroxide as an intermediate in a parallel two-electron transfer reaction The rate constants of the intermediate reaction steps were calculated from the ring-disk data for various potentials and electrolyte concentrations. The characteristics of the reaction were found to be markedly dependent on the concentration of phosphoric acid. These results are interpreted in terms of changes in oxygen solubility, proton activity, and double laye characteristics when passing over from a water to a phosphoric acid solvent structure.

  4. 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.

  5. The electrochemistry of quinizarin revealed through its mediated reduction of oxygen

    PubMed Central

    Batchelor-McAuley, Christopher; Dimov, Ivan B.; Aldous, Leigh; Compton, Richard G.

    2011-01-01

    After 35 years the hunt for improved anthracycline antibiotics is unabated but has yet to achieve the levels of clinical success desired. Electrochemical techniques provide a large amount of kinetic and thermodynamic information, but the use of such procedures is hindered by issues of sensitivity and selectivity. This work demonstrates how by harnessing the mechanism of catalytic reduction of oxygen by the quinone functionality present within the anthracycline structure it is possible to study the reactive moiety in nanomolar concentration. This methodology allows electrochemical investigation of the intercalation of quinizarin into DNA and, in particular, the quinone oxidation and degradation mechanism. The reversible reduction of the quinizarin, which in the presence of oxygen leads to the formation of reactive oxygen species, is found to occur at -0.535 V (vs. SCE) pH 6.84 and the irreversible oxidation leading to the molecules degradation occurs at +0.386 V (vs. SCE) pH 6.84. PMID:22109547

  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).

  7. Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

    PubMed

    Sarkar, A; Kerr, J B; Cairns, E J

    2013-07-22

    Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases

    NASA Astrophysics Data System (ADS)

    Bhagi-Damodaran, Ambika; Michael, Matthew A.; Zhu, Qianhong; Reed, Julian; Sandoval, Braddock A.; Mirts, Evan N.; Chakraborty, Saumen; Moënne-Loccoz, Pierre; Zhang, Yong; Lu, Yi

    2017-03-01

    Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.

  9. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases

    NASA Astrophysics Data System (ADS)

    Bhagi-Damodaran, Ambika; Michael, Matthew A.; Zhu, Qianhong; Reed, Julian; Sandoval, Braddock A.; Mirts, Evan N.; Chakraborty, Saumen; Moënne-Loccoz, Pierre; Zhang, Yong; Lu, Yi

    2016-11-01

    Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.

  10. Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases.

    PubMed

    Bhagi-Damodaran, Ambika; Michael, Matthew A; Zhu, Qianhong; Reed, Julian; Sandoval, Braddock A; Mirts, Evan N; Chakraborty, Saumen; Moënne-Loccoz, Pierre; Zhang, Yong; Lu, Yi

    2017-03-01

    Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.

  11. Oxygen reduction mediated by single nanodroplets containing attomoles of vitamin B12: electrocatalytic nano-impacts method.

    PubMed

    Cheng, Wei; Compton, Richard G

    2015-06-08

    We report the use of single Vitamin B12 nanodroplets to mediate the reduction of oxygen in neutral buffer. Electron transfer to single Vitamin B12 nanodroplets is observed using the nano-impacts method and shown to be quantitative. The mechanism of mediated oxygen reduction by single VB12 droplets is revealed as via both Co(II) and Co(I) reduced from Co(III) in VB12 through one or two electron transfer followed by the four-electron reduction of oxygen.

  12. 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.

  13. Continuous-flow mass production of silicon nanowires via substrate-enhanced metal-catalyzed electroless etching of silicon with dissolved oxygen as an oxidant.

    PubMed

    Hu, Ya; Peng, Kui-Qing; Liu, Lin; Qiao, Zhen; Huang, Xing; Wu, Xiao-Ling; Meng, Xiang-Min; Lee, Shuit-Tong

    2014-01-13

    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.

  14. 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

  15. 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.

  16. Remarkable Differences in Reactivity between Benzothiazoline and Hantzsch Ester as a Hydrogen Donor in Chiral Phosphoric Acid Catalyzed Asymmetric Reductive Amination of Ketones.

    PubMed

    Kim, Kyung-Hee; Akiyama, Takahiko; Cheon, Cheol-Hong

    2016-01-01

    Described herein are differences in behavior between a Hantzsch ester and a benzothiazoline as hydrogen donors in the chiral phosphoric acid catalyzed asymmetric reductive amination of ketones with p-anisidine. The asymmetric reductive amination of ketones with a Hantzsch ester as a hydrogen donor provided the corresponding chiral amines exclusively, regardless of the structures of the ketones, whereas a similar transformation with a benzothiazoline provided chiral amines and p-methoxyphenyl-protected primary amines in variable yields, depending on the structures of both the ketones and benzothiazolines. Because a benzothiazoline has an N,S-acetal moiety that is vulnerable to p-anisidine, the primary amine can be formed through transimination of the benzothiazoline with p-anisidine followed by reduction of the resulting aldimine with remaining benzothiazoline.

  17. 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.

  18. Electronic Coupling of Cobalt Nanoparticles to Nitrogen-Doped Graphene for Oxygen Reduction and Evolution Reactions.

    PubMed

    Xu, Chaohe; Lu, Meihua; Yan, Binggong; Zhan, Yi; Balaya, Palani; Lu, Li; Lee, Jim Yang

    2016-11-09

    The rational design of nonprecious-metal electrocatalysts with activities comparable to or greater than that of platinum is extremely valuable to the development of high energy density metal-air batteries. Herein, the two-step preparation of a highly active oxygen electrocatalyst based on ultrasmall cobalt nanoparticles stabilized in a nitrogen-doped graphene matrix is reported. The catalyst performs as well as the commercial Pt/C catalyst in the oxygen reduction reaction, and better than the Pt/C catalyst in the oxygen evolution reaction. This particular electrocatalyst could significantly lower the overpotentials of oxygen electrochemical reactions in aqueous lithium-air batteries to attain a round-trip efficiency of about 79.0 % at a current density of 0.1 mA cm(-2) , thereby surpassing the performance of the commercial Pt/C catalyst. The good performance may be attributed to strong metal-support interactions, maximized by a high dispersion of ultrasmall cobalt nanocrystals in a nitrogen-doped graphene matrix, which yields electrocatalytic properties greater than the sum of its parts. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Scalable synthesis of palladium icosahedra in plug reactors for the production of oxygen reduction reaction catalysts

    DOE PAGES

    Wang, Helan; Niu, Guangda; Zhou, Ming; ...

    2016-03-10

    We have synthesized Pd icosahedra with uniform, controllable sizes in plug reactors separated by air. The oxygen contained in the air segments not only contributed to the generation of a reductant from diethylene glycol in situ, but also oxidized elemental Pd back to the ionic form by oxidative etching and thus slowed down the reduction kinetics. Compared to droplet reactors involving silicone oil or fluorocarbon, the use of air as a carrier phase could reduce the production cost by avoiding additional procedures for the separation of products from the oil. The average diameters of the Pd icosahedra could be readilymore » controlled in the range of 12–20 nm. The Pd icosahedra were further employed as seeds for the production of Pd@Pt2–3L core-shell icosahedra, which could serve as a catalyst toward the oxygen reduction reaction with greatly enhanced activity. As a result, we believe that the plug reactors could be extended to other types of noble-metal nanocrystals for their scale-up production.« less

  20. Scalable synthesis of palladium icosahedra in plug reactors for the production of oxygen reduction reaction catalysts

    SciTech Connect

    Wang, Helan; Niu, Guangda; Zhou, Ming; Wang, Xue; Park, Jinho; Bao, Shixiong; Chi, Miaofang; Cai, Zaisheng; Xia, Younan

    2016-03-10

    We have synthesized Pd icosahedra with uniform, controllable sizes in plug reactors separated by air. The oxygen contained in the air segments not only contributed to the generation of a reductant from diethylene glycol in situ, but also oxidized elemental Pd back to the ionic form by oxidative etching and thus slowed down the reduction kinetics. Compared to droplet reactors involving silicone oil or fluorocarbon, the use of air as a carrier phase could reduce the production cost by avoiding additional procedures for the separation of products from the oil. The average diameters of the Pd icosahedra could be readily controlled in the range of 12–20 nm. The Pd icosahedra were further employed as seeds for the production of Pd@Pt2–3L core-shell icosahedra, which could serve as a catalyst toward the oxygen reduction reaction with greatly enhanced activity. As a result, we believe that the plug reactors could be extended to other types of noble-metal nanocrystals for their scale-up production.

