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Sample records for oxygenic two-light reaction

  1. Oxygen evolution reaction catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

    2016-09-06

    An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

  2. Enhancing Activity for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

    2014-01-01

    Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies...... of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides....

  3. Oxygen evolution reaction in nanoconfined carbon nanotubes

    Science.gov (United States)

    Li, Ying; Lu, Xuefeng; Li, Yunfang; Zhang, Xueqing

    2018-05-01

    Improving oxygen electrochemistry through nanoscopic confinement has recently been highlighted as a promising strategy. In-depth understanding the role of confinement is therefore required. In this study, we simulate the oxygen evolution reaction (OER) on iron oxide nanoclusters under confinement of (7,7) and (8,8) armchair carbon nanotubes (CNTs). The free energies of the four proton coupled electron transfer (PCET) steps and the OER overpotentials are calculated. The Fe4O6 nanocluster confined in (7,7) CNT is found to be the most active for OER among the systems considered in this work. This leads to an increase in catalytic efficiency of OER compared to the hematite (110) surface, which was reported recently as an active surface towards OER. The calculated results show that the OER overpotential depends strongly on the magnetic properties of the iron oxide nanocluster. These findings are helpful for experimental design of efficient catalyst for water splitting applications.

  4. A Reaction Involving Oxygen and Metal Sulfides.

    Science.gov (United States)

    Hill, William D. Jr.

    1986-01-01

    Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

  5. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...

  6. Kinetics of liquid lithium reaction with oxygen-nitrogen mixtures

    International Nuclear Information System (INIS)

    Gil, T.K.; Kazimi, M.S.

    1986-01-01

    A series of experiments have been conducted in order to characterize the kinetics of lithium chemical reaction with a mixture of oxygen and nitrogen. Three mixed gas compositions were used; 80% N 2 and 20% O 2 , 90% N 2 and 10% O 2 , and 95% N 2 and 5% O 2 . The reaction rate was obtained as a function of lithium temperature and the oxygen fraction. Liquid lithium temperature varied from 400 to 1100 0 C. By varying the composition, the degree of inhibition of the lithium-nitrogen reaction rate due to the presence of oxygen was observed. The results indicate that the lithium-nitrogen reaction rate depended on both the fraction of oxygen present and lithium temperature. The lithium nitride layer formed from the reaction also had a significant inhibition effect on the lithium-nitrogen reaction rate while the lithium-oxygen reaction rate was not as greatly hindered. LITFIRE, a computer code which simulates temperature and pressure history in a containment building following lithium spills, was modified by including (1) an improved model for the lithium-nitrogen reaction rate and (2) a model for the lithium-CO 2 reaction. LITFIRE was used to simulate HEDL's LC-2 and LA-5 experiments, and the predicted temperatures and pressures were in a reasonable agreement. Furthermore, LITFIRE was applied to a prototypical fusion reactor containment in order to simulate the consequences of a lithium spill accident. The result indicated that if nitrogen was used as containment building gas during the accident, the consequences of the accident would be less severe than those with air. The pressure rise in the building was found to be reduced by 50% and the maximum temperature of the combustion zone was limited to 900 0 C instead of 1200 0 C in the case of air

  7. The oxygen evolution reaction on cobalt Part I. Reaction order experiments and impedance measurements

    NARCIS (Netherlands)

    Kobussen, A.G.C.; Willems, H.; Wit, J.H.W. de; Broers, G.H.J.

    1984-01-01

    It was found that the oxygen evolution reaction on cobalt in concentrated KOH solutions can be described differently for low and high overpotentials. In the overpotential range from 150 to 280 mV, the reaction has a Tafel slope of approximately 40 mV and a reaction order with respect to the KOH

  8. Determination of rate constants for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

    2008-07-01

    The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

  9. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Science.gov (United States)

    Morales, Javier; Günther, Germán; Zanocco, Antonio L; Lemp, Else

    2012-01-01

    Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  10. Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study

    Science.gov (United States)

    Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else

    2012-01-01

    Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966

  11. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Directory of Open Access Journals (Sweden)

    Javier Morales

    Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  12. Pulse radiolysis study of reaction of bull serum albumin electron adduct with oxygen. Polychromatic kinetics of reaction with adsorbed oxygen

    International Nuclear Information System (INIS)

    Pribush, A.G.

    1986-01-01

    By the method of pulse radiolysis the reaction of bull serum albumin electron adduct with oxygen is investigated. As pulsed radiation source electron linear accelerators with particle energy of 8.0 and 4.5 MeV and pulse time of 40 ns and 2.2 μs, respectively have been used. It is assumed that the disappearance of protein electron adduct occurs in the course of its interaction with oxygen adsorbed on protein globular molecule

  13. Online Measurement of Oxygen-Dependent Enzyme Reaction Kinetics

    DEFF Research Database (Denmark)

    Meissner, Murray Peter; Nordblad, Mathias; Woodley, John M

    2018-01-01

    accurate measurement of the oxygen mass balance in the gas-phase of a reactor. The method was successfully validated and demonstrated using two model reactions: firstly the oxidation of glucose by glucose oxidase and secondly the Baeyer-Villiger oxidation of macrocyclic ketones to lactones. Initial...

  14. Beyond the volcano limitations in electrocatalysis - oxygen evolution reaction

    DEFF Research Database (Denmark)

    Halck, Niels Bendtsen; Petrykin, Valery; Krtil, Petr

    2014-01-01

    Oxygen evolution catalysis is restricted by the interdependence of adsorption energies of the reaction intermediates and the surface reactivity. The interdependence reduces the number of degrees of freedom available for catalyst optimization. Here it is demonstrated that this limitation can be re...

  15. Molecular controls of the oxygenation and redox reactions of hemoglobin.

    Science.gov (United States)

    Bonaventura, Celia; Henkens, Robert; Alayash, Abdu I; Banerjee, Sambuddha; Crumbliss, Alvin L

    2013-06-10

    The broad classes of O(2)-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O(2)-binding functions. The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes.

  16. Thermal ion-molecule reactions in oxygen-containing molecules

    International Nuclear Information System (INIS)

    Kumakura, Minoru

    1981-02-01

    The energetics of ions and the thermal ion-molecule reactions in oxygen-containing molecules have been studied with a modified time-of-flight mass spectrometer. It was found that the translational energy of ion can be easily obtained from analysis of the decay curve using the time-of-flight mass spectrometer. The condensation-elimination reactions proceeded via cross- and homo-elimination mechanism in which the nature of intermediate-complex could be correlated with the nature of reactant ion. It was elucidated that behavior of poly-atomic oxygen-containing ions on the condensation-elimination reactions is considerably influenced by their oxonium ion structures having functional groups. In addition, the rate constants of the condensation-elimination reactions have affected with the energy state of reactant ion and the dipole moment and/or the polarizability of neutral molecule. It was clarified that the rate constants of the ion-molecule clustering reactions in poly-atomic oxygen-containing molecules such as cyclic ether of six member rings are very large and the cluster ions are stable owing to the large number of vibrational degree of freedom in the cluster ions. (author)

  17. Molecular Controls of the Oxygenation and Redox Reactions of Hemoglobin

    Science.gov (United States)

    Henkens, Robert; Alayash, Abdu I.; Banerjee, Sambuddha; Crumbliss, Alvin L.

    2013-01-01

    Abstract Significance: The broad classes of O2-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O2-binding functions. Recent Advances: The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. Critical Issues: An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. Future Directions: This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes. Antioxid. Redox Signal. 18, 2298–2313. PMID:23198874

  18. The reactions of oxygen and hydrogen with liquid sodium

    International Nuclear Information System (INIS)

    Ullmann, H.

    1981-01-01

    Results so far available as to the reactions and chemical equilibrium of oxygen and hydrogen with liquid sodium have been analyzed critically. The enthalpy values of the reactions have been discussed and supplemented on the basis of corresponding BORN-HABER cycles. The concentration and temperature functions of the hydrogen equilibrium pressure were deduced from experimental results. In relation to the solubility data the solid phases coexisting with liquid sodium in the ternary system Na-O-H have been discussed. The reaction of oxygen with hydrogen in diluted solution in liquid sodium has been investigated in more detail. Interaction coefficients, and the temperature functions of the free energy of formation and the equilibrium constant have been determined. (orig.)

  19. Hyperbaric oxygen treatment in radiation reactions; Hyperbar oksygenbehandling ved straalereaksjoner

    Energy Technology Data Exchange (ETDEWEB)

    Aanderud, Leif; Thorsen, Einar; Bratteboe, Guttorm; Forland, Martha; Kristensen, Gunnar

    2000-07-01

    Background: A national hyperbaric centre was established in 1994 at Haukeland Hospital with responsibility of all hyperbaric oxygen (HBO) treatment in Norway. In hypoxic tissues with symptomatic radiation reactions, hyperbaric oxygen induces the formation of collagen and angiogenesis resulting in permanently improved local microcirculation. Material and method: 234 patients received elective HBO treatment at Haukeland Hospital in 12997 with total of 4048 treatments. All 47 patients treated for radiation reactions in the pelvic area in 1997 received a questionnaire 3-15 months after HBO therapy, 81% reported. Results: Rectal bleeding and haematuria were reported as much improved in 61% and 55% respectively, while bladder incontinence was much improved in 46%. Interpretation: this treatment modality may be an alternative in symptomatic radiation reactions at the urinary bladder and the bowel when conventional treatment has given unsatisfactory results.

  20. Insights into the importance of oxygen functional groups in carbon reactions with oxygen containing gases

    International Nuclear Information System (INIS)

    John Zhu, Max Lu

    2005-01-01

    The role of pore structure of carbon in carbon-related adsorptions and reactions has been extensively investigated. However the studies on the role of surface chemistry of carbon are limited. In this paper, we present the importance of oxygen functional groups in carbon reactions with oxygen-containing gases. It is found that there is a good correlation between the electronic structures and reactivities of carbon edge sites. Zigzag sites are more active in oxygen adsorption because of the unpaired electrons and armchair sites are less active in oxygen adsorption due to the triple character. However, the desorption of semi-quinone oxygen from zigzag sites needs a bond energy ca. 30% higher than that of o-quinone oxygen from armchair edge sites. CO 2 and H 2 O adsorb on carbon surface much less favorably than O 2 . H 2 O is first physically adsorbed on the virgin graphite surface followed by chemisorption through oxygen atom approaching the carbon edge site and the movements of two hydrogen atoms to produce H 2 . The adsorption mechanism of H 2 O is different from that for CO 2 , but the final result is quite similar, i.e. producing only semi-quinone oxygen. Based upon the above studies, a new generalized mechanism, as shown in Fig. 1, is developed and can account for all the important kinetic phenomena of carbon-gas reactions. The key point is that in CO 2 /H 2 O-carbon reaction only semi-quinone formed; while, in O 2 -carbon reaction, semi-quinone, o-quinone (at lower pressure), and off-plane epoxy oxygen (at relatively higher pressure) can be formed. This is the main reason for the different reaction kinetics of O 2 -carbon reaction and CO 2 /H 2 O-carbon reactions as observed experimentally. The oxygen functional groups of carbon can be characterized by XPS, PZC (point of zero charge), IEP (isoelectric point) and TPD (temperature-programmed desorption), which were used in our previous studies. We treated the carbon surface with different acids, finding that HNO 3

  1. Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

    International Nuclear Information System (INIS)

    Feng Yongjun; Gago, Aldo; Timperman, Laure; Alonso-Vante, Nicolas

    2011-01-01

    This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru x Se y ) and non-precious transition metals (M x X y : M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru x Se y ), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.

  2. Benchmarking the Stability of Oxygen Evolution Reaction Catalysts

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Paoli, Elisa Antares; Knudsen, Brian Peter

    2014-01-01

    Because of the rising need for energy storage, potentially facilitated by electrolyzers, improvements to the catalysis of the oxygen evolution reaction (OER) become increasingly relevant. Standardized protocols have been developed for determining critical figures of merit, such as the electrochem......Because of the rising need for energy storage, potentially facilitated by electrolyzers, improvements to the catalysis of the oxygen evolution reaction (OER) become increasingly relevant. Standardized protocols have been developed for determining critical figures of merit...... coupled plasma mass spectrometry (ICP–MS). We show that a meaningful estimation of the stability cannot be achieved based on purely electrochemical tests. On the catalysts tested, the anodic dissolution current was four orders of magnitude lower than the total current. We propose that even if long......-term testing cannot be replaced, a useful evaluation of the stability can be achieved with short-term tests by using EQCM or ICP–MS....

  3. High-temperature reaction of ''anisotropic'' pyrolitic graphite with oxygen

    International Nuclear Information System (INIS)

    Lavrenko, V.A.; Pomytkin, A.P.; Neshpor, V.S.; Vinokur, F.L.

    1980-01-01

    Investigated is the kinetics of initial interaction stages of highly dense crystalloorientated pyrographite with oxygen. Oxidation was carried out in pure oxygen within 0.1-740 mm Hg pressure range and 500-1100 deg C temperature range. It is stated, that at the temperatures below 700 deg C pyrographite oxidation is subjected to a linear law. Above 700-800 deg C the linear law is preserved only at the initial oxidation stage, then the process is described by a parabolic law. Extension of the linear site is decreased in time with the reduction of oxygen pressure. The reaction has apparent fractional order. Activation energy of pyrogrpahite oxidation by the linear low constitutes approximately 58 kcal/mol within 600-800 deg C range and 14 kcal/mol within 800-1100 deg C range. The apparent activation energy constitutes approximately 13 kcal/mol in the region of correspondence to the parabolic law

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

    2017-04-15

    Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: 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-N{sub x} 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.

  6. Effect of Oxygen on the Mg-H Reaction

    DEFF Research Database (Denmark)

    Vigeholm, B.; Kjøller, John; Larsen, Bent

    1984-01-01

    Two identical samples of magnesium powder (purity, 99.58%) were hydrogenated at approximately 30 bar and 380 °C and dehydrogenated under vacuum at the same temperature about 500 times. The first sample was exposed to pure hydrogen (purity, 99.9999%) and the second was exposed to hydrogen containi...... absorption measurement performed after the cycling experiment. Despite the decreased absorption rate, which was mainly observed at higher degrees of reaction, little change in the desorption kinetics was observed....... 85 ppm O and 8 ppm H2O vapour. In both experiments a moderate overall reduction in the amount of hydrogen absorbed and desorbed was observed. This can be ascribed to a reduced absorption rate with increased number of cycles. The effect of oxygen was negligible, and this was confirmed by a precision...

  7. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela; Shinagawa, Tatsuya; Qureshi, Muhammad; Dhawale, Dattatray Sadashiv; Takanabe, Kazuhiro

    2016-01-01

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER

  8. Pulse radiolysis investigation of the reaction of the electronic adduct of bovine serum albumin with oxygen. Polychromatic kinetics of the reaction with adsorbed oxygen

    International Nuclear Information System (INIS)

    Pribush, A.G.

    1986-01-01

    The method of pulse radiolysis was used to investigate the reaction of the electronic adduct of bovine serum albumin with oxygen. It was suggested that the disappearance of the electronic adduct of the protein occurs in the course of its interaction with oxygen adsorbed on the globular protein molecule

  9. Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

  10. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    International Nuclear Information System (INIS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-01-01

    Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  11. Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Barik, Atanu; Indira Priyadarsini, K; Mohan, Hari; Bajaj, P N; Sapre, A V; Mittal, J P; Mukherjee, T [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

    2006-10-15

    Singlet molecular oxygen ({sup 1}O{sub 2}) is an excited state of molecular oxygen, having antiparallel spin in the same {pi} antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

  12. Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

    International Nuclear Information System (INIS)

    Barik, Atanu; Indira Priyadarsini, K.; Hari Mohan; Bajaj, P.N.; Sapre, A.V.; Mittal, J.P.; Mukherjee, T.

    2006-10-01

    Singlet molecular oxygen ( 1 O 2 ) is an excited state of molecular oxygen, having antiparallel spin in the same π antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

  13. Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

    Science.gov (United States)

    Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

    2014-06-01

    The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

  14. Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

    Energy Technology Data Exchange (ETDEWEB)

    Buss, R.J.; Baseman, R.J.; Guozhong, H.; Lee, Y.T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  15. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    Science.gov (United States)

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  16. Computational screening of doped αMnO2 catalystsfor the oxygen evolution reaction

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Hansen, Heine Anton; Vegge, Tejs

    2018-01-01

    Minimizing energy and materials costs for driving the oxygen evolution reaction (OER) is paramount for the commercialization of water electrolysis cells and rechargeable metal-air batteries. Using density functional theory calculations, we analyze the structural stability, catalytic activity...

  17. Temperature sensitivity of the oxygenation reaction of stripped ...

    African Journals Online (AJOL)

    -operativity (n) at all three experimental temperatures compared to L. capensis. The heat of oxygenation (",H) between 8"C (pH 7,63) and. 23"C (pH 7,49) calculated for L capensis haemoglobin (-56,3 kJ.mol ') exceeded that of C. gariepinus ...

  18. OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

    Energy Technology Data Exchange (ETDEWEB)

    Byrn, Marianne; Calvin, Melvin

    1965-12-01

    Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

  19. Quantitative analysis of oxygen depth distribution by means of deuteron reaction

    International Nuclear Information System (INIS)

    Dyumin, A.N.; Eremin, V.K.; Konnikov, S.G.

    1993-01-01

    Experimentally are investigated and realized possibilities for using the reaction for quantitative determination of the depth profiles of the oxygen distribution in HTSC structures in layers up to 10 4 A. It is concluded that in the near-surface layers when profiling the oxygen content is achieved the spatial resolution of 150 A

  20. Formation and Migration of Oxygen Vacancies in SrCoO3 and their effect on Oxygen Evolution Reactions

    KAUST Repository

    Tahini, Hassan A.

    2016-07-18

    Perovskite SrCoO3 is a potentially useful material for promoting the electrocatalytic oxygen evolution reaction, with high activities predicted theoretically and observed experimentally for closely related doped perovskite materials. However, complete stoichiometric oxidation is very difficult to realize experimentally – in almost all cases there are significant fractions of oxygen vacancies present. Here, using first principles calculations we study oxygen vacancies in perovskite SrCoO3 from thermodynamic, electronic and kinetic points of view. We find that an oxygen vacancy donates two electrons to neighboring Co sites in the form of localized charge. The formation energy of a single vacancy is very low and estimated to be 1.26 eV in the dilute limit. We find that a vacancy is quite mobile with a migration energy of ~0.5 eV. Moreover, we predict that oxygen vacancies exhibit a tendency towards clustering which is in accordance with the material’s ability to form a variety of oxygen-deficient structures. These vacancies have a profound effect on the material’s ability to facilitate OER, increasing the overpotential from ~0.3 V for the perfect material to ~0.7 for defective surfaces. A moderate compressive biaxial strain (2%) is predicted here to increase the surface oxygen vacancy formation energy by ca. 30%, thus reducing the concentration of surface vacancies and thereby preserving the OER activity of the material.

  1. Formation and Migration of Oxygen Vacancies in SrCoO3 and their effect on Oxygen Evolution Reactions

    KAUST Repository

    Tahini, Hassan A.; Tan, Xin; Schwingenschlö gl, Udo; Smith, Sean C.

    2016-01-01

    Perovskite SrCoO3 is a potentially useful material for promoting the electrocatalytic oxygen evolution reaction, with high activities predicted theoretically and observed experimentally for closely related doped perovskite materials. However, complete stoichiometric oxidation is very difficult to realize experimentally – in almost all cases there are significant fractions of oxygen vacancies present. Here, using first principles calculations we study oxygen vacancies in perovskite SrCoO3 from thermodynamic, electronic and kinetic points of view. We find that an oxygen vacancy donates two electrons to neighboring Co sites in the form of localized charge. The formation energy of a single vacancy is very low and estimated to be 1.26 eV in the dilute limit. We find that a vacancy is quite mobile with a migration energy of ~0.5 eV. Moreover, we predict that oxygen vacancies exhibit a tendency towards clustering which is in accordance with the material’s ability to form a variety of oxygen-deficient structures. These vacancies have a profound effect on the material’s ability to facilitate OER, increasing the overpotential from ~0.3 V for the perfect material to ~0.7 for defective surfaces. A moderate compressive biaxial strain (2%) is predicted here to increase the surface oxygen vacancy formation energy by ca. 30%, thus reducing the concentration of surface vacancies and thereby preserving the OER activity of the material.

  2. Vibrationally Excited Carbon Monoxide Produced via a Chemical Reaction Between Carbon Vapor and Oxygen

    Science.gov (United States)

    Jans, Elijah R.; Eckert, Zakari; Frederickson, Kraig; Rich, Bill; Adamovich, Igor V.

    2017-06-01

    Measurements of the vibrational distribution function of carbon monoxide produced via a reaction between carbon vapor and molecular oxygen has shown a total population inversion on vibrational levels 4-7. Carbon vapor, produced using an arc discharge to sublimate graphite, is mixed with an argon oxygen flow. The excited carbon monoxide is vibrationally populated up to level v=14, at low temperatures, T=400-450 K, in a collision-dominated environment, 15-20 Torr, with total population inversions between v=4-7. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of the reaction enthalpy. Kinetic modeling of the flow reactor, including state specific vibrational processes, was performed to infer the vibrational distribution of the products of the reaction. The results show viability of developing of a new chemical CO laser from the reaction of carbon vapor and oxygen.

  3. Realization of two light particle correlation experiments: behaviour to very low relative momenta (measurement with a magnetic spectrometer) and influence of the violence of reaction on the emission sources (measured by the neutron detector ORION

    International Nuclear Information System (INIS)

    Sezac, L.

    1993-01-01

    The correlation measurements between light particles emitted during heavy ion collisions allow to estimate the time-space extension of the emitting sources. This report about the preliminaries of two correlation experiments is split into two parts. The first one describes a test experiment, performed to study the feasibility of a correlation experiment at very low relative momenta with the help of a magnetic spectrometer. The results will allow to determine the still unknown relative effects from the final state interaction and the combination of both Coulomb interaction and quantum statistics. A correlation study without experimental selection of the impact parameter gives unclear answers about the sizes and the temporal characteristics of the emitting systems. The second part analyses the sources of the alpha particles detected in the reaction chamber of the multidetector ORION used as a violence of the reaction filter. The results show that it is possible to consider as a good filter a fast information called 'prompt peak' (correlated to the neutron multiplicity detected with ORION). Under such conditions a study of two particle correlations from equilibrated systems with a reasonable statistics becomes thinkable. The results obtained allow to characterize the emitting sources (speed, intensity, temperature) as a function of the violence of the reaction for the system 208 Pb + 93 Nb at 29 MeV/u. (author)

  4. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.

    Science.gov (United States)

    McCrory, Charles C L; Jung, Suho; Peters, Jonas C; Jaramillo, Thomas F

    2013-11-13

    Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm(-2) per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing the aforementioned surface area measurements, one can determine electrocatalyst turnover frequencies. The reported protocol was used to examine the oxygen-evolution activity of the following systems in acidic and alkaline solutions: CoO(x), CoPi, CoFeO(x), NiO(x), NiCeO(x), NiCoO(x), NiCuO(x), NiFeO(x), and NiLaO(x). The oxygen-evolving activity of an electrodeposited IrO(x) catalyst was also investigated for comparison. Two general observations are made from comparing the catalytic performance of the OER catalysts investigated: (1) in alkaline solution, every non-noble metal system achieved 10 mA cm(-2) current densities at similar operating overpotentials between 0.35 and 0.43 V, and (2) every system but IrO(x) was unstable under oxidative conditions in acidic solutions.