  1. Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

    DOE PAGES

    Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; ...

    2016-12-16

    Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stable undermore » the strongly reducing conditions found in CO2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

  2. Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

    SciTech Connect

    Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; Osterwalder, Jurg; Liu, Chang; Favaro, Marco; Crumlin, Ethan J.; Ogasawara, Hirohito; Friebel, Daniel; Pettersson, Lars G. M.; Nilsson, Anders

    2016-12-16

    Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stable under the strongly reducing conditions found in CO2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.

  3. Improved oxygen reduction activity on Pt{sub 3}Ni(111) via increased surface site availability.

    SciTech Connect

    Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G.; Ross, P. N.; Lucus, C. A.; Markovic, N. M.; Materials Science Division; LBNL; Univ. Liverpool; Univ. of South Carolina

    2007-01-01

    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 Pt{sub 3}Ni(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 Pt{sub 3}Ni(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 O{sub 2} adsorption.

  4. Superoxide generation from the reduction of oxygen at the carbon-oil-water triple phase boundary.

    PubMed

    Nissim, Rita; Compton, Richard G

    2013-07-28

    The reduction of oxygen is studied in aqueous solutions of pH 6.22-8.01, at a carbon paste electrode fabricated from dioctyl phthalate (oil) and graphite. Two two-electron voltammetric waves are usually seen on carbon electrodes, associated with the formation of hydrogen peroxide and water, respectively. However, an additional signal is seen on the carbon paste electrode, which can attributed to the initial formation of the superoxide radical anion, O2˙(-). Data is presented to show that the predominant source of oxygen for this reaction is that dissolved in the carbon paste material, rather than in the aqueous solution, and that the superoxide is likely formed at the graphite-oil-water triple phase boundary. Kinetic and thermodynamic parameters for the O2/O2˙(-) redox couple are reported.

  5. 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

  6. 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

  7. Total Synthesis of Pumiliotoxins 209F and 251D via Late-Stage, Nickel-Catalyzed Epoxide-Alkyne Reductive Cyclization

    PubMed Central

    Woodin, Katrina S.; Jamison, Timothy F.

    2011-01-01

    Pumiliotoxins 209F and 251D were synthesized using highly selective nickel-catalyzed epoxide-alkyne reductive cyclizations as the final step. The exocyclic (Z)-alkene found in the majority of the pumiliotoxins was formed stereospecifically and regioselectively, without the use of a directing group on the alkyne, and the epoxide underwent ring opening exclusively at the less hindered carbon to provide the requisite tertiary alcohol. The epoxides were prepared using diastereoselective addition of a sulfoxonium anion to a proline-derived methyl ketone. PMID:17696401

  8. 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

    2015-06-05

    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.

  9. Manganese(I)‐Catalyzed C−H Activation: The Key Role of a 7‐Membered Manganacycle in H‐Transfer and Reductive Elimination

    PubMed Central

    Yahaya, Nasiru P.; Appleby, Kate M.; Teh, Magdalene; Wagner, Conrad; Troschke, Erik; Bray, Joshua T. W.; Duckett, Simon B.; Hammarback, L. Anders; Ward, Jonathan S.; Milani, Jessica; Pridmore, Natalie E.; Whitwood, Adrian C.

    2016-01-01

    Abstract Manganese‐catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven‐membered MnI intermediate is detected and characterized that is effective for H‐transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at MnI by judicious choice of an electron‐deficient 2‐pyrone substrate containing a 2‐pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry. PMID:27603008

  10. Redox-Active Oxygen-Containing Functional Groups in Activated Carbon Facilitate Microbial Reduction of Ferrihydrite.

    PubMed

    Wu, Song; Fang, Guodong; Wang, Yujun; Zheng, Yue; Wang, Chao; Zhao, Feng; Jaisi, Deb P; Zhou, Dongmei

    2017-09-05

    Carbonaceous materials are commonly used in agronomic and environmental applications primarily as geosorbents, but their redox properties that may affect biogeochemical reactions are rarely documented. Herein, the role of activated carbon (AC) mediating microbial reduction of ferrihydrite is studied. Our batch experiment results show that AC facilitated the reduction of ferrihydrite by Shewanella oneidensis MR-1, but the pretreatment of AC with HNO3 further increased the rate of reduction. The redox-active oxygen-containing functional groups in AC were found to be responsible for the enhancement of the microbial reduction of ferrihydrite. This conclusion was supported by the electrochemical evidence that showed that the electron exchange capacity (EEC) of AC was facilitated due to the presence of quinone/hydroquinone groups and strongly positively correlated with the content of C═O groups. Moreover, the coprecipitation of vivianite and siderite was found in the products in the presence of AC, but siderite only was present in the absence of AC. The proper identification of potential functional groups in AC-mediating electron transfer during microbial reduction of ferrihydrite provides insights into the mechanism of reaction and potential roles carbonaceous materials may play in biogeochemical redox processes and, consequently, the fate of contaminants in the environment.

  11. Increased reactive oxygen species production during reductive stress: The roles of mitochondrial glutathione and thioredoxin reductases.

    PubMed

    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 be targeted to increase cancer cell death or modulate H2O2-induced redox signaling to protect the heart against ischemia/reperfusion damage.

  12. Computational screening of core@shell nanoparticles for the hydrogen evolution and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Corona, Benjamin; Howard, Marco; Zhang, Liang; Henkelman, Graeme

    2016-12-01

    Using density functional theory calculations, a set of candidate nanoparticle catalysts are identified based on reactivity descriptors and segregation energies for the oxygen reduction and hydrogen evolution reactions. Trends in the data were identified by screening over 700 core@shell 2 nm transition metal nanoparticles for each reaction. High activity was found for nanoparticles with noble metal shells and a variety of core metals for both reactions. By screening for activity and stability, we obtain a set of interesting bimetallic catalysts, including cases that have reduced noble metal loadings and a higher predicted activity as compared to monometallic Pt nanoparticles.

  13. 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.

  14. Theory, Synthesis, and Oxygen Reduction Catalysis of Fe-Porphyrin-Like Carbon Nanotube

    NASA Astrophysics Data System (ADS)

    Lee, Duck Hyun; Lee, Won Jun; Lee, Won Jong; Kim, Sang Ouk; Kim, Yong-Hyun

    2011-04-01

    We report the synthesis of a Fe-porphyrin-like carbon nanotube from conventional plasma-enhanced chemical vapor deposition. Covalent but seamless incorporation of the 5-6-5-6 porphyrinic Fe-N4 moiety into the graphene hexagonal side wall was elucidated by x-ray and ultraviolet photoemission spectroscopies and first-principles electronic structure calculations. The resulting biomimetic nanotube exhibits an excellent oxygen reduction catalytic activity with the extreme structural stability over 0.1×106 cycles, vastly superior to the commercial Pt-C catalyst.

  15. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction.

    PubMed

    Garsany, Yannick; Baturina, Olga A; Swider-Lyons, Karen E; Kocha, Shyam S

    2010-08-01

    A tutorial is provided for methods to accurately and reproducibly determine the activity of Pt-based electrocatalysts for the oxygen reduction reaction in proton exchange membrane fuel cells and other applications. The impact of various experimental parameters on electrocatalyst activity is demonstrated, and explicit experimental procedures and measurement protocols are given for comparison of electrocatalyst activity to fuel cell standards. (To listen to a podcast about this article, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  16. Oleylamine-functionalized palladium nanoparticles with enhanced electrocatalytic activity for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Shi, Yi; Yin, Shengkang; Ma, Yanrong; Lu, Dingkun; Chen, Yu; Tang, Yawen; Lu, Tianhong

    2014-01-01

    The oleylamine (OAm)-functionalized Pd nanoparticles (Pd-OAm) have been conveniently synthesized through direct thermal decomposition method of low cost palladium acetate. The morphology, crystalline structure and composition of the Pd-OAm are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Fourier transform infrared (FT-IR) spectroscopy, XPS and zeta potential analysis confirm the successful immobilization of OAm molecules on the Pd nanoparticles surface. The Pd-OAm displays an enhanced electrocatalytic activity and formic acid-tolerant ability for the oxygen reduction reaction (ORR), suggesting a potential application in cathodic catalyst for direct formic acid fuel cells.

  17. 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.