  5. Communications: Elementary oxygen electrode reactions in the aprotic Li-air battery

    DEFF Research Database (Denmark)

    Hummelshøj, Jens Strabo; Blomquist, Jakob; Datta, Soumendu

    2010-01-01

    We discuss the electrochemical reactions at the oxygen electrode of an aprotic Li-air battery. Using density functional theory to estimate the free energy of intermediates during the discharge and charge of the battery, we introduce a reaction free energy diagram and identify possible origins...

  6. Rate of reaction of dimethylmercury with oxygen atoms in the gas phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge

    1986-01-01

    The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...

  7. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  8. The effect of temperature and pressure on the oxygen reduction reactions in polyelectrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

    1997-12-31

    The effect of temperature and pressure on the oxygen reduction reaction in polyelectrolyte membranes was described. Polyelectrolytes chosen for the experiment differed in composition, weight and flexibility of the polymer chains. The study was conducted in a solid state electrochemical cell at temperatures between 30 and 95 degrees C and in the pressure range of 1 to 5 atm. The solubility of oxygen in these membranes was found to follow Henry`s Law, while the diffusion coefficient decreased with pressure. The effect of temperature on the solubility of oxygen and the diffusion coefficient of oxygen in the membranes was similar to that observed in solution electrolytes. 2 refs., 3 figs.

  9. Importance of the support and the grade of Pt in the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Enriquez M, O.; Fernandez V, S.M.

    2004-01-01

    The technology of the fuel cells type Proton Exchange Membrane (PEM), needs to define clearly the influence of the different involved parameters, this is made in general using methods of electrochemical impedance, in which the involved reactions can be presupposed. Another form of making is identifying experimentally the influence of the different parameters. In this work the obtained results are reported with for the oxygen reduction reaction using as electro catalyst platinum analytical grade and fuel cell grade and like support graphite and vulcan. It was found that as much the support as the particle size modify the over potential for the oxygen reduction reaction (Orr). (Author)

  10. Optical emissions from oxygen atom reactions with adsorbates

    Science.gov (United States)

    Oakes, David B.; Fraser, Mark E.; Gauthier-Beals, Mitzi; Holtzclaw, Karl W.; Malonson, Mark; Gelb, Alan H.

    1992-12-01

    Although most optical materials are inert to the ambient low earth orbit environment, high velocity oxygen atoms will react with adsorbates to produce optical emissions from the ultraviolet into the infrared. The adsorbates arise from chemical releases or outgassing from the spacecraft itself. We have been investigating kinetic and spectral aspects of these phenomenon by direct observation of the 0.2 to 13 micrometers chemiluminescence from the interaction of a fast atomic oxygen beam with a continuously dosed surface. The dosing gases include fuels, combustion products and outgassed species such as unsymmetrical dimethylhydrazine (UDMH), NO, H2O and CO. The surface studied include gold and magnesium fluoride. In order to relate the results to actual spacecraft conditions these phenomena have been explored as a function of O atom velocity, dosant flux and substrate temperature. UDMH dosed surfaces exhibit spectra typical (wavelength and intensity) of carbonaceous surfaces. The primary emitters are CO, CO2, and OH. H2O dosed surfaces are dominated by OH and /or H2O emission while CO dosed surfaces are dominated by CO and CO2 emissions. The nitric oxide dosed surface produces a glow from 0.4 to 5.4 micrometers due to NO2* continuum emission. The emission was observed to increase by a factor of two upon cooling the surface from 20 degree(s)C to -35 degree(s)C.

  11. Molecular Beam Chemistry: Reactions of Oxygen Atoms with Halogen Molecules.

    Science.gov (United States)

    1982-10-15

    nonlinear one has s = 3, r = 1, and n = 3/2. In the "loose" complex the bending modes go over to free rotation of the product diatomit molecule; thus s...contains no adjustable parameters. All observable properties *l of the reaction may be predicted including product velocity and angular dis- tributions...example, P. R. Bevington, Data Reduction and Error Analysis for the Physical Sciences (McGraw-Hill Book Co., New York, 1969). 65. Equation (3) is strictly

  12. Singlet Oxygen and Free Radical Reactions of Retinoids and Carotenoids—A Review

    Science.gov (United States)

    Truscott, T. George

    2018-01-01

    We report on studies of reactions of singlet oxygen with carotenoids and retinoids and a range of free radical studies on carotenoids and retinoids with emphasis on recent work, dietary carotenoids and the role of oxygen in biological processes. Many previous reviews are cited and updated together with new data not previously reviewed. The review does not deal with computational studies but the emphasis is on laboratory-based results. We contrast the ease of study of both singlet oxygen and polyene radical cations compared to neutral radicals. Of particular interest is the switch from anti- to pro-oxidant behavior of a carotenoid with change of oxygen concentration: results for lycopene in a cellular model system show total protection of the human cells studied at zero oxygen concentration, but zero protection at 100% oxygen concentration. PMID:29301252

  13. Critical appraisal on the role of catalysts for the oxygen reduction reaction in lithium-oxygen batteries

    International Nuclear Information System (INIS)

    Lodge, Andrew W.; Lacey, Matthew J.; Fitt, Matthew; Garcia-Araez, Nuria; Owen, John R.

    2014-01-01

    This work reports a detailed characterization of the reduction of oxygen in pyrrolidinium-based ionic liquids for application to lithium-oxygen batteries. It is found that, in the absence of Li + , all electron transfer kinetics are fast, and therefore, the reactions are limited by the mass transport rate. Reversible reduction of O 2 to O 2 • − and O 2 • − to O 2 2− take place at E 0 = 2.1 V and 0.8 V vs. Li + /Li, respectively. In the presence of Li + , O 2 is reduced to LiO 2 first and then to Li 2 O 2 . The solubility product constant of Li 2 O 2 is found to be around 10 −51 , corroborating the hypothesis that electrode passivation by Li 2 O 2 deposition is an important issue that limits the capacity delivered by lithium-oxygen batteries. Enhancing the rate of Li 2 O 2 formation by using different electrode materials would probably lead to faster electrode passivation and hence smaller charge due to oxygen reduction (smaller capacity of the battery). On the contrary, soluble redox catalysts can not only increase the reaction rate of Li 2 O 2 formation but also avoid electrode passivation since the fast diffusion of the soluble redox catalyst would displace the formation of Li 2 O 2 at a sufficient distance from the electrode surface

  14. Reactions of oxygen containing structures in coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Hodek, W.; Kirschstein, J.; Van Heek, K.-H. (DMT-Gesellschaft fuer Forschung und Pruefung mbH, Essen (Germany, F.R.))

    1991-03-01

    In coal pyrolysis O-containing structures such as ether bridges and phenolic groups play an important role. Their reactions were studied by non-isothermal pyrolysis of a high volatile bituminous coal and some model polymers with gas chromatographic detection of the gaseous pyrolysis products. The coal was separated into the maceral groups vitrinite, exinite and inertinite, which showed markedly different pyrolysis behaviour. The formation of CO, methane and benzene was measured versus temperature. By comparison with polyphenyleneoxide and phenol-formaldehyde resins, it was found that the main volatilization, during which most of the tar is evolved, is initiated by cleavage of alkyl-aryl-ethers. Rearrangements of the primarily formed radicals lead to the formation of CO and methane at higher temperatures. 5 refs., 8 figs., 1 tab.

  15. Reaction of oxygen with the respiratory chain in cells and tissues.

    Science.gov (United States)

    Chance, B

    1965-09-01

    This paper considers the way in which the oxygen reaction described by Dr. Nicholls and the ADP control reactions described by Dr. Racker could cooperate to establish a purposeful metabolic control phenomenon in vivo. This has required an examination of the kinetic properties of the respiratory chain with particular reference to methods for determinations of oxygen affinity (K(m)). The constant parameter for tissue respiration is k(1), the velocity constant for the reaction of oxygen with cytochrome oxidase. Not only is this quantity a constant for a particular tissue or mitochondria; it appears to vary little over a wide range of biological material, and for practical purposes a value of 5 x 10(7) at 25 degrees close to our original value (20) is found to apply with adequate accuracy for calculation of K(m) for mammalia. The quantity which will depend upon the tissue and its metabolic state is the value of K(m) itself, and K(m) may be as large as 0.5 microM and may fall to 0.05 microM or less in resting, controlled, or inhibited states. The control characteristic for ADP may depend upon the electron flux due to the cytochrome chain (40); less ADP is required to activate the slower electron transport at lower temperatures than at higher temperatures. The affinity constants for ADP control appear to be less dependent upon substrate supplied to the system. The balance of ADP and oxygen control in vivo is amply demonstrated experimentally and is dependent on the oxygen concentration as follows. In the presence of excess oxygen, control may be due to the ADP or phosphate (or substrate), and the kinetics of oxygen utilization will be independent of the oxygen concentration. As the oxygen concentration is diminished, hemoglobin becomes disoxygenated, deep gradients of oxygen concentration develop in the tissue, and eventually cytochrome oxidase becomes partially and then completely reduced. DPN at this point will become reduced and the electron flow diminished. The rate

  16. High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.

    2017-01-18

    The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

  17. Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

    International Nuclear Information System (INIS)

    Sato, S.

    1987-01-01

    Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

  18. Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect.

    Science.gov (United States)

    Yao, Xiahui; Dong, Qi; Cheng, Qingmei; Wang, Dunwei

    2016-09-12

    As an electrochemical energy-storage technology with the highest theoretical capacity, lithium-oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round-trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium-oxygen batteries for high-performance operations and how to eventually materialize the full potentials of this promising technology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  19. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    OpenAIRE

    Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

    2018-01-01

    The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

  20. Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

    2006-01-01

    Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

  1. Oxygen consumption through metabolism and photodynamic reactions in cells cultured on microbeads

    International Nuclear Information System (INIS)

    Schunck, T.; Poulet, P.

    2000-01-01

    Oxygen consumption by cultured cells, through metabolism and photosensitization reactions, has been calculated theoretically. From this result, we have derived the partial oxygen pressure P O 2 in the perfusion medium flowing across sensitized cultured cells during photodynamic experiments. The P O 2 variations in the perfusate during light irradiation are related to the rate of oxygen consumption through photoreactions, and to the number of cells killed per mole of oxygen consumed through metabolic processes. After irradiation, the reduced metabolic oxygen consumption yields information on the cell death rate, and on the photodynamic cell killing efficiency. The aim of this paper is to present an experimental set-up and the corresponding theoretical model that allows us to control the photodynamic efficiency for a given cell-sensitizer pair, under well defined and controlled conditions of irradiation and oxygen supply. To demonstrate the usefulness of the methodology described, CHO cells cultured on microbeads were sensitized with pheophorbide a and irradiated with different light fluence rates. The results obtained, i.e. oxygen consumption of about 0.1 μMs -1 m -3 under a light fluence rate of 1 W m -2 , 10 5 cells killed per mole of oxygen consumed and a decay rate of about 1 h -1 of living cells after irradiation, are in good agreement with the theoretical predictions and with previously published data. (author)

  2. Reaction of hydrogen sulfide with oxygen in the presence of sulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, O.; Tsao, L.

    1983-01-14

    Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

  3. Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

    Energy Technology Data Exchange (ETDEWEB)

    Weres, Oleh; Tsao, Leon

    1983-01-01

    Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

  4. Oxygen Reduction Reaction on Pt Overlayers Deposited onto a Gold Film: Ligand, Strain, and Ensemble Effect

    DEFF Research Database (Denmark)

    Deng, Yu-Jia; Tripkovic, Vladimir; Rossmeisl, Jan

    2016-01-01

    We study the oxygen reduction reaction (ORR), the catalytic process occurring at the cathode in fuel cells, on Pt layers prepared by electrodeposition onto an Au substrate. Using a nominal Pt layer by layer deposition method previously proposed, imperfect layers of Pt on Au are obtained. The ORR...

  5. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

    2010-01-01

    We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

  6. Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

    DEFF Research Database (Denmark)

    Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

    2011-01-01

    Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the ca...

  7. Reactions of oxygen and hydrogen with liquid sodium - a critical survey

    International Nuclear Information System (INIS)

    Ullmann, H.

    1982-01-01

    The fundamentals of solvation chemistry are presented with appropriate components formulated. Methods of investigation and kinetics of the reactions are described. The hydrogen equilibrium pressure and saturation solubilities are described. The chemical equilibrium between O and H in solution is presented with detailed tabulation of the saturation solutions of oxygen, hydrogen and hydroxide in liquid sodium. Agreements and differences with the literature are presented

  8. Efficient oxygen reduction reaction using ruthenium tetrakis(diaquaplatinum)octacarboxyphthalocyanine catalyst supported on MWCNT platform

    CSIR Research Space (South Africa)

    Maxakato, NW

    2011-02-01

    Full Text Available -1 Electroanalysis 2011, 23, No. 2, 325 ? 329 Efficient Oxygen Reduction Reaction Using Ruthenium Tetrakis(diaquaplatinum)Octacarboxyphthalocyanine Catalyst Supported on MWCNT Platform Nobanathi W. Maxakato,a Solomon A. Mamuru,a Kenneth I. Ozoemena*a, b a...

  9. Ruthenium supported on nitrogen-doped carbon nanotubes for the oxygen reduction reaction in alkaline

    CSIR Research Space (South Africa)

    Mabena, LF

    2012-10-01

    Full Text Available between 0 and 10 wt.%. The activity of the prepared nanocatalysts toward the oxygen reduction reaction (ORR) was characterized using the rotating disk electrode and voltammetry techniques. The ORR activity was higher at lower concentrations of Ru on N...

  10. Molecular dynamics simulation of the first electron transfer step in the oxygen reduction reaction

    NARCIS (Netherlands)

    Hartnig, C.B.; Koper, M.T.M.

    2002-01-01

    We present a molecular dynamics simulation of solvent reorganization in the first electron transfer step in the oxygen reduction reaction, i.e. O2+e-¿O2-, modeled as taking place in the outer Helmholtz plane. The first electron transfer step is usually considered the rate-determining step from many

  11. Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Yan, Xiao-Yan; Tong, Xi-Li; Zhang, Yue-Fei; Han, Xiao-Dong; Wang, Ying-Yong; Jin, Guo-Qiang; Qin, Yong; Guo, Xiang-Yun

    2012-02-11

    Cuprous oxide (Cu(2)O) nanoparticles dispersed on reduced graphene oxide (RGO) were prepared by reducing copper acetate supported on graphite oxide using diethylene glycol as both solvent and reducing agent. The Cu(2)O/RGO composite exhibits excellent catalytic activity and remarkable tolerance to methanol and CO in the oxygen reduction reaction. This journal is © The Royal Society of Chemistry 2012

  12. Electroenzymatic Reactions With Oxygen on Laccase-Modified Electrodes in Anhydrous (Pure) Organic Solvent

    DEFF Research Database (Denmark)

    Yarapolov, A.; Shleev, S.; Zaitseva, E.

    2007-01-01

    in two different ways: (i) by studying the electroreduction of oxygen in anhydrous DMSO via a direct electron transfer mechanism without proton donors and (ii) by doing the same experiments in the presence of laccase substrates, which display in pure organic solvents both the properties of electron......The electroenzymatic reactions of Trametes hirsuta laccase in the pure organic solvent dimethyl sulfoxide (DMSO) have been investigated within the framework for potential use as a catalytic reaction scheme for oxygen reduction. The bioelectrochemical characteristics of laccase were investigated...... donors as well as the properties of weak acids. The results obtained with laccase in anhydrous DMSO were compared with those obtained previously in aqueous buffer. It was shown that in the absence of proton donors under oxygenated conditions, formation of superoxide anion radicals is prevented at bare...

  13. Electrocatalytic behavior of thin Co-Te-O films in oxygen evolution and reduction reactions

    International Nuclear Information System (INIS)

    Rashkova, V.; Kitova, S.; Vitanov, T.

    2007-01-01

    Co-Te-O catalytic films, obtain by vacuum co-evaporation of Co and TeO 2 are investigated as electrocatalysts for oxygen reactions in alkaline media. Bifunctional gas-diffusion oxygen electrodes (gde) are prepared by direct deposition of catalyst films on gas-diffusion membranes (gdm) consisting of hydrophobized carbon blacks or hydrophobized 'Ebonex' (suboxides of titanium dioxide). Thus obtained electrodes with different atomic ratio R Co/Te of the catalyst, treated at different temperatures were electrochemically tested by means of cyclic voltammetry and steady-state voltammetry. It is shown that the electrodes exhibit high catalytic activity toward oxygen evolution and reduction reaction despite very low catalyst loading of about 0.05-0.5 mg cm -2

  14. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  15. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    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.

  16. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Powell, J; Kaplan, A F H [Department of Applied Physics and Mechanical Engineering, Luleaa University of Technology, SE-971 87 Luleaa (Sweden); Petring, D [Fraunhofer-Institute for Laser Technology (ILT), Steinbachstrasse 15, Aachen (Germany); Kumar, R V [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ (United Kingdom); Al-Mashikhi, S O; Voisey, K T [Department of Mechanical, Materials and Manufacturing Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)], E-mail: jpowell@laserexp.co.uk

    2009-01-07

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  17. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    International Nuclear Information System (INIS)

    Powell, J; Kaplan, A F H; Petring, D; Kumar, R V; Al-Mashikhi, S O; Voisey, K T

    2009-01-01

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  18. Rate constant for the reaction of atomic oxygen with phosphine at 298 K

    Science.gov (United States)

    Stief, L. J.; Payne, W. A.; Nava, D. F.

    1987-01-01

    The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

  19. Adverse reactions of hyperbaric oxygen therapy - case description of a generalised seizure

    Directory of Open Access Journals (Sweden)

    Grobelska Kinga

    2016-03-01

    Full Text Available Hyperbaric oxygen therapy (HBOT is a safe treatment, provided fulfilling certain rules of patient qualifications to treatment, as well as supervision over the course of therapy by qualified medical staff. Side effects reported in the literature are rare, and are usually mild and transient. Professional medical staff allows minimising the adverse events occurrence. The scale of complications is unknown, especially in Polish hyperbaric center. Careful analysis could be used to develop prevention procedures for patients of hyperbaric oxygen therapy. Hyperbaric Oxygen Centre and Wound Treatment in Bydgoszcz during 28 months performed hyperbaric oxygen therapy (HBOT in case of 423 patients. During this period, adverse events occurred occasionally. 17 cases have been reported. Authors described study case 77 year-old patient who was admitted due to non-healing wound-left lower abdomen (state after radiotherapy. During the fourth session, on decompression phase patient have had a generalized seizure (tonic-clonic. The decompression was stopped, the oxygen supply was disconnected but only after the drug administration seizures terminated. The most likely causative agent of the adverse reactions of the patient treated with HBOT was the oxygen toxic effect on the brain tissue. However, analyzing the circumstances of the seizure termination: phase of decompression at the pressure 2ATA and lack of oxygen disconnection response, it cannot be excluded other causes of this complication.

  20. Promotion of multi-electron transfer for enhanced photocatalysis: A review focused on oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Changhua [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); College of Chemistry and Biology, Beihua University, Jilin 132013 (China); Zhang, Xintong, E-mail: xtzhang@nenu.edu.cn [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China); Liu, Yichun [Centre for Advanced Optoelectronic Functional Materials Research, and Key Laboratory for UV-Emitting Materials and Technology of Ministry of Education, Northeast Normal University, Changchun 130024 (China)

    2015-12-15

    Highlights: • Oxygen reduction reaction (ORR) in photocatalysis process is focused. • Multi-electron transfer ORR is reviewed. • This review provides a guide to access to enhanced photocatalysis via multi-electron transfer. - Abstract: Semiconductor photocatalysis has attracted significant interest for solar light induced environmental remediation and solar fuel generation. As is well known, photocatalytic performance is determined by three steps: photoexcitation, separation and transport of photogenerated charge carriers, and surface reactions. To achieve higher efficiency, significant efforts have been made on improvement of efficiency of above first two steps, which have been well documented in recent review articles. In contrast, this review intends to focus on strategies moving onto the third step of improvement for enhanced photocatalysis wherein active oxygen species including superoxide radical, hydrogen peroxide, hydroxyl radical are in situ detected. Particularly, surface electron-transfer reduction of oxygen over single component photocatalysts is reviewed and systems enabling multi-electron transfer induced oxygen reduction reaction (ORR) are highlighted. It is expected this review could provide a guideline for readers to better understand the critical role of ORR over photocatalyst in charge carrier separation and transfer and obtain reliable results for enhanced aerobic photocatalysis.

  1. Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

    International Nuclear Information System (INIS)

    Yamada, Y.; Kawase, Y.

    2006-01-01

    In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%

  2. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  3. Electro catalyst of platinum prepared by CVD for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

    2004-01-01

    In this work it is reported the preparation and characterization of platinum films obtained by the technique of chemical vapor deposition at low pressure, better well-known as LPCVD for their initials in English (Low Pressure Chemical Vapor Deposition). The technique has several industrial applications and in this work it is explored their possible use to prepare applicable electrocatalysts in fuel cells. The films were characterized by XRD, SEM, EDS and they were proven for to determine their acting in the Oxygen reduction reaction (Orr) in sulfuric acid 0.5 M, the results show that the material presents good activity for the reaction in study. (Author)

  4. Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

    2016-08-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

  5. Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

    DEFF Research Database (Denmark)

    Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

    2014-01-01

    Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this tec......Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation...... using electrochemical measurements, low energy electron diffraction, ion scattering spectroscopy, angle resolved X-ray photoelectron spectroscopy, temperature programmed desorption of CO, and synchrotron based X-ray absorption spectroscopy and surface sensitive X-ray diffraction. These measurements were...

  6. Pt Catalyst Supported within TiO2 Mesoporous Films for Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Huang, Dekang; Zhang, Bingyan; Bai, Jie; Zhang, Yibo; Wittstock, Gunther; Wang, Mingkui; Shen, Yan

    2014-01-01

    In this study, dispersed Pt nanoparticles into mesoporous TiO 2 thin films are fabricated by a facile electrochemical deposition method as electro-catalysts for oxygen reduction reaction. The mesoporous TiO 2 thin films coated on the fluorine-doped tin oxide glass by screen printing allow a facile transport of reactants and products. The structural properties of the resulted Pt/TiO 2 electrode are evaluated by field emission scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy. Cyclic voltammetry measurements are performed to study the electrochemical properties of the Pt/TiO 2 electrode. Further study demonstrates the stability of the Pt catalyst supported within TiO 2 mesoporous films for the oxygen reduction reaction

  7. Synthesis and characterization of cobalt-nichel oxides for the oxygen formation reaction

    International Nuclear Information System (INIS)

    Morales G, P.