  18. Blood pressure reduction does not reduce perihematoma oxygenation: a CT perfusion study.

    PubMed

    Kate, Mahesh P; Hansen, Mikkel B; Mouridsen, Kim; Østergaard, Leif; Choi, Victor; Gould, Bronwen E; McCourt, Rebecca; Hill, Michael D; Demchuk, Andrew M; Coutts, Shelagh B; Dowlatshahi, Dariush; Emery, Derek J; Buck, Brian H; Butcher, Kenneth S

    2014-01-01

    Blood pressure (BP) reduction after intracerebral hemorrhage (ICH) is controversial, because of concerns that this may cause critical reductions in perihematoma perfusion and thereby precipitate tissue damage. We tested the hypothesis that BP reduction reduces perihematoma tissue oxygenation.Acute ICH patients were randomized to a systolic BP target of <150 or <180 mm Hg. Patients underwent CT perfusion (CTP) imaging 2 hours after randomization. Maps of cerebral blood flow (CBF), maximum oxygen extraction fraction (OEF(max)), and the resulting maximum cerebral metabolic rate of oxygen (CMRO2(max)) permitted by local hemodynamics, were calculated from raw CTP data.Sixty-five patients (median (interquartile range) age 70 (20)) were imaged at a median (interquartile range) time from onset to CTP of 9.8 (13.6) hours. Mean OEF(max) was elevated in the perihematoma region (0.44±0.12) relative to contralateral tissue (0.36±0.11; P<0.001). Perihematoma CMRO2(max) (3.40±1.67 mL/100 g per minute) was slightly lower relative to contralateral tissue (3.63±1.66 mL/100 g per minute; P=0.025). Despite a significant difference in systolic BP between the aggressive (140.5±18.7 mm Hg) and conservative (163.0±10.6 mm Hg; P<0.001) treatment groups, perihematoma CBF was unaffected (37.2±11.9 versus 35.8±9.6 mL/100 g per minute; P=0.307). Similarly, aggressive BP treatment did not affect perihematoma OEF(max) (0.43±0.12 versus 0.45±0.11; P=0.232) or CMRO2(max) (3.16±1.66 versus 3.68±1.85 mL/100 g per minute; P=0.857). Blood pressure reduction does not affect perihematoma oxygen delivery. These data support the safety of early aggressive BP treatment in ICH.

  19. 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.

  20. Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals.

    PubMed

    Gao, Yuxian; Li, Rongtan; Chen, Shilong; Luo, Liangfeng; Cao, Tian; Huang, Weixin

    2015-12-21

    Reduction behaviors, oxygen vacancies and hydroxyl groups play decisive roles in the surface chemistry and catalysis of oxides. Employing isothermal H2 reduction we simultaneously reduced CeO2 nanocrystals with different morphologies, created oxygen vacancies and produced hydroxyl groups. The morphology of CeO2 nanocrystals was observed to strongly affect the reduction process and the resultant oxygen vacancy structure. The resultant oxygen vacancies are mainly located on the surfaces of CeO2 cubes and rods but in the subsurface/bulk of CeO2 octahedra. The reactivity of isolated bridging hydroxyl groups on CeO2 nanocrystals was found to depend on the local oxygen vacancy concentration, in which they reacted to produce water at low local oxygen vacancy concentrations but to produce both water and hydrogen with increasing local oxygen vacancy concentration. These results reveal a morphology-dependent interplay among the reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals, which deepens the fundamental understanding of the surface chemistry and catalysis of CeO2.

  1. Molecular electrocatalysis for oxygen reduction by cobalt porphyrins adsorbed at liquid/liquid interfaces.

    PubMed

    Su, Bin; Hatay, Imren; Trojánek, Antonín; Samec, Zdenek; Khoury, Tony; Gros, Claude P; Barbe, Jean-Michel; Daina, Antoine; Carrupt, Pierre-Alain; Girault, Hubert H

    2010-03-03

    Molecular electrocatalysis for oxygen reduction at a polarized water/1,2-dichloroethane (DCE) interface was studied, involving aqueous protons, ferrocene (Fc) in DCE and amphiphilic cobalt porphyrin catalysts adsorbed at the interface. The catalyst, (2,8,13,17-tetraethyl-3,7,12,18-tetramethyl-5-p-amino-phenylporphyrin) cobalt(II) (CoAP), functions like conventional cobalt porphyrins, activating O(2) via coordination by the formation of a superoxide structure. Furthermore, due to the hydrophilic nature of the aminophenyl group, CoAP has a strong affinity for the water/DCE interface as evidenced by lipophilicity mapping calculations and surface tension measurements, facilitating the protonation of the CoAP-O(2) complex and its reduction by ferrocene. The reaction is electrocatalytic as its rate depends on the applied Galvani potential difference between the two phases.

  2. Active Pt3Ni (111) Surface of Pt3Ni Icosahedron for Oxygen Reduction.

    PubMed

    Zhu, Jianbing; Xiao, Meiling; Li, Kui; Liu, Changpeng; Zhao, Xiao; Xing, Wei

    2016-11-09

    Highly active, durable oxygen reduction reaction (ORR) electrocatalysts are extremely important for fuel cell applications. Herein, we provide an efficient way to synthesis of activity Pt3M icosahedra by the one-pot hydrothermal method in the presence of glucosamine which can well adjust the reduction rate of Pt(4+) and efficiently control the morphology of final catalysts. Compared to Pt/C, the Pt3Ni icosahedra show 32-fold and 12-fold enhancement in specific and mass activity, respectively. Furthermore, robust durability was also observed in the accelerated durability test. Thus, this Pt3Ni icosahedron is found among the best Pt-based ORR catalysts, moreover, the findings also demonstrate how to mimic active extended surfaces in nanoscale.

  3. 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.

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

    SciTech Connect

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

    2006-01-01

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

  5. Simple preparation of Pd-Pt nanoalloy catalysts for methanol-tolerant oxygen reduction

    NASA Astrophysics Data System (ADS)

    He, Wei; Liu, Juanying; Qiao, Yongjin; Zou, Zhiqing; Zhang, Xiaogang; Akins, Daniel L.; Yang, Hui

    Carbon-supported Pd-Pt bimetallic nanoparticles of different atomic ratios (Pd-Pt/C) have been prepared by a simple procedure involving the complexing of Pd and Pt species with sodium citrate followed by ethylene glycol reduction. As-prepared Pd-Pt alloy nanoparticles evidence a single-phase fcc disordered structure, and the degree of alloying is found to increase with Pd content. Both X-ray diffraction and transmission electron microscopy characterizations indicate that all the Pd-Pt/C catalysts possess a similar mean particle size of ca. 2.8 nm. The highest mass and specific activity of the oxygen reduction reaction (ORR) using the Pd-Pt/C catalysts are found with a Pd:Pt atomic ratio of 1:2. Moreover, all Pd-Pt alloy catalysts exhibit significantly enhanced methanol tolerance during the ORR than the Pt/C catalyst, ensuring a higher ORR performance while diminishing Pt utilization.

  6. 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.

  7. Evaluation of bimetallic catalyst PtAg/C as a glucose-tolerant oxygen reduction cathode

    NASA Astrophysics Data System (ADS)

    Guerra-Balcázar, M.; Cuevas-Muñiz, F. M.; Álvarez-Contreras, L.; Arriaga, L. G.; Ledesma-García, J.

    2012-01-01

    PtAg/C nanoparticles were synthesized by chemical reduction and evaluated for the oxygen reduction reaction (ORR) in the absence and presence of glucose. PtAg/C catalyst formed onion-like layered structures, which are uniformly distributed on the support. PtAg/C showed activity comparable to that of Pt/C ETEK for ORR. Further, the catalyst exhibited high selectivity for ORR in the presence of glucose. PtAg/C was evaluated as cathode in a microfluidic fuel cell operated with high concentration of glucose (100 mM) as fuel. The results demonstrated that the use of PtAg/C as cathode electrode achieved higher selectivity and better performance compared with Pt/C catalyst.

  8. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-01

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  9. A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface.

    PubMed

    Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

    2017-09-13

    Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of [Formula: see text] hydrogenation reaction is much lower than that of [Formula: see text] dissociation, indicating that [Formula: see text] hydrogenation reaction is more appropriate at the first step than [Formula: see text] dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e (-) ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e (-) reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

  10. 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

  11. 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.