    2001-01-01

    In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co 3 O 4 and the Ni O as the mixtures Ni O/Co 3 O 4 were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co 3 O 4 and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co 3 O 4 mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)

  8. Kinetics of the high temperature oxygen exchange reaction on {sup 238}PuO{sub 2} powder

    Energy Technology Data Exchange (ETDEWEB)

    Whiting, Christofer E., E-mail: chris.whiting@udri.udayton.edu [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States); Du, Miting; Felker, L. Kevin; Wham, Robert M. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Barklay, Chadwick D.; Kramer, Daniel P. [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States)

    2015-12-15

    Oxygen exchange reactions performed on PuO{sub 2} suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO{sub 2}. Previous CeO{sub 2} surrogate studies exhibit similar behavior, confirming that CeO{sub 2} is a good qualitative surrogate for PuO{sub 2}, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO{sub 2} oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO{sub 2} Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  9. Manganese dioxide-supported silver bismuthate as an efficient electrocatalyst for oxygen reduction reaction in zinc-oxygen batteries

    International Nuclear Information System (INIS)

    Sun, Yanzhi; Yang, Meng; Pan, Junqing; Wang, Pingyuan; Li, Wei; Wan, Pingyu

    2016-01-01

    In this paper, we present a new efficient composite electrocatalyst, manganese dioxide-supported silver bismuthate (Ag 4 Bi 2 O 5 /MnO 2 ), for oxygen reduction reaction (ORR) in alkaline media. The new electrocatalyst was characterized with scanning electron microscope (SEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements indicate that the Ag 4 Bi 2 O 5 /MnO 2 composite is a very efficient electrocatalyst for ORR in alkaline media. The physical and electrochemical characterization results suggest that the high activity is ascribed to the support effects from MnO 2 and the synergetic effects among Ag 4 Bi 2 O 5 and MnO 2 . The analysis of rotating disk electrode (RDE) results shows that the ORR occurs via a four-electron pathway on the surface of the Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst. This electrocatalyst was further tested in a designed zinc–oxygen (Zn–O 2 ) battery. This battery can offer a discharge time of 225 h at 120 mA cm −2 , increasing by more than 492% as compared with pure MnO 2 electrocatalyst. It demonstrates that this inexpensive Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst is a viable alternative to platinum electrocatalyst for energy conversion devices.

  10. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    CERN Document Server

    Park, Y T; Kim, M S; Kwon, J H

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  11. Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

    Energy Technology Data Exchange (ETDEWEB)

    Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

    2017-08-24

    Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

  12. Hot oxygen atoms: Their generation and chemistry. [Production by sputtering; reaction with butenes

    Energy Technology Data Exchange (ETDEWEB)

    Ferrieri, R.A.; Chu, Yung Y.; Wolf, A.P.

    1987-01-01

    Oxygen atoms with energies between 1 and 10 eV have been produced through ion beam sputtering from metal oxide targets. Argon ion beams were used on Ta/sub 2/O/sub 5/ and V/sub 2/O/sub 5/. Results show that some control may be exerted over the atom's kinetic energy by changing the target. Reactions of the hot O(/sup 3/P) with cis- and trans-butenes were investigated. (DLC)

  13. Mesoporous Ruthenium/Ruthenium Oxide Thin Films: Active Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Kibsgaard, Jakob; Hellstern, Thomas R.; Choi, Shin-Jung

    2017-01-01

    We report the first synthesis of a fully contiguous large area supported thin film of highly ordered mesoporous Ru and RuO2 and investigate the electrocatalytic properties towards the oxygen evolution reaction (OER). We find that the nanoscale porous network of these catalysts provides significant...... enhancements in geometric OER activity without any loss in specific activity. This work demonstrates a strategy for engineering materials at the nanoscale that can simultaneously decrease precious metal loading and increase electrode activity....

  14. Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

    OpenAIRE

    Preuss, Kathrin; Kannuchamy, Vasanth Kumar; Marinovic, Adam; Isaacs, Mark; Wilson, Karen; Abrahams, Isaac; Titirici, Maria-Magdalena

    2016-01-01

    We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a po...

  15. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

    2002-09-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  16. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    International Nuclear Information System (INIS)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed

  17. KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

    Science.gov (United States)

    He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

    In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

  18. The effect of loading and particle size on the oxygen reaction in CGO impregnated Pt electrodes

    DEFF Research Database (Denmark)

    Lund, Anders; Hansen, Karin Vels; Jacobsen, Torben

    2012-01-01

    Porous platinum electrodes impregnated with Gd x Ce1−x O2−δ (CGO) are investigated to characterise how nano-sized CGO grains affect the oxygen reaction. Impedance measurements were performed at temperatures between 450 and 750 °C and at oxygen partial pressures of 0.2 and 5 × 10−5 bar for electro......Porous platinum electrodes impregnated with Gd x Ce1−x O2−δ (CGO) are investigated to characterise how nano-sized CGO grains affect the oxygen reaction. Impedance measurements were performed at temperatures between 450 and 750 °C and at oxygen partial pressures of 0.2 and 5 × 10−5 bar...... for electrodes with various CGO loadings and electrodes annealed at various temperatures. The morphology was characterised by scanning electron microscopy and the CGO grain size was determined from X-ray diffraction peak broadening. The results showed that the polarisation resistance decreased with increasing...

  19. A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction.

    Science.gov (United States)

    Lee, Lanlee; Kang, Byungwuk; Han, Suyoung; Kim, Hee-Eun; Lee, Moo Dong; Bang, Jin Ho

    2018-05-27

    A thermal reaction route that induces grain fracture instead of grain growth is devised and developed as a top-down approach to prepare nanostructured oxides from bulk solids. This novel synthesis approach, referred to as the sequential oxygen-nitrogen exchange (SONE) reaction, exploits the reversible anion exchange between oxygen and nitrogen in oxides that is driven by a simple two-step thermal treatment in ammonia and air. Internal stress developed by significant structural rearrangement via the formation of (oxy)nitride and the creation of oxygen vacancies and their subsequent combination into nanopores transforms bulk solid oxides into nanostructured oxides. The SONE reaction can be applicable to most transition metal oxides, and when utilized in a lithium-ion battery, the produced nanostructured materials are superior to their bulk counterparts and even comparable to those produced by conventional bottom-up approaches. Given its simplicity and scalability, this synthesis method could open a new avenue to the development of high-performance nanostructured electrode materials that can meet the industrial demand of cost-effectiveness for mass production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

  1. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    DEFF Research Database (Denmark)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

    2012-01-01

    The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

  2. Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

    International Nuclear Information System (INIS)

    Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

    2012-01-01

    Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

  3. Oxygen depth profiling using the 16O(d,α)14N nuclear reaction

    International Nuclear Information System (INIS)

    Khubeis, I.; Al-Rjob, R.

    1997-01-01

    The excitation function of the 16 O(d,α) 14 N nuclear reaction has been determined in the deuteron energy range of 0.88-2.28 MeV. Major resonances are observed at deuteron energies of 0.98, 1.31, 1.53, 1.60, 1.73 and 2.22 MeV. The present results show good agreement with those of Haase and Khubeis, however there is a shift of 60 keV in the first resonance compared with the measurements of Amsel. The use of a thin surface barrier detector (t=22 μm) and a bias voltage of +20 V coupled with a proper pile-up rejection circuit has allowed the determination of the oxygen depth profiling to a resolution of 16 nm for thick targets. This method is efficient in eliminating interferences from other nuclear reactions such as 16 O(d,p) 17 O and 12 C(d,p) 19 C, where emitted protons have severely obscured α-particles from the 16 O(d,α) 14 N reaction. A 1.08 MeV deuteron beam has been employed to increase the α-yield from the target. The target has been tilted at 70 to enhance depth resolution. This reaction is well suited for the determination of oxygen concentration in oxides of high temperature superconductors. (orig.)

  4. Nitric oxide formation from the reaction of nitrite with carp and rabbit hemoglobin at intermediate oxygen saturations

    DEFF Research Database (Denmark)

    Jensen, Frank Bo

    2008-01-01

    The nitrite reductase activity of deoxyhemoglobin has received much recent interest because the nitric oxide produced in this reaction may participate in blood flow regulation during hypoxia. The present study used spectral deconvolution to characterize the reaction of nitrite with carp and rabbit...... hemoglobin at different constant oxygen tensions that generate the full range of physiological relevant oxygen saturations. Carp is a hypoxia-tolerant species with very high hemoglobin oxygen affinity, and the high R-state character and low redox potential of the hemoglobin is hypothesized to promote...... NO generation from nitrite. The reaction of nitrite with deoxyhemoglobin leads to a 1 : 1 formation of nitrosylhemoglobin and methemoglobin in both species. At intermediate oxygen saturations, the reaction with deoxyhemoglobin is clearly favored over that with oxyhemoglobin, and the oxyhemoglobin reaction...

  5. Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

    Science.gov (United States)

    Stolbov, Sergey; Alcántara Ortigoza, Marisol

    2012-02-01

    The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

  6. A Gibbs Energy Minimization Approach for Modeling of Chemical Reactions in a Basic Oxygen Furnace

    Science.gov (United States)

    Kruskopf, Ari; Visuri, Ville-Valtteri

    2017-12-01

    In modern steelmaking, the decarburization of hot metal is converted into steel primarily in converter processes, such as the basic oxygen furnace. The objective of this work was to develop a new mathematical model for top blown steel converter, which accounts for the complex reaction equilibria in the impact zone, also known as the hot spot, as well as the associated mass and heat transport. An in-house computer code of the model has been developed in Matlab. The main assumption of the model is that all reactions take place in a specified reaction zone. The mass transfer between the reaction volume, bulk slag, and metal determine the reaction rates for the species. The thermodynamic equilibrium is calculated using the partitioning of Gibbs energy (PGE) method. The activity model for the liquid metal is the unified interaction parameter model and for the liquid slag the modified quasichemical model (MQM). The MQM was validated by calculating iso-activity lines for the liquid slag components. The PGE method together with the MQM was validated by calculating liquidus lines for solid components. The results were compared with measurements from literature. The full chemical reaction model was validated by comparing the metal and slag compositions to measurements from industrial scale converter. The predictions were found to be in good agreement with the measured values. Furthermore, the accuracy of the model was found to compare favorably with the models proposed in the literature. The real-time capability of the proposed model was confirmed in test calculations.

  7. Amorphous metallic alloys for oxygen reduction reaction in a polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Huerta, R.; Guerra-Martinez, I.; Lopez, J.S. [Inst. Politecnico Nacional, ESIQIE, Mexico City (Mexico). Lab. de Electroquimica; Pierna, A.R. [Basque Country Univ., San Sebastian (Spain). Dept. of Chemical Engineering and Environment; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica

    2010-07-15

    Direct methanol fuel cells (DMFC) and polymer electrolyte membrane fuel cells (PEMFC) represent an important, environmentally clean energy source. This has motivated extensive research on the synthesis, characterization and evaluation of novel and stable oxygen reduction electrocatalysts for the direct four-electron transfer process to water formation. Studies have shown that amorphous alloyed compounds can be used as electrode materials in electrochemical energy conversion devices. Their use in PEMFCs can optimize the electrocatalyst loading in the membrane electrode assembly (MEA). In this study, amorphous metallic PtSn, PtRu and PtRuSn alloys were synthesized by mechanical milling and used as cathodes for the oxygen reduction reaction (ORR) in sulphuric acid and in a single PEM fuel cell. Two different powder morphologies were observed before and after the chemical activation in a hydrofluoric acid (HF) solution at 25 degrees C. The kinetics of the ORR on the amorphous catalysts were investigated. The study showed that the amorphous metallic PtSn electrocatalyst was the most active of the 3 electrodes for the cathodic reaction. Fuel cell experiments were conducted at various temperatures at 30 psi for hydrogen (H{sub 2}) and at 34 psi for oxygen (O{sub 2}). MEAs made of Nafion 115 and amorphous metallic PtSn dispersed on carbon powder in a PEMFC had a power density of 156 mW per cm{sup 2} at 0.43V and 80 degrees C. 12 refs., 1 tab., 5 figs.

  8. Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

    Science.gov (United States)

    Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

    2014-01-01

    Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

  9. Nanostructured Mn{sub x}O{sub y} for oxygen reduction reaction (ORR) catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Delmondo, Luisa, E-mail: luisa.delmondo@polito.it [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Salvador, Gian Paolo; Muñoz-Tabares, José Alejandro; Sacco, Adriano; Garino, Nadia; Castellino, Micaela [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Gerosa, Matteo; Massaglia, Giulia [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Chiodoni, Angelica; Quaglio, Marzia [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy)

    2016-12-01

    Highlights: • Good performance catalysts for oxygen reduction reaction. • Nanostructured low-cost catalysts respect to platinum ones. • Synthesis using environmental benign chemical reagents. - Abstract: 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 (Mn{sub x}O{sub y}) 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 Mn{sub x}O{sub y} 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.

  10. Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

    KAUST Repository

    Nurlaela, Ela

    2016-01-25

    The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

  11. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitly...... molecules binding to bridging oxygens. The third chain interacts weakly and predominantly with the H2O molecules of the second layer, resembling bulk water. We find that the stability of the water layer close to the oxide surface is almost the same as the one found on flat metal surfaces, such as the Pt(111...... of RuO2 and IrO2, while it is increased by similar to 0.4 eV for TiO2....

  12. Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

    2018-01-01

    Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

  13. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamá s; Varga, Á gnes Tí mea; Ballai, Gergő; Haspel, Henrik; Kukovecz, Á kos; Kó nya, Z.

    2018-01-01

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close

  14. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

    2013-01-01

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine

  15. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-12-15

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

  16. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Ohsaka, Takeo

    2009-01-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

  17. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

    2010-01-01

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

  18. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

    2009-10-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

  19. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail: aerawat27@gmail.com; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)

    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.

  20. Preparation and Characterization of Nicke-iron Alloy Film as Freestanding Electrode for Oxygen Evolution Reaction

    Directory of Open Access Journals (Sweden)

    Yao Mengqi

    2018-01-01

    Full Text Available This work reports the porous nicke-iron alloy film supported on stainless steel mesh as freestanding electrode for enhanced oxygen evolution reaction (OER catalyst prepared from an one step electrodeposition method. Results indicated that the porous nickle-iron alloy film exhibits a low overpotential of 270 mV at 10 mA cm-2 and excellent electroconductibility. The superior OER properties can be attributed to its novel synthetic process, conductive substrate and porous structure. This work will provide a new strategy to fabricate alloy film for OER electrocatalyst.

  1. Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

    Science.gov (United States)

    Orellana, Walter

    2012-07-01

    The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

  2. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L S; Kenny, M J; Wieczorek, L [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1994-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  3. Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

  4. Controllable synthesis of Co3O4 nanocrystals as efficient catalysts for oxygen reduction reaction

    Science.gov (United States)

    Li, Baoying; Zhang, Yihe; Du, Ruifeng; Liu, Lei; Yu, Xuelian

    2018-03-01

    The electrochemical oxygen reduction reaction (ORR) has received great attention due to its importance in fuel cells and metal-air batteries. Here, we present a simple approach to prepare non-noble metal catalyst-Co3O4 nanocrystals (NCs). The particle size and shape were simply controlled by different types and concentrations of metal precursor. Furthermore, different sizes and shapes of Co3O4 NCs are explored as electrocatalysts for ORR, and it has been observed that particles with a similar shape, and smaller particle size led to greater catalytic current densities because of the greater surface area. For particles with a comparable size, the shape or crystalline structure governed the activity of the electrocatalytic reactions. Most importantly, the 9 nm-Co3O4 were demonstrated to act as low-cost catalysts for the ORR with a similar performance to that of Pt catalysts.

  5. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Hyung Chul; Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States); Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho [Energy Lab, Samsung Advanced Institute of Technology, Samsung Electronics Co., Ltd., Suwon (Korea, Republic of); Kwon, Kyungjung [Department of Energy and Mineral Resources Engineering, Sejong University, Seoul 143-747 (Korea, Republic of)

    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.

  6. Structure, activity, and stability of platinum alloys as catalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Vej-Hansen, Ulrik Grønbjerg

    In this thesis I present our work on theoretical modelling of platinum alloys as catalysts for the Oxygen Reduction Reaction (ORR). The losses associated with the kinetics of the ORR is the main bottleneck in low-temperature fuel cells for transport applications, and more active catalysts...... are essential for wide-spread use of this technology. platinum alloys have shown great promise as more active catalysts, which are still stable under reaction conditions. We have investigated these systems on multiple scales, using either Density Functional Theory (DFT) or Effective Medium Theory (EMT......), depending on the length and time scales involved. Using DFT, we show how diffusion barriers in transition metal alloys in the L12 structure depend on the alloying energy, supporting the assumption that an intrinsically more stable alloy is also more stable towards diffusion-related degradation...

  7. Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

    Science.gov (United States)

    Liu, Jie; Huang, Yan

    2018-05-01

    Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

  8. Rate constants for the reactions of free radicals with oxygen in solution

    International Nuclear Information System (INIS)

    Maillard, B.; Ingold, K.U.; Scaiano, J.C.

    1983-01-01

    The kinetics of the rections of several free radicals with oxygen have been examined in solution at 300 K using laser flash photolysis techniques. The reactions of resonance-stabilized radicals are only slightly slower than those of nonstabilized radicals: for example, for tert-butyl (in cyclohexane), 4.93 x 10 9 ; benzyl, 2.36 x 10 9 (in cyclohexane); cyclohexadienyl (in benzene), 1.64 x 10 9 M -1 s -1 . The reaction of butyl-tin (n-Bu 3 Sn.) radicals is unusually fast (7.5 x 10 9 M -1 s -1 ), a fact that has been tentatively attributed to a relaxation of spin selection rules due to heavy atom effects. 1 table

  9. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    International Nuclear Information System (INIS)

    Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

    2013-01-01

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd 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 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

  10. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    Science.gov (United States)

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  11. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  12. Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla; Aumann, Thomas [TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerse (United States); Paschalis, Stefanos [TU Darmstadt, Darmstadt (Germany); Nociforo, Chiara [GSI, Darmstadt (Germany); Collaboration: R3B-Collaboration

    2015-07-01

    Recent experiments have shown a reduction of spectroscopic strengths to about 60-70% for stable nuclei. When going to drip lines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with secondary beams containing {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  13. Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Feng Yongjun; Alonso-Vante, Nicolas

    2012-01-01

    Highlights: ► Cubic CoSe 2 a non-precious metal electrocatalyst for oxygen reduction in KOH. ► The catalyst shows four-electron transfer pathway in overall reaction. ► Catalyst has higher methanol tolerance than commercial Pt/C catalyst. - Abstract: A Carbon-supported CoSe 2 nanocatalyst has been developed as an alternative non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in alkaline medium. The catalyst was prepared via a surfactant-free route and its electrocatalytic activity for the ORR has been investigated in detail in 0.1 M KOH electrolyte at 25 °C using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The prepared catalyst showed promising catalytic activity towards ORR in a four-electron transfer pathway and higher tolerance to methanol compared to commercial Pt/C catalyst in 0.1 M KOH. To some extent, the increase of CoSe 2 loading on the electrode favors a faster reduction of H 2 O 2 intermediate to H 2 O.

  14. MOF derived Ni/Co/NC catalysts with enhanced properties for oxygen evolution reaction

    Science.gov (United States)

    Hu, Jiapeng; Chen, Juan; Lin, Hao; Liu, Ruilai; Yang, Xiaobing

    2018-03-01

    Designing efficient electrocatalysts for oxygen evolution reaction (OER) is very important for renewable energy storage and conversion devices. In this paper, we introduced a new strategy to synthesize Ni doped Co/NC catalysts (NC is the abbreviation of nitrogen-doped graphitic carbon), which were derived from ZIF-67. All catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and oxygen evolution reaction (OER). The results show that Ni was well doped in the Ni/Co/NC catalysts and the doping of Ni has great influence on the OER activity of Ni/Co/NC catalysts. Among these catalysts, 0.50Ni/Co/NC exhibits the highest OER activity. The onset potential of 0.50Ni/Co/NC is 1.47 V, which is superior than the onset potential of Co/NC (1.54 V), 0.25Ni/Co/NC (1.48 V), 1.00Ni/Co/NC (1.53 V). The excellent OER activity of 0.50Ni/Co/NC catalyst makes its potential to be used on renewable energy storage.

  15. Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

    Science.gov (United States)

    Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

    2017-11-01

    With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

  16. Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

    International Nuclear Information System (INIS)

    Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

    2006-04-01

    Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load

  17. Hydrogen-Oxygen Reaction Assessment in the HANARO Cold Neutron Source

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jung Woon; Kim, Hark Rho; Lee, Kye Hong; Han, Young Soo; Kim, Young Ki; Kim, Seok Hoon; Jeong, Jong Tae

    2006-04-15

    Liquid hydrogen, filled in the moderator cell of the in-pool assembly (IPA), is selected as a moderator to moderate thermal neutrons into cold neutrons for the HANARO Cold Neutron Source. Since the IPA will be installed in the vertical CN hole of the reflector tank at HANARO, the vacuum chamber (VC), the pressure boundary against the reactor, should withstand the detonation pressure so as to avoid any physical damage on the reactor under the hydrogen-oxygen chemical reaction. Accordingly, not only will the vacuum chamber be designed to keep its integrity against the hydrogen accident, but also the hydrogen and vacuum system will be designed with the leak-tight concept and also designed to be surrounded by the inert gas blanket system to prevent any air intrusion into the system. Also, in order to confirm the design concept of the CNS as well as VC integrity against the hydrogen accident, the hydrogen-oxygen chemical reaction is evaluated in this report by several methodologies: AICC methodology, Equivalent TNT detonation methodology, Explosion test result, and Calculation of VC strain under the maximum reflected explosion load.

  18. Preparation of nitrogen-doped graphitic carboncages as electrocatalyst for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Yan, Jing; Meng, Hui; Yu, Wendan; Yuan, Xiaoli; Lin, Worong; Ouyang, Wenpeng; Yuan, Dingsheng

    2014-01-01

    Nitrogen-doped carbon nanomaterials have been attracted increasing research interests in lithium-O 2 and Zinc-O 2 batteries, ultracapacitors and fuel cells. Herein, nitrogen-doped graphitic carboncages (N-GCs) have been prepared by mesoporous Fe 2 O 3 as a catalyst and lysine as a nitrogen doped carbon source. Due to the catalysis of Fe 2 O 3 , the N-GCs have a high graphitization degree at a low temperature, which is detected by X-ray diffraction and Raman spectrometer. Simultaneously, the heteroatom nitrogen is in-situ doped into carbon network. Therefore, the excellent electrocatalysis performance for oxygen reduction reaction is expected. The electrochemical measurement indicates that The N-GCs for oxygen reduction reaction in O 2 -saturated 0.1 mol L −1 KOH show a four-electron transfer process and exhibit excellent electrocatalytic activity (E ORR = -0.05 V vs. Ag/AgCl) and good stability (i/i 0 = 90% at -0.35 V after 4000 s with a rotation rate of 1600 rpm)

  19. Effect of different chemical modification of carbon nanotubes for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Dumitru, Anca; Mamlouk, M.; Scott, K.