  12. Reductive detoxification as a mechanism of fungal resistance to singlet oxygen-generating photosensitizers.

    PubMed

    Daub, M E; Leisman, G B; Clark, R A; Bowden, E F

    1992-10-15

    Fungi that are resistant or sensitive to the singlet oxygen-generating toxin cercosporin were assayed for their ability to detoxify it by reduction. Cercosporin reduction was assayed microscopically by using bandpass filters to differentiate between fluorescence emission from cercosporin and reduced cercosporin. Hyphae of the resistant Cercospora and Alternaria species emitted a green fluorescence, indicative of reduced cercosporin. Hyphae of nonviable cultures and of cercosporin-sensitive fungi did not reduce cercosporin. Sensitive fungi occasionally reduced cercosporin when incubated with reducing agents that protect against cercosporin toxicity. Cercosporin could not be efficiently photoreduced in the absence of the fungus. Cercospora species were also resistant to eosin Y but were sensitive to rose bengal. Microscopic observation demonstrated that Cercospora species were not capable of reducing rose bengal but were capable of reducing eosin Y. These observations were supported by in vitro electrochemical measurements that revealed the following order with respect to ease of reduction: cercosporin > eosin Y > rose bengal. The formal redox potential (E 0') of cercosporin at pH 7.5 was found to be -0.14 V vs. the normal hydrogen electrode. We conclude that Cercospora species protect themselves against cercosporin by the reduction and detoxification of the toxin molecule.

  13. A study of the catalysis of cobalt hydroxide towards the oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Wang, Yi; Zhang, Dun; Liu, Huaiqun

    A cobalt hydroxide modified glassy carbon (Co(OH) 2/GC) electrode has been fabricated by a galvanostatic electrodeposition method. The catalytic activity for the oxygen (O 2) reduction reaction (ORR) of this electrode in alkaline media is studied by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring-disk electrode voltammetry. The O 2 reduction at the Co(OH) 2/GC disk electrode has been found to undergo an electrochemical process followed by sequential disproportionation of the electrochemical reduction intermediates, i.e., superoxide anion (O 2 rad -) and hydrogen peroxide anion (HO 2 -) in 0.1 M KOH solution. The Co(OH) 2 is first found to possess an excellent catalytic activity not only for the disproportionation of the O 2 rad - produced into O 2 and HO 2 - but also for that of the HO 2 - produced, combined with electrochemical reduction of O 2 mediated by surface functional groups at the carbon electrode surface. The Co(OH) 2 is a potential electrode material for the ORR in alkaline fuel cells and metal-air batteries.

  14. 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

    2016-08-16

    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.

  15. Effects of Sulfidation, Magnetization, and Oxygenation on Azo Dye Reduction by Zerovalent Iron.

    PubMed

    Xu, Chunhua; Zhang, Bingliang; Wang, Yahao; Shao, Qianqian; Zhou, Weizhi; Fan, Dimin; Bandstra, Joel Z; Shi, Zhenqing; Tratnyek, Paul G

    2016-11-01

    Applications of zerovalent iron (ZVI) for water treatment under aerobic conditions include sequestration of metals (e.g., in acid mine drainage) and decolorization of dyes (in wastewaters from textile manufacturing). The processes responsible for contaminant removal can be a complex mixture of reduction, oxidation, sorption, and coprecipitation processes, which are further complicated by the dynamics of oxygen intrusion, mixing, and oxide precipitation. To better understand such systems, the removal of an azo dye (Orange I) by micron-sized granular ZVI at neutral pH was studied in open (aerobic) stirred batch reactors, by measuring the kinetics of Orange I decolorization and changes in "geochemical" properties (DO, Fe(II), and Eh), with and without two treatments that might improve the long-term performance of this system: sulfidation by pretreatment with sulfide and magnetization by application of a weak magnetic field (WMF). The results show that the changes in solution chemistry are coupled to the dynamics of oxygen intrusion, which was modeled as analogous to dissolved oxygen sag curves. Both sulfidation and magnetization increased Orange I removal rates 2.4-71.8-fold, but there was little synergistic benefit to applying both enhancements together. Respike experiments showed that the enhancement from magnetization carries over from magnetization to sulfidation, but not the reverse.

  16. Electrocatalysts Derived from Metal-Organic Frameworks for Oxygen Reduction and Evolution Reactions in Aqueous Media.

    PubMed

    Qian, Yuhong; Khan, Inayat Ali; Zhao, Dan

    2017-10-01

    Electrochemical energy conversion and storage devices such as fuel cells and metal-air batteries have been extensively studied in recent decades for their excellent conversion efficiency, high energy capacity, and low environmental impact. However, sluggish kinetics of the oxygen-related reactions at air cathodes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are still worth improving. Noble metals such as platinum (Pt), iridium (Ir), ruthenium (Ru) and their oxides are considered as the benchmark ORR and OER electrocatalysts, but they are expensive and prone to be poisoned due to the fuel crossover effect, and may suffer from agglomeration and leaching after long-term usage. To mitigate these limits, it is highly desirable to design alternative ORR/OER electrocatalysts with prominent performance. Metal-organic frameworks (MOFs) are a class of porous crystalline materials consisting metal ions/clusters coordinated by organic ligands. Their crystalline structure, tunable pore size and high surface area afford them wide opportunities as catalytic materials. This Review covers MOF-derived ORR/OER catalysts in electrochemical energy conversion, with a focus on the different strategies of material design and preparation, such as composition control and nanostructure fabrication, to improve the activity and durability of MOF-derived electrocatalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Phasic availability of terminal electron acceptor on oxygen reduction reaction in microbial fuel cell.

    PubMed

    Shanthi Sravan, J; Butti, Sai Kishore; Verma, Anil; Venkata Mohan, S

    2017-10-01

    Oxygen-reduction reactions (ORR) plays a pivotal role in determining microbial fuel cells (MFC) performance. In this study, an attempt to determine the influence of the phasic availability of terminal electron acceptor (TEA) on ORR was made. Two MFCs operated with dissolved oxygen (MFC-DC) and air (MFC-SC) as TEA were constructed and analyzed in continuous mode under open and closed circuit conditions. The bio-electrochemical analysis showed a marked influence of dissolved oxygen resulting in a maximum power density with MFC-DC (769mW/m(2)) compared to MFC-SC (684mW/m(2)). The availability of O2 in dissolved phase has lowered the activation losses during the MFC operation as a result of effective ORR. The cyclic voltammetry analysis revealed the TEA dependent biocatalyst activity of NADH and cytochrome complex which enabled electron transfer kinetics and improved substrate utilization. Finally, the study evidenced the critical role of TEA phasic availability to regulate the bio-electrogenic and substrate degradation potential in MFC. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. 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

  19. Shell-anchor-core structures for enhanced stability and catalytic oxygen reduction activity

    NASA Astrophysics Data System (ADS)

    Ramirez-Caballero, Gustavo E.; Hirunsit, Pussana; Balbuena, Perla B.

    2010-10-01

    Density functional theory is used to evaluate activity and stability properties of shell-anchor-core structures. The structures consist of a Pt surface monolayer and a composite core having an anchor bilayer where C atoms in the interstitial sites lock 3d metals in their locations, thus avoiding their surface segregation and posterior dissolution. The modified subsurface geometry induces less strain on the top surface, thus exerting a favorable effect on the surface catalytic activity where the adsorption strength of the oxygenated species becomes more moderate: weaker than on pure Pt(111) but stronger than on a Pt monolayer having a 3d metal subsurface. Here we analyze the effect of changing the nature of the 3d metal in the subsurface anchor bilayer, and we also test the use of a Pd monolayer instead of Pt on the surface. It is found that a subsurface constituted by two layers with an approximate composition of M2C (M=Fe, Ni, and Co) provides a barrier for the migration of subsurface core metal atoms to the surface. Consequently, an enhanced resistance against dissolution in parallel to improved oxygen reduction activity is expected, as given by the values of adsorption energies of reaction intermediates, delayed onset of water oxidation, and/or low coverage of oxygenated species at surface oxidation potentials.

  20. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    NASA Astrophysics Data System (ADS)

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-08-01

    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.

  1. 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.

  2. 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

  3. Novel osmium-based electrocatalysts for oxygen reduction and hydrogen oxidation in acid conditions

    NASA Astrophysics Data System (ADS)

    Uribe-Godínez, J.; Castellanos, R. H.; Borja-Arco, E.; Altamirano-Gutiérrez, A.; Jiménez-Sandoval, O.