    2014-01-01

    The electrochemical reduction of oxygen on chemically modified multi-walled carbon nanotubes (CNTs) electrodes in 1 M KOH solution has been studied using the rotating ring disc electrode (RDE). The surface modification of CNTs has been estimated by XPS and Raman spectroscopy. The effect of different oxygen functionalities on the surface of carbon nanotube for the oxygen reduction reaction (ORR) is considered in terms of the number of electrons (n) involved. Electrochemical studies indicate that in the case of the modification of CNTs with citric acid and diazonium salts the n values were close to two in the measured potential range, and the electrochemical reduction is limited to the production of peroxide as the final product. In the case of the modification of carbon nanotubes with peroxymonosulphuric acid, in the measured potential range, the n value is close to 4 indicating the four-electron pathway for the ORR. By correlating ORR measurements with the XPS analysis, we propose that the increase in electrocatalytic activity towards the ORR, for CNT can be attributed to the increase in C-O groups on the surface of CNTs after modification with peroxymonosulphuric acid

  20. The antioxidant action of Polypodium leucotomos extract and kojic acid: reactions with reactive oxygen species

    Directory of Open Access Journals (Sweden)

    A.J. Gomes

    2001-11-01

    Full Text Available Two natural products Polypodium leucotomos extract (PL and kojic acid (KA were tested for their ability to scavenge reactive oxygen species (·OH, ·O2-, H2O2, ¹O2 in phosphate buffer. Hydroxyl radicals were generated by the Fenton reaction, and the rate constants of scavenging were 1.6 x 10(9 M-1 s-1 for KA and 1.0 x 10(9 M-1 s-1 for PL, similar to that of ethanol (1.4 x 10(9 M-1 s-1. With superoxide anions generated by the xanthine/hypoxanthine system, KA and PL (0.2-1.0 mg/ml inhibited ·O2-dependent reduction of nitroblue tetrazolium by up to 30 and 31%, respectively. In the detection of ¹O2 by rose bengal irradiation, PL at 1.0 mg/ml quenched singlet oxygen by 43% relative to azide and KA by 36%. The present study demonstrates that PL showed an antioxidant effect, scavenging three of four reactive oxygen species tested here. Unlike KA, PL did not significantly scavenge hydrogen peroxide.

  1. On the influence of hydronium and hydroxide ion diffusion on the hydrogen and oxygen evolution reactions in aqueous media

    DEFF Research Database (Denmark)

    Wiberg, Gustav Karl Henrik; Arenz, Matthias

    2015-01-01

    We present a study concerning the influence of the diffusion of H+ and OH- ions on the hydrogen and oxygen evolution reactions (HER and OER) in aqueous electrolyte solutions. Using a rotating disk electrode (RDE), it is shown that at certain conditions the observed current, i.e., the reaction rate...

  2. Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

    Energy Technology Data Exchange (ETDEWEB)

    Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

    2006-07-01

    Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

  3. High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

    Science.gov (United States)

    Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

    2018-02-26

    The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

  4. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2016-12-15

    Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  5. Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

    Science.gov (United States)

    Strom, Matthew James

    Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled

  6. Electrocatalysis of anodic oxygen-transfer reactions at modified lead dioxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Yun-Lin.

    1990-09-21

    The electrocatalytic activities were compared for pure and chloride-doped beta-PbO{sub 2} (Cl-PbO{sub 2}) films on gold and platinum substrates. Rate constants were increased significantly for oxidations of Mn{sup 2+}, toluene, benzyl alcohol, dimethylsulphoxide (DMSO) and benzaldehyde in acidic media by the incorporation of Cl{sup {minus}} into the oxide films. These reactions are concluded to occur by the electrocatalytic transfer of oxygen from H{sub 2}O to the reaction products. Results of x-ray diffraction studies indicate the Cl-PbO{sub 2} film continues to have the slightly distorted rutile structure of pure beta-PbO{sub 2}. The observed electrocatalytic phenomena are concluded to be the beneficial consequence of surface defects generated when Cl{sup {minus}} serves for charge compensation within the surface matrix and, thereby, increases the number of surface sites capable of adsorbing hydroxyl radicals which are transferred in the electrocatalytic O-transfer reactions. 91 refs., 44 figs., 10 tabs.

  7. Study on fine particles influence on sodium sulfite and oxygen gas-liquid reaction

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Shuchang; Zhao, Bo; Wang, Shujuan; Zhuo, Yuqun; Chen, Changhe [Tsinghua Univ., Beijing (China). Dept. of Thermal Engineering; Ministry of Education, Beijing (China). Key Lab. for Thermal Science and Power Engineering

    2013-07-01

    Wet limestone scrubbing is the most common flue gas desulfurization process for control of sulfur dioxide emissions from the combustion of fossil fuels, and forced oxidation is a key part of the reaction. During the reaction which controlled by gas-liquid mass transfer, the fine particles' characteristic, size, solid loading and temperature has a great influence on gas-liquid mass transfer. In the present work is to explain how these factors influence the reaction between Na{sub 2}SO{sub 3} and O{sub 2} and find the best react conditions through experiment. The oxidation rate was experimentally studied by contacting pure oxygen with a sodium sulfite solution with active carbon particle in a stirred tank, and the system pressure drop was record by the pressure sensor. At the beginning the pressure is about 215 kPa and Na{sub 2}SO{sub 3} is about 0.5mol/L. The temperature is 40, 50, 60, 70, 80 C. Compare the results of no particles included, we can conclude that high temperature, proper loadings and smaller particles resulting in higher mass transfer coefficients k{sub L}.

  8. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    Directory of Open Access Journals (Sweden)

    Oyunbileg G

    2018-02-01

    Full Text Available The oxygen reduction reaction (ORR is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM and a transmission electron microscope (TEM analyses confirm the formation of the star-shaped nanoparticles. Among the investigated nanostar catalysts, an AuNS5 with smaller size and a few branches showed the higher electrocatalytic activity towards ORR than other catalysts with a bigger size. In addition, the electron numbers transferred for all the catalysts are approximately two. The present study results infer that the size of the Au-based nanostars may influence greatly on their catalytic activity. The present study results show that the further improvement is needed for Au-based nanostar catalysts towards the ORR reaction.

  9. A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

    Science.gov (United States)

    Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

    2018-06-01

    The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

  10. Quasifree (p , 2 p ) Reactions on Oxygen Isotopes: Observation of Isospin Independence of the Reduced Single-Particle Strength

    Science.gov (United States)

    Atar, L.; Paschalis, S.; Barbieri, C.; Bertulani, C. A.; Díaz Fernández, P.; Holl, M.; Najafi, M. A.; Panin, V.; Alvarez-Pol, H.; Aumann, T.; Avdeichikov, V.; Beceiro-Novo, S.; Bemmerer, D.; Benlliure, J.; Boillos, J. M.; Boretzky, K.; Borge, M. J. G.; Caamaño, M.; Caesar, C.; Casarejos, E.; Catford, W.; Cederkall, J.; Chartier, M.; Chulkov, L.; Cortina-Gil, D.; Cravo, E.; Crespo, R.; Dillmann, I.; Elekes, Z.; Enders, J.; Ershova, O.; Estrade, A.; Farinon, F.; Fraile, L. M.; Freer, M.; Galaviz Redondo, D.; Geissel, H.; Gernhäuser, R.; Golubev, P.; Göbel, K.; Hagdahl, J.; Heftrich, T.; Heil, M.; Heine, M.; Heinz, A.; Henriques, A.; Hufnagel, A.; Ignatov, A.; Johansson, H. T.; Jonson, B.; Kahlbow, J.; Kalantar-Nayestanaki, N.; Kanungo, R.; Kelic-Heil, A.; Knyazev, A.; Kröll, T.; Kurz, N.; Labiche, M.; Langer, C.; Le Bleis, T.; Lemmon, R.; Lindberg, S.; Machado, J.; Marganiec-Gałązka, J.; Movsesyan, A.; Nacher, E.; Nikolskii, E. Y.; Nilsson, T.; Nociforo, C.; Perea, A.; Petri, M.; Pietri, S.; Plag, R.; Reifarth, R.; Ribeiro, G.; Rigollet, C.; Rossi, D. M.; Röder, M.; Savran, D.; Scheit, H.; Simon, H.; Sorlin, O.; Syndikus, I.; Taylor, J. T.; Tengblad, O.; Thies, R.; Togano, Y.; Vandebrouck, M.; Velho, P.; Volkov, V.; Wagner, A.; Wamers, F.; Weick, H.; Wheldon, C.; Wilson, G. L.; Winfield, J. S.; Woods, P.; Yakorev, D.; Zhukov, M.; Zilges, A.; Zuber, K.; R3B Collaboration

    2018-01-01

    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R3B /LAND setup with incident beam energies in the range of 300 - 450 MeV /u . The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type O A (p ,2 p )N-1A have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  11. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

    2015-01-01

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  12. Effect of electron injection on defect reactions in irradiated silicon containing boron, carbon, and oxygen

    Science.gov (United States)

    Makarenko, L. F.; Lastovskii, S. B.; Yakushevich, H. S.; Moll, M.; Pintilie, I.

    2018-04-01

    Comparative studies employing Deep Level Transient Spectroscopy and C-V measurements have been performed on recombination-enhanced reactions between defects of interstitial type in boron doped silicon diodes irradiated with alpha-particles. It has been shown that self-interstitial related defects which are immobile even at room temperatures can be activated by very low forward currents at liquid nitrogen temperatures. Their activation is accompanied by the appearance of interstitial carbon atoms. It has been found that at rather high forward current densities which enhance BiOi complex disappearance, a retardation of Ci annealing takes place. Contrary to conventional thermal annealing of the interstitial boron-interstitial oxygen complex, the use of forward current injection helps to recover an essential part of charge carriers removed due to irradiation.

  13. A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

    2017-12-01

    Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

  14. Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

    KAUST Repository

    Ohnishi, R.; Katayama, M.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

    2013-01-01

    Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

  15. Modified Graphene as Electrocatalyst towards Oxygen Reduction Reaction for Fuel Cells

    International Nuclear Information System (INIS)

    Qazzazie, D; Yurchenko, O; Beckert, M; Mülhaupt, R; Urban, G

    2014-01-01

    This paper reports modified graphene-based materials as metal-free electrocatalysts for oxygen reduction reaction (ORR) with outstanding electrocatalytic activity in alkaline conditions. Nitrogen-doped graphene samples are synthesized by a novel procedure. The defect density in the structure of the prepared materials is investigated by Raman spectroscopy. Further structural characterization by X-ray photoelectron spectroscopy reveals the successful nitrogen doping of graphene. The electrochemical characterization of graphene and nitrogen-doped graphene in 0.1 M KOH solution demonstrates the material's electrocatalytic activity towards ORR. For graphene an onset potential of – 0.175 V vs. Ag/AgCl reference electrode is determined, while for nitrogen-doped graphene the determined onset potential is – 0.160 V. Thus, the electrocatalytic activity of nitrogen-doped graphene towards ORR is enhanced which can be ascribed to the effect of nitrogen doping

  16. Modified Graphene as Electrocatalyst towards Oxygen Reduction Reaction for Fuel Cells

    Science.gov (United States)

    Qazzazie, D.; Beckert, M.; Mülhaupt, R.; Yurchenko, O.; Urban, G.

    2014-11-01

    This paper reports modified graphene-based materials as metal-free electrocatalysts for oxygen reduction reaction (ORR) with outstanding electrocatalytic activity in alkaline conditions. Nitrogen-doped graphene samples are synthesized by a novel procedure. The defect density in the structure of the prepared materials is investigated by Raman spectroscopy. Further structural characterization by X-ray photoelectron spectroscopy reveals the successful nitrogen doping of graphene. The electrochemical characterization of graphene and nitrogen-doped graphene in 0.1 M KOH solution demonstrates the material's electrocatalytic activity towards ORR. For graphene an onset potential of - 0.175 V vs. Ag/AgCl reference electrode is determined, while for nitrogen-doped graphene the determined onset potential is - 0.160 V. Thus, the electrocatalytic activity of nitrogen-doped graphene towards ORR is enhanced which can be ascribed to the effect of nitrogen doping.

  17. Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

    KAUST Repository

    Ohnishi, R.