    In this work, novel osmium electrocatalysts for oxygen reduction and hydrogen oxidation in 0.5 M H 2SO 4, have been developed. The syntheses were performed by thermolysis of Os 3(CO) 12 and Os 3(CO) 12/Vulcan ®, in two reaction media, N 2 (in the absence of solvents) and n-octane, in order to evaluate the effect of these parameters on the electrocatalytic activity of the new materials. In the solvent-free pathway, different reaction temperatures (in the 120-320 °C range) and times (5, 7 and 10 h) were explored; the syntheses in n-octane were done at reflux temperature, for 30 and 72 h. The products were characterized structurally by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy, and electrochemically by room temperature rotating disk electrode measurements, using cyclic and linear sweep voltammetry. Some materials prepared in both reaction media can efficiently perform the hydrogen oxidation and/or oxygen reduction reaction, i.e. those prepared by pyrolysis of Os 3(CO) 12/Vulcan ® in N 2, at 180 °C/7 h, 320 °C/5 h, 320 °C/7 h and 320 °C/10 h, as well as the materials synthesized in n-octane (from both Os precursors); the latter, in addition, have the important property of being tolerant to carbon monoxide to some extent, in contrast to platinum, which is easily deactivated even by traces of CO.

  4. 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.

  5. 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.

  6. Determination of the oxygen content in superconducting and related cuprates using temperature-programmed reduction

    NASA Astrophysics Data System (ADS)

    Halasz, Istvan; Jen, Hung-Wen; Brenner, Alan; Shelef, Mordecai; Kao, Sendjaja; Simon Ng, K. Y.

    1991-06-01

    The oxygen content and reducibilities of four base metal oxides, six nonconducting cuprates, and three superconducting cuprates were investigated by temperature-programmed reduction (TPR) from 30 to 900°C. It was shown that the copper, bismuth, and thallium ions of these oxides were reduced to the zero valence state. Thus, TPR is a useful technique for determining the actual oxygen stoichiometry of cuprates. For multiphase Bi 2CaSr 2Cu 2O 8+ x and Tl 2CaBa 2Cu 2O 8+ x superconductors pretreated in air, x was found to be 2 ± 0.2 and 1 ± 0.2, respectively. Both values are significantly higher than previously reported. The reduction of superconducting and related cuprates required higher temperatures than CuO, but the reducibility of CuO decreased when it was calcined in air at 940°C. The Bi- and Y-based superconducting cuprates exhibited the lowest reducibility among the samples investigated.

  7. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination.

    PubMed

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-10

    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.

  8. Controlled synthesis of Pd-Pt alloy hollow nanostructures with enhanced catalytic activities for oxygen reduction.

    PubMed

    Hong, Jong Wook; Kang, Shin Wook; Choi, Bu-Seo; Kim, Dongheun; Lee, Sang Bok; Han, Sang Woo

    2012-03-27

    Pd-Pt alloy nanocrystals (NCs) with hollow structures such as nanocages with porous walls and dendritic hollow structures and Pd@Pt core-shell dendritic NCs could be selectively synthesized by a galvanic replacement method with uniform Pd octahedral and cubic NCs as sacrificial templates. Fine control over the degree of galvanic replacement of Pd with Pt allowed the production of Pd-Pt NCs with distinctly different morphologies. The synthesized hollow NCs exhibited considerably enhanced oxygen reduction activities compared to those of Pd@Pt core-shell NCs and a commercial Pt/C catalyst, and their electrocatalytic activities were highly dependent on their morphologies. The Pd-Pt nanocages prepared from octahedral Pd NC templates exhibited the largest improvement in catalytic performance. We expect that the present work will provide a promising strategy for the development of efficient oxygen reduction electrocatalysts and can also be extended to the preparation of other hybrid or hetero-nanostructures with desirable morphologies and functions. © 2012 American Chemical Society

  9. 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

  10. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

    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

  11. 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.

  12. Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction.

    PubMed

    Ye, Feng; Liu, Hui; Hu, Weiwei; Zhong, Junyu; Chen, Yingying; Cao, Hongbin; Yang, Jun

    2012-03-14

    Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.

  13. ABTS-modified multiwalled carbon nanotubes as an effective mediating system for bioelectrocatalytic reduction of oxygen.

    PubMed

    Karnicka, Katarzyna; Miecznikowski, Krzysztof; Kowalewska, Barbara; Skunik, Magdalena; Opallo, Marcin; Rogalski, Jerzy; Schuhmann, Wolfgang; Kulesza, Pawel J

    2008-10-01

    The ability of such a common redox mediator as 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) to undergo sorption on carbon surfaces is explored here to convert multiwalled carbon nanotubes (CNTs) into a stable colloidal solution of ABTS-modified carbon nanostructures, the diameters of which are approximately 10 nm (as determined by transmission electron microscopy). Subsequently, inks composed of fungal laccase (Cerrena unicolor) mixed with the dispersion of ABTS-modified CNTs and stabilized with Nafion, were deposited on glassy carbon and successfully employed to the reduction of oxygen in McIlvain buffer at pH 5.2. For comparison, the systems utilizing only ABTS-free CNTs and laccase as well as ABTS-modified CNTs did not show appreciable activity toward the oxygen reduction. The three-dimensionally distributed ABTS-modified CNTs are expected to improve the film's overall conductivity and to facilitate electrical connection between the electrode and the enzyme. The network film of ABTS-modified CNTs is rigid, and it is characterized by charge propagation capabilities comparable to the conventional redox polymers. The whole concept of utilization of CNTs modified with ultrathin films of redox mediators in the preparation of efficient bioelectrocatalytic films seems to be of general importance to electroanalytical chemistry and to the development of biosensors.

  14. Electrochemical doping of three-dimensional graphene networks used as efficient electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Zhijuan; Cao, Xiehong; Ping, Jianfeng; Wang, Yixian; Lin, Tingting; Huang, Xiao; Ma, Qinglang; Wang, Fuke; He, Chaobin; Zhang, Hua

    2015-05-01

    Three-dimensional graphene networks (3DGNs) doped with a mono-heteroatom of N or B, or dual-heteroatoms of N and B were fabricated, which exhibit excellent oxygen reduction reaction (ORR) performance. Importantly, the onset potential and current density of N and B co-doped 3DGNs are comparable to those of the commercial Pt (30%)/C catalyst.Three-dimensional graphene networks (3DGNs) doped with a mono-heteroatom of N or B, or dual-heteroatoms of N and B were fabricated, which exhibit excellent oxygen reduction reaction (ORR) performance. Importantly, the onset potential and current density of N and B co-doped 3DGNs are comparable to those of the commercial Pt (30%)/C catalyst. Electronic supplementary information (ESI) available: Details of the N-3DGN, B-3DGN and NB-3DGN fabrication process. Description of characterization. Rotating disk electrode linear sweep voltammograms of 3DGN and Pt (30%)/C in O2-saturated 0.1 M KOH with various rotation rates at a scan rate of 5 mV s-1. Koutecky-Levich plots of 3DGN, Pt (30%)/C, N-3DGN, B-3DGN and NB-3DGN at different electrode potentials. See DOI: 10.1039/c4nr06631f

  15. 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.

  16. Carbon nanotube-templated synthesis of covalent porphyrin network for oxygen reduction reaction.

    PubMed

    Hijazi, Ismail; Bourgeteau, Tiphaine; Cornut, Renaud; Morozan, Adina; Filoramo, Arianna; Leroy, Jocelyne; Derycke, Vincent; Jousselme, Bruno; Campidelli, Stéphane

    2014-04-30

    The development of innovative techniques for the functionalization of carbon nanotubes that preserve their exceptional quality, while robustly enriching their properties, is a central issue for their integration in applications. In this work, we describe the formation of a covalent network of porphyrins around MWNT surfaces. The approach is based on the adsorption of cobalt(II) meso-tetraethynylporphyrins on the nanotube sidewalls followed by the dimerization of the triple bonds via Hay-coupling; during the reaction, the nanotube acts as a template for the formation of the polymeric layer. The material shows an increased stability resulting from the cooperative effect of the multiple π-stacking interactions between the porphyrins and the nanotube and by the covalent links between the porphyrins. The nanotube hybrids were fully characterized and tested as the supported catalyst for the oxygen reduction reaction (ORR) in a series of electrochemical measurements under acidic conditions. Compared to similar systems in which monomeric porphyrins are simply physisorbed, MWNT-CoP hybrids showed a higher ORR activity associated with a number of exchanged electrons close to four, corresponding to the complete reduction of oxygen into water.

  17. 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

  18. Evaluation of the participation of ferredoxin in oxygen reduction in the photosynthetic electron transport chain of isolated pea thylakoids.

    PubMed

    Kozuleva, Marina A; Ivanov, Boris N

    2010-07-01

    The contribution to reduction of oxygen by ferredoxin (Fd) to the overall reduction of oxygen in isolated pea thylakoids was studied in the presence of Fd versus Fd + NADP(+). The overall rate of electron transport was measured using a determination of Photosystem II quantum yield from chlorophyll fluorescence parameters, and the rate of oxidation of Fd was measured from the light-induced redox changes of Fd. At low light intensity, increasing Fd concentration from 5 to 30 microM in the absence of NADP(+) increased the proportion of oxygen reduction by Fd from 25-35 to 40-60% in different experiments. This proportion decreased with increasing light intensity. When NADP(+) was added in the presence of 15 microM Fd, which was optimal for the NADP(+) reduction rate, the participation of Fd in the reduction of oxygen was low, no more than 10%, and it also decreased with increasing light intensity. At high light intensity, the overall oxygen reduction rates in the presence of Fd + NADP(+) and in the presence of Fd alone were comparable. The significance of reduction of dioxygen either by water-soluble Fd or by the membrane-bound carriers of the photosynthetic electron transport chain for redox signaling under different light intensities is discussed.

  19. 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.

  20. Cobalt-Catalyzed Reductive Multicomponent Synthesis of β-Hydroxy- and β-Aminocarbonyl Compounds under Mild Conditions.

    PubMed

    Paul, Jérôme; Presset, Marc; Cantagrel, Frédéric; Le Gall, Erwan; Léonel, Eric

    2017-01-05

    The cobalt-catalyzed multicomponent reaction between sp(2) -hybridized organic halides, Michael acceptors, and unsaturated electrophiles has been developed. The reaction proceeds through a formal conjugate addition/aldol or aza-aldol (Mannich) tandem reaction initiated by the in situ metalation of the organic halide by cobalt catalysis. The essentially new reaction conditions that have been developed are very mild and atom-economic. Under these conditions, a broad range of β-hydroxy- and β-aminocarbonyl compounds are obtained in good to high yields.

  1. Reduction of Flavodoxin by Electron Bifurcation and Sodium Ion-dependent Reoxidation by NAD+ Catalyzed by Ferredoxin-NAD+ Reductase (Rnf).

    PubMed

    Chowdhury, Nilanjan Pal; Klomann, Katharina; Seubert, Andreas; Buckel, Wolfgang

    2016-06-03

    Electron-transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) from Acidaminococcus fermentans catalyze the endergonic reduction of ferredoxin by NADH, which is also driven by the concomitant reduction of crotonyl-CoA by NADH, a process called electron bifurcation. Here we show that recombinant flavodoxin from A. fermentans produced in Escherichia coli can replace ferredoxin with almost equal efficiency. After complete reduction of the yellow quinone to the blue semiquinone, a second 1.4 times faster electron transfer affords the colorless hydroquinone. Mediated by a hydrogenase, protons reoxidize the fully reduced flavodoxin or ferredoxin to the semi-reduced species. In this hydrogen-generating system, both electron carriers act catalytically with apparent Km = 0.26 μm ferredoxin or 0.42 μm flavodoxin. Membrane preparations of A. fermentans contain a highly active ferredoxin/flavodoxin-NAD(+) reductase (Rnf) that catalyzes the irreversible reduction of flavodoxin by NADH to the blue semiquinone. Using flavodoxin hydroquinone or reduced ferredoxin obtained by electron bifurcation, Rnf can be measured in the forward direction, whereby one NADH is recycled, resulting in the simple equation: crotonyl-CoA + NADH + H(+) = butyryl-CoA + NAD(+) with Km = 1.4 μm ferredoxin or 2.0 μm flavodoxin. This reaction requires Na(+) (Km = 0.12 mm) or Li(+) (Km = 0.25 mm) for activity, indicating that Rnf acts as a Na(+) pump. The redox potential of the quinone/semiquinone couple of flavodoxin (Fld) is much higher than that of the semiquinone/hydroquinone couple. With free riboflavin, the opposite is the case. Based on this behavior, we refine our previous mechanism of electron bifurcation.

  2. 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

  3. Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N,N -dimethylformamide

    DOE PAGES

    Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.; ...

    2015-12-07

    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 frommore » 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. Here, 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.« less

  4. 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.

  5. 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.

  6. Reduction in Post-Marathon Peak Oxygen Consumption: Sign of Cardiac Fatigue in Amateur Runners?

    PubMed

    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

    2016-02-01

    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. To verify if there are changes in the cardiopulmonary capacity, and cardiac inotropy and lusitropy in amateur marathoners after running a marathon. 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. 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). 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.

  7. Zinc chloride-catalyzed reactions of oxygen- and sulfur-containing compounds which model structures in coal

    SciTech Connect

    Mobley, D.P.

    1980-05-01

    Ether structures are believed to play a key role in linking the macromolecular units present in coal. A number of compounds which model the ether and sulfur structures found in coal were subjected to reaction in the presence of zinc chloride. Reactions were carried out in a batch autoclave at temperatures between 136/sup 0/C and 327/sup 0/C and under hydrogen or nitrogen pressure up to 16.8 MPa. Both cyclic and non-cyclic ethers reacted, provided that at least one methylene group was adjacent to the ether oxygen atom. Complete elimination of oxygen to form water was achieved with dibenzyl and cycloaliphatic ethers, but oxygen bonded directly to a phenyl or naphthyl group was converted to an unreactive phenolic hydroxyl group. As for the sulfur compounds, zinc chloride was found to promote removal of sulfur from sulfides and disulfides in which sulfur is bonded to a methylene group, but had no effect on diaryl sulfides, diaryl disulfides, or thiophenic structures. In those cases where sulfur was removed, a significant portion was found to be retained in the ZnCl/sub 2/ phase. The reaction products observed in both cases can be explained in terms of carbonium ion mechanisms similar to those used to explain Friedel-Crafts chemistry. In these mechanisms, the ZnCl/sub 2/ may be active in either a Lewis acid or a Bronsted acid form. Catalytic effects of nickel, zinc and magnesium and also the sulfides of nickel, zinc, iron and molybdenum on the reactions of dibenzyl ether and zinc chloride were also investigated. The presence of the metallic component enhanced the hydrogenolysis of dibenzyl ether, whereas the presence of ZnCl/sub 2/ reduced the activity of the NiS.

  8. 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.

  9. Phosphoric acid impurities in phosphoric acid fuel cell electrolytes. 2: Effects on the oxygen reduction reaction at platinum electrodes

    SciTech Connect

    Sugishima, Noboru; Hinatsu, J.T.; Foulkes, F.R. . Dept. of Chemical Engineering and Applied Chemistry)

    1994-12-01

    The effects of phosphorus acid additions on the oxygen reduction reaction at platinum electrodes in concentrated phosphoric acid were studied. The oxygen reduction currents decreased, and the Tafel slopes became more negative upon the addition of small concentrations of phosphorus acid. In addition,the phosphorus acid oxidation current tended to complete with the oxygen reduction current. These effects became more pronounced at higher phosphorus acid concentrations and at higher temperatures. Upon the addition of phosphorus acid the number of electrons involved in the oxygen reduction reaction decreased from a value close to four to a value approaching two, suggesting promotion of a two-electron reduction to peroxide. Therefore, in studies of the electrochemical reduction of oxygen in hot concentrated phosphoric acid or in fuel cell systems using hot concentrated phosphoric acid as electrolyte, it is recommended that precautions be taken against the inadvertent formation of the phosphorus acid. The removal of phosphorus acid from concentrated phosphoric acid by repeated potential cycling at 100 mV/s between + 0.5 and +1.50 V (vs. dynamic hydrogen electrode) was demonstrated.

  10. 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.

  11. 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

  12. 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

  13. Niobium oxide-supported platinum ultra-low amount electrocatalysts for oxygen reduction.

    PubMed

    Sasaki, K; Zhang, L; Adzic, R R

    2008-01-07

    We demonstrate a new approach to synthesizing high-activity electrocatalysts for the O(2) reduction reaction with ultra low Pt content. The synthesis involves placing a small amount of Pt, the equivalent of a monolayer, on carbon-supported niobium oxide nanoparticles (NbO(2) or Nb(2)O(5)). Rotating disk electrode measurements show that the Pt/NbO(2)/C electrocatalyst has three times higher Pt mass activity for the O(2) reduction reaction than a commercial Pt/C electrocatalyst. The observed high activity of the Pt deposit is attributed to the reduced OH adsorption caused by lateral repulsion between PtOH and oxide surface species. The new electrocatalyst also exhibits improved stability against Pt dissolution under a potential cycling regime (30,000 cycles from 0.6 V to 1.1 V). These findings demonstrate that niobium-oxide (NbO(2)) nanoparticles can be adequate supports for Pt and facilitate further reducing the noble metal content in electrocatalysts for the oxygen reduction reaction.

  14. Hydrogen and oxygen plasma enhancement in the Cu electrodeposition and consolidation processes on BDD electrode applied to nitrate reduction

    NASA Astrophysics Data System (ADS)

    Couto, A. B.; Santos, L. C. D.; Matsushima, J. T.; Baldan, M. R.; Ferreira, N. G.

    2011-09-01

    Copper nanoparticle electrodeposition and consolidation processes were studied on boron doped diamond (BDD) electrode submitted to hydrogen and oxygen plasma treatments. The modified BDD films were applied as electrodes for nitrate electroreduction. The results showed that both treatments have a strong influence on the copper deposition and dissolution processes. For BDD treated with hydrogen plasma the copper electrodeposit was homogeneous with high particle density. This behavior was attributed to the BDD surface hydrogenation that improved its conductivity. On the other hand, the treatment with oxygen plasma was important for the copper nanoparticle consolidation on BDD surface, confirmed by the result's reproducibility for nitrate reduction. This performance may be associated with the formation of oxygen groups that can act as anchor points for Cu-clusters, enhancing the interfacial adhesion between diamond and the metal coating. The best electrochemical nitrate reduction response was obtained in acid media, where occurred the separation of the nitrate reduction process and the water reduction reaction.

  15. A combinatorial study of platinum-based oxygen reduction electrocatalysts for hydrogen fuel cells

    NASA Astrophysics Data System (ADS)

    Bonakdarpour, Arman

    This thesis presents measurements of the stability and activities of Pt-based oxygen reduction reaction (ORR) electrocatalysts for proton exchange membrane fuel cells (PEMFC). Because more than 70% of electrochemical losses originate from the cathodic reduction of oxygen, research on ORR catalysts remains very active. Numerous combinatorial libraries of Pt1-xMx (M = Fe, Ni, Mn; 0 ≤ x ≤ 1) and Pt1-x-yMxMy ' (M, M' = Co, Ni, Mn, Fe) were prepared by magnetron sputtering using high surface area nano-structured thin film (NSTF) supports as substrates. The libraries were studied for the corrosion stability of the transition metal elements by acid leaching experiments. The results show that after exposing these libraries to 0.5M H2SO4 (or HClO4) at 80°C for several days, significant amounts of transition metals leach off. When the transition metal content was about 60% or less mostly surface leaching occurred and for more than 60% surface and bulk leaching were observed. The composition of these libraries after acid treatment was very close to the electrocatalysts tested in hydrogen fuel cells, thus showing that acid treatment can mimic the fuel cell environment very well. Alloys of Pt-Ta, on the other hand, showed no dissolution of Ta. However, the presence of more than 10% Ta in the alloy, significantly reduces the ORR activity. The rotating ring-disk electrode technique was used to measure the ORR activity of sputtered Pt1-xCox (0 < x < 0.5) films. After heat treatment a 1.7x gain in the specific current densities were observed. There are claims in the literature that very high activities (about 10x) can be achieved by Pt alloys such as Pt-Co with similar preparation methods. Poor experimental setups are most likely the sources of these observations. High surface area Pt and Pt-Co-Mn catalysts, sputtered onto NSTF supports were studied using the RRDE technique. The Pt-Co-Mn alloy showed a kinetic gain of about 20 mV over Pt for ORR. This is in agreement with the

  16. Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone.

    PubMed

    Lee, Jeong-Yub; Hozalski, Raymond M; Arnold, William A

    2007-02-01

    Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l(-1)) conditions. The effect of short-term (25-105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l(-1), the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l(-1), the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by

  17. Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption.

    PubMed

    Maimaiti, Yasheng; Nolan, Michael; Elliott, Simon D

    2014-02-21

    We studied the reduction of CuO(111) surface using density functional theory (DFT) with the generalized gradient approximation corrected for on-site Coulomb interactions (GGA + U) and screened hybrid DFT (HSE06 functional). The surface reduction process by oxygen vacancy formation and H2 adsorption on the CuO(111) surface is investigated as two different reduction mechanisms. It is found that both GGA + U and HSE06 predict the same trend in the relative stability of oxygen vacancies. We found that loss of the subsurface oxygen is initially thermodynamically favourable. As the oxygen vacancy concentration increases, mixture of subsurface and surface vacancies is energetically preferred over full reduction of the surface or subsurface monolayer. The reduction of Cu(2+) to Cu(+) is found to be more favourable than that of Cu(+) to Cu(0) in the most stable vacancy structures at all concentrations. Consistent with the oxygen vacancy calculations, H2 adsorption occurs initially on under-coordinated surface oxygen. Water molecules are formed upon the adsorption of H2 and this gives a mechanism for H2 reduction of CuO to Cu. Ab initio atomistic thermodynamics shows that reducing CuO to metallic Cu at the surface is more energetically difficult than in the bulk so that the surface oxide protects the bulk from reduction. Using H2 as the reducing agent, it is found that the CuO surface is reduced to Cu2O at approximately 360 K and that complete reduction from Cu2O to metallic Cu occurs at 780 K.

  18. Effects of endogenous neurotoxin quinolinic acid on reactive oxygen species production by Fenton reaction catalyzed by iron or copper

    PubMed Central

    Kubicova, Lenka; Hadacek, Franz; Weckwerth, Wolfram; Chobot, Vladimir

    2015-01-01

    The tryptophan metabolite, quinolinic (2,3-pyridinedicarboxylic) acid, is known as an endogenous neurotoxin. Quinolinic acid can form coordination complexes with iron or copper. The effects of quinolinic acid on reactive oxygen species production in the presence of iron or copper were explored by a combination of chemical assays, classical site-specific and ascorbic acid-free variants of the deoxyribose degradation assay, and mass spectrometry (ESI–MS). Quinolinic acid showed evident antioxidant activity in chemical assays, but the effect was more pronounced in the presence of copper as transition metal catalyst than in presence of iron. Nano-ESI–MS confirmed the ability of quinolinic acid to form coordination complexes with iron(II) or copper(II) and quinolinic acid stability against oxidative attack by hydroxyl radicals. The results illustrate a highly milieu-dependent quinolinic acid chemistry when it enters reactions as competitive ligand. PMID:25892824

  19. Carbonyl reductase 1 catalyzes 20β-reduction of glucocorticoids, modulating receptor activation and metabolic complications of obesity.

    PubMed

    Morgan, Ruth A; Beck, Katharina R; Nixon, Mark; Homer, Natalie Z M; Crawford, Andrew A; Melchers, Diana; Houtman, René; Meijer, Onno C; Stomby, Andreas; Anderson, Anna J; Upreti, Rita; Stimson, Roland H; Olsson, Tommy; Michoel, Tom; Cohain, Ariella; Ruusalepp, Arno; Schadt, Eric E; Björkegren, Johan L M; Andrew, Ruth; Kenyon, Christopher J; Hadoke, Patrick W F; Odermatt, Alex; Keen, John A; Walker, Brian R

    2017-09-06

    Carbonyl Reductase 1 (CBR1) is a ubiquitously expressed cytosolic enzyme important in exogenous drug metabolism but the physiological function of which is unknown. Here, we describe a role for CBR1 in metabolism of glucocorticoids. CBR1 catalyzes the NADPH- dependent production of 20β-dihydrocortisol (20β-DHF) from cortisol. CBR1 provides the major route of cortisol metabolism in horses and is up-regulated in adipose tissue in obesity in horses, humans and mice. We demonstrate that 20β-DHF is a weak endogenous agonist of the human glucocorticoid receptor (GR). Pharmacological inhibition of CBR1 in diet-induced obesity in mice results in more marked glucose intolerance with evidence for enhanced hepatic GR signaling. These findings suggest that CBR1 generating 20β-dihydrocortisol is a novel pathway modulating GR activation and providing enzymatic protection against excessive GR activation in obesity.

  20. Artesunate Activates Mitochondrial Apoptosis in Breast Cancer Cells via Iron-catalyzed Lysosomal Reactive Oxygen Species Production*

    PubMed Central

    Hamacher-Brady, Anne; Stein, Henning A.; Turschner, Simon; Toegel, Ina; Mora, Rodrigo; Jennewein, Nina; Efferth, Thomas; Eils, Roland; Brady, Nathan R.

    2011-01-01

    The antimalarial agent artesunate (ART) activates programmed cell death (PCD) in cancer cells in a manner dependent on the presence of iron and the generation of reactive oxygen species. In malaria parasites, ART cytotoxicity originates from interactions with heme-derived iron within the food vacuole. The analogous digestive compartment of mammalian cells, the lysosome, similarly contains high levels of redox-active iron and in response to specific stimuli can initiate mitochondrial apoptosis. We thus investigated the role of lysosomes in ART-induced PCD and determined that in MCF-7 breast cancer cells ART activates lysosome-dependent mitochondrial outer membrane permeabilization. ART impacted endolysosomal and autophagosomal compartments, inhibiting autophagosome turnover and causing perinuclear clustering of autophagosomes, early and late endosomes, and lysosomes. Lysosomal iron chelation blocked all measured parameters of ART-induced PCD, whereas lysosomal iron loading enhanced death, thus identifying lysosomal iron as the lethal source of reactive oxygen species upstream of mitochondrial outer membrane permeabilization. Moreover, lysosomal inhibitors chloroquine and bafilomycin A1 reduced ART-activated PCD, evidencing a requirement for lysosomal function during PCD signaling. ART killing did not involve activation of the BH3-only protein, Bid, yet ART enhanced TNF-mediated Bid cleavage. We additionally demonstrated the lysosomal PCD pathway in T47D and MDA-MB-231 breast cancer cells. Importantly, non-tumorigenic MCF-10A cells resisted ART-induced PCD. Together, our data suggest that ART triggers PCD via engagement of distinct, interconnected PCD pathways, with hierarchical signaling from lysosomes to mitochondria, suggesting a potential clinical use of ART for targeting lysosomes in cancer treatment. PMID:21149439

  1. 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.

  2. Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

    SciTech Connect

    Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C.; King, P. W.

    2016-04-21

    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.

  3. 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.

  4. Nitrogen-rich mesoporous carbon derived from melamine with high electrocatalytic performance for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Rongfang; Zhou, Tiaobao; Li, Hao; Wang, Hui; Feng, Hanqing; Goh, Jonathan; Ji, Shan

    2014-09-01

    Melamine-derived N-doped mesoporous carbon (MNMC) is synthesized by the pyrolysis of lysine and melamineunder at nitrogen atmosphere using ferric chloride as a dopant and SiO2 nanoparticles as hard templates to form mesoporous architecture. The N content in the bulk of carbon materials is as high as 11.3% and ca. 40.6% of N is in the form of pyridinic-N. The surface area of MNMC is ca. 650 m2 g-1 with a pore size distribution in the range of 2.2-34.5 nm. Compared to commercial Pt/C (20 wt%), MNMC exhibits much better electrocatalytic activity, better durability, and higher methanol tolerance for oxygen reduction reaction (ORR) in alkaline medium. Particularly, the onset ORR potential and half-wave ORR potential of MNMC are 1.059 and 0.871 V vs. RHE respectively, which are higher than those of commercial Pt/C.

  5. 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.

  6. Pt monolayer shell on nitrided alloy core — A path to highly stable oxygen reduction catalyst

    DOE PAGES

    Hu, Jue; Kuttiyiel, Kurian A.; Sasaki, Kotaro; ...

    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

  7. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    SciTech Connect

    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.

  8. Conducting metallopolymers as precursors to fabricate palladium nanoparticle/polymer hybrids for oxygen reduction.

    PubMed

    Edelman, Kate R; Stevenson, Keith J; Holliday, Bradley J

    2012-04-13

    The novel conducting metallopolymer [N,N'-((2,2'-dimethyl)propyl)bis(5-(2,2'-bithiophene-5-yl)salcylideniminato-palladium(II)](n) prepared by electropolymerization provides a polymer matrix in which the palladium metal centers are evenly distributed. The metal centers embedded directly in the conducting metallopolymer backbone serve as seed points for size-controlled palladium nanoparticle (NP) growth of 3.8 to 4.9 nm NPs within the conducting metallopolymer film. The palladium NP/conducting metallopolymer hybrid material has demonstrated electrocatalytic behavior toward oxygen reduction with peak current densities around 400 μA/cm(2) in acidic aqueous conditions. These results demonstrate a promising new method for the production of electrocatalytically active hybrid materials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Pt3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

    SciTech Connect

    Raciti, David; Kubal, Joseph; Ma, Cheng; Barclay, Michael; Gonzalez, Matthew; Chi, Miaofang; Greeley, Jeffrey; More, Karren L.; Wang, Chao

    2015-12-25

    Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well as Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.

  10. Pt3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

    DOE PAGES

    Raciti, David; Kubal, Joseph; Ma, Cheng; ...

    2015-12-25

    Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well as Densitymore » Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less

  11. 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.

  12. Boron doped graphene wrapped silver nanowires as an efficient electrocatalyst for molecular oxygen reduction

    PubMed Central

    Nair, Anju K.; Thazhe veettil, Vineesh; Kalarikkal, Nandakumar; Thomas, Sabu; Kala, M. S.; Sahajwalla, Veena; Joshi, Rakesh K.; Alwarappan, Subbiah

    2016-01-01

    Metal nanowires exhibit unusually high catalytic activity towards oxygen reduction reaction (ORR) due to their inherent electronic structures. However, controllable synthesis of stable nanowires still remains as a daunting challenge. Herein, we report the in situ synthesis of silver nanowires (AgNWs) over boron doped graphene sheets (BG) and demonstrated its efficient electrocatalytic activity towards ORR for the first time. The electrocatalytic ORR efficacy of BG-AgNW is studied using various voltammetric techniques. The BG wrapped AgNWs shows excellent ORR activity, with very high onset potential and current density and it followed four electron transfer mechanism with high methanol tolerance and stability towards ORR. The results are comparable to the commercially available 20% Pt/C in terms of performance. PMID:27941954

  13. 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).

  14. N-Doped Carbon Xerogels as Pt Support for the Electro-Reduction of Oxygen

    PubMed Central

    Alegre, Cinthia; Gálvez, María E.; Baquedano, Estela; Moliner, Rafael; Aricò, Antonino S.

    2017-01-01

    Durability and limited catalytic activity are key impediments to the commercialization of polymer electrolyte fuel cells. Carbon materials employed as catalyst support can be doped with different heteroatoms, like nitrogen, to improve both catalytic activity and durability. Carbon xerogels are nanoporous carbons that can be easily synthesized in order to obtain N-doped materials. In the present work, we introduced melamine as a carbon xerogel precursor together with resorcinol for an effective in-situ N doping (3–4 wt % N). Pt nanoparticles were supported on nitrogen-doped carbon xerogels and their activity for the oxygen reduction reaction (ORR) was evaluated in acid media along with their stability. Results provide new evidences of the type of N groups aiding the activity of Pt for the ORR and of a remarkable stability for N-doped carbon-supported Pt catalysts, providing appropriate physico-chemical features. PMID:28926984

  15. High-performance oxygen reduction catalyst derived from porous, nitrogen-doped carbon nanosheets

    NASA Astrophysics Data System (ADS)

    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.

  16. 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

  17. 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.

  18. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    SciTech Connect

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  19. Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction

    SciTech Connect

    Lim, B.; Tao, J.; Jiang, M.; Camargo, P.H.C.; Cho, E.C.; Lu, X.; Zhu, Y.; Xia, Y.

    2009-06-05

    Controlling the morphology of Pt nanostructures can provide a great opportunity to improve their catalytic properties and increase their activity on a mass basis. We synthesized Pd-Pt bimetallic nanodendrites consisting of a dense array of Pt branches on a Pd core by reducing K{sub 2}PtCl{sub 4} with L-ascorbic acid in the presence of uniform Pd nanocrystal seeds in an aqueous solution. The Pt branches supported on faceted Pd nanocrystals exhibited relatively large surface areas and particularly active facets toward the oxygen reduction reaction (ORR), the rate-determining step in a proton-exchange membrane fuel cell. The Pd-Pt nanodendrites were two and a half times more active on the basis of equivalent Pt mass for the ORR than the state-of-the-art Pt/C catalyst and five times more active than the first-generation supportless Pt-black catalyst.

  20. 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