    2013-03-12

    Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

  18. Alloys of Pt and Rare Earths for the Oxygen Electroreduction Reaction

    DEFF Research Database (Denmark)

    Malacrida, Paolo

    This thesis presents the development and characterization of a new class of Pt alloys for catalyzing the Oxygen Reduction Reaction (ORR), in perspective of a future substitution of traditional Pt-based catalysts at the cathode of Polymer Electrolyte Membrane Fuel Cells (PEMFCs). Focused on spectr....... A number of bimetallic alloys based on Pt and a rare earth, like the Pt-Y system or more recently proposed Pt-lanthanide phases, have been tested and characterized. Polycrystalline Pt5La and Pt5Ce exhibited more than a factor of 3 enhancement in specific activity relative to state......-Y nanoparticles are among the most active ORR catalysts ever reported, although they lose 37 % of this activity after stability test. Similar to the case of polycrystals, after immersion in the acidic electrolyte and testing the active phase consists of a Pt shell surrounding an alloyed core. Also in this case...

  19. Non-Fermi Liquids as Highly Active Oxygen Evolution Reaction Catalysts.

    Science.gov (United States)

    Hirai, Shigeto; Yagi, Shunsuke; Chen, Wei-Tin; Chou, Fang-Cheng; Okazaki, Noriyasu; Ohno, Tomoya; Suzuki, Hisao; Matsuda, Takeshi

    2017-10-01

    The oxygen evolution reaction (OER) plays a key role in emerging energy conversion technologies such as rechargeable metal-air batteries, and direct solar water splitting. Herein, a remarkably low overpotential of ≈150 mV at 10 mA cm -2 disk in alkaline solutions using one of the non-Fermi liquids, Hg 2 Ru 2 O 7 , is reported. Hg 2 Ru 2 O 7 displays a rapid increase in current density and excellent durability as an OER catalyst. This outstanding catalytic performance is realized through the coexistence of localized d-bands with the metallic state that is unique to non-Fermi liquids. The findings indicate that non-Fermi liquids could greatly improve the design of highly active OER catalysts.

  20. Positron annihilation investigation and nuclear reaction analysis of helium and oxygen-implanted zirconia

    International Nuclear Information System (INIS)

    Grynszpan, R.I.; Saude, S.; Anwand, W.; Brauer, G.

    2005-01-01

    Since irradiation affects in-service properties of zirconia, we investigated the fluence dependence on production and thermal stability of defects induced by helium and oxygen-ion implantation in single crystals of yttria-fully-stabilized zirconia. In either case, depth profiling by slow positron implantation spectroscopy (SPIS) detects a distribution of vacancy-type defects peaking at 60% of the projected ion range R p . Owing to the saturation of positron-trapping occurring for low fluences, which depends on the ion mass, we could estimate a critical size of clusters ranging from 0.4 to 1.6 nm. The lack of SPIS-evidence of an open-volume excess at R p is explained by the presence of over-pressurized gas bubbles. This assumption is confirmed by Nuclear Reaction Analysis of 3 He concentration profiles, which shows that helium remains partly trapped at R p , even after annealing above 400 o C

  1. Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

    Directory of Open Access Journals (Sweden)

    Qiliang Wei

    2015-09-01

    Full Text Available Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs and nitrogen-doped graphene (NG, have attracted increasing attention for oxygen reduction reaction (ORR in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

  2. Modelling chemical reactions in dc plasma inside oxygen bubbles in water

    International Nuclear Information System (INIS)

    Takeuchi, N; Ishii, Y; Yasuoka, K

    2012-01-01

    Plasmas generated inside oxygen bubbles in water have been developed for water purification. Zero-dimensional numerical simulations were used to investigate the chemical reactions in plasmas driven by dc voltage. The numerical and experimental results of the concentrations of hydrogen peroxide and ozone in the solution were compared with a discharge current between 1 and 7 mA. Upon increasing the water vapour concentration inside bubbles, we saw from the numerical results that the concentration of hydrogen peroxide increased with discharge current, whereas the concentration of ozone decreased. This finding agreed with the experimental results. With an increase in the discharge current, the heat flux from the plasma to the solution increased, and a large amount of water was probably vaporized into the bubbles.

  3. Modelling chemical reactions in dc plasma inside oxygen bubbles in water

    Science.gov (United States)

    Takeuchi, N.; Ishii, Y.; Yasuoka, K.

    2012-02-01

    Plasmas generated inside oxygen bubbles in water have been developed for water purification. Zero-dimensional numerical simulations were used to investigate the chemical reactions in plasmas driven by dc voltage. The numerical and experimental results of the concentrations of hydrogen peroxide and ozone in the solution were compared with a discharge current between 1 and 7 mA. Upon increasing the water vapour concentration inside bubbles, we saw from the numerical results that the concentration of hydrogen peroxide increased with discharge current, whereas the concentration of ozone decreased. This finding agreed with the experimental results. With an increase in the discharge current, the heat flux from the plasma to the solution increased, and a large amount of water was probably vaporized into the bubbles.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Chemical reaction of atomic oxygen with evaporated films of copper, part 4

    Science.gov (United States)

    Fromhold, A. T.; Williams, J. R.

    1990-01-01

    Evaporated copper films were exposed to an atomic oxygen flux of 1.4 x 10(exp 17) atoms/sq cm per sec at temperatures in the range 285 to 375 F (140 to 191 C) for time intervals between 2 and 50 minutes. Rutherford backscattering spectroscopy (RBS) was used to determine the thickness of the oxide layers formed and the ratio of the number of copper to oxygen atoms in the layers. Oxide film thicknesses ranged from 50 to 3000 A (0.005 to 0.3 microns, or equivalently, 5 x 10(exp -9) to 3 x 10(exp -7); it was determined that the primary oxide phase was Cu2O. The growth law was found to be parabolic (L(t) varies as t(exp 1/2)), in which the oxide thickness L(t) increases as the square root of the exposure time t. The analysis of the data is consistent with either of the two parabolic growth laws. (The thin-film parabolic growth law is based on the assumption that the process is diffusion controlled, with the space charge within the growing oxide layer being negligible. The thick-film parabolic growth law is also based on a diffusion controlled process, but space-charge neutrality prevails locally within very thick oxides.) In the absence of a voltage measurement across the growing oxide, a distinction between the two mechanisms cannot be made, nor can growth by the diffusion of neutral atomic oxygen be entirely ruled out. The activation energy for the reaction is on the order of 1.1 eV (1.76 x 10(exp -19) joule, or equivalently, 25.3 kcal/mole).

  6. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  7. Investigation of Au-Pt/C electro-catalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Lin Rui; Zhang Haiyan; Zhao Tiantian; Cao Chunhui; Yang Daijun; Ma Jianxin

    2012-01-01

    Highlights: ► Au-Pt core shell catalyst. ► Seed-mediated growth method. ► Au-Pt (2:4)/C best activity toward ORR. ► Four-electron pathway in acid solution. ► Single cell performance. - Abstract: Carbon-supported Au-Pt core shell nano-structured catalysts were synthesized by the seed-mediated growth method. The nano-structured catalysts were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) techniques. The oxygen reduction reaction (ORR) activity of the Au-Pt/C was tested by means of linear sweep voltammetry (LSV) by employing rotating disk electrode (RDE). It revealed that Au-Pt (2:4)/C (atomic ratio) catalyst exhibited the best catalytic activity toward ORR. Au-Pt (2:4)/C proceeded by an approximately four-electron pathway in acid solution, through which molecular oxygen was directly reduced to water. The stability of Au-Pt (2:4)/C is tested by cyclic voltammetry for 500 cycles. The performance of the membrane electrode assembly (MEA) prepared by Au-Pt (2:4)/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) generated a maximum power density of 479 mW cm −2 at 0.431 V using H 2 and O 2 at 80 °C.

  8. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  9. Oxygen reduction reaction of Pt–In alloy: Combined theoretical and experimental investigations

    International Nuclear Information System (INIS)

    Pašti, Igor A.; Gavrilov, Nemanja M.; Baljozović, Miloš; Mitrić, Miodrag; Mentus, Slavko V.

    2013-01-01

    Graphical abstract: Upon DFT prediction of improved electrocatalytic activity of Pt–In alloys toward ORR, the alloy Pt-10 at% In was synthesized on glassy carbon disc, simultaneously with pure Pt reference catalyst. Improved catalytic activity of the alloy was evidenced by voltammetry on RDE in 0.1 mol dm −3 KOH solution. -- Highlights: •The adsorption of O atoms on Pt–In alloys model surfaces was investigated by DFT. •The improvement of catalytic activity toward ORR was predicted by DFT. •Pt-10 at% In alloy was synthesized on glassy carbon disk surface. •By voltammetry on RDE improvement of activity toward ORR was evidenced. -- Abstract: By means of the density functional theory (DFT) calculations, using the adsorption energy of oxygen on single crystal surfaces as criterion, it was predicted that the alloying of Pt with In should improve kinetics of oxygen reduction reaction (ORR). To prove this, the Pt–In alloy having nominal composition Pt 9 In was synthesized by heating H 2 PtCl 6 –InCl 3 mixture in hydrogen stream. The XRD characterization confirmed that Pt–In alloy was formed. The electrochemical measurements by rotating disk technique in alkaline 0.1 mol dm −3 KOH solution evidenced faster ORR kinetics for factor 2.6 relative to the one on pure platinum. This offers the possibility of searching for new ORR electrocatalysts by alloying platinum with p-elements

  10. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    KAUST Repository

    Shinagawa, Tatsuya

    2017-03-27

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 °C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeOx electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cmgeo(-2) .

  11. Boosting the performance of the nickel anode in the oxygen evolution reaction by simple electrochemical activation

    Energy Technology Data Exchange (ETDEWEB)

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro [King Abdullah Univ. of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Div. PSE, Thuwal (Saudi Arabia)

    2017-04-24

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeO{sub x} electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cm{sub geo}{sup -2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Size-selective electrocatalytic activity of (Pt)n/MoS2for oxygen reduction reaction

    DEFF Research Database (Denmark)

    Bothra, Pallavi; Pandey, Mohnish; Pati, Swapan K.

    2016-01-01

    In the present work, we have investigated the electrocatalytic activity of the oxygen reduction reaction (ORR), O2 + 4H+ + 4e− → 2H2O, for (Pt)n clusters (n = 1, 2, 3, 5, 7, 10 and 12) adsorbed on semiconducting (2H) and metallic (1T) MoS2 monolayers using first principles density functional theory....... We have considered four elementary reactions involved in ORR within a unified electrochemical thermodynamic framework and the corresponding Gibbs adsorption free energies of the key intermediates (*OOH, *O, *OH) associated with each step have been calculated. The results indicate that the reduction...... of adsorbed hydroxyl (*OH) to water (*OH + H+ + e− → H2O) is the bottleneck step in the ORR process. The adsorption free energy of *OH (ΔG*OH) is found to be the thermodynamic descriptor for the present systems. Eventually, the ORR activity has been described as a function of ΔG*OH and a volcano plot...

  13. PTFE effect on the electrocatalysis of the oxygen reduction reaction in membraneless microbial fuel cells.

    Science.gov (United States)

    Guerrini, Edoardo; Grattieri, Matteo; Faggianelli, Alessio; Cristiani, Pierangela; Trasatti, Stefano

    2015-12-01

    Influence of PTFE in the external Gas Diffusion Layer (GDL) of open-air cathodes applied to membraneless microbial fuel cells (MFCs) is investigated in this work. Electrochemical measurements on cathodes with different PTFE contents (200%, 100%, 80% and 60%) were carried out to characterize cathodic oxygen reduction reaction, to study the reaction kinetics. It is demonstrated that ORR is not under diffusion-limiting conditions in the tested systems. Based on cyclic voltammetry, an increase of the cathodic electrochemical active area took place with the decrease of PTFE content. This was not directly related to MFC productivity, but to the cathode wettability and the biocathode development. Low electrodic interface resistances (from 1 to 1.5 Ω at the start, to near 0.1 Ω at day 61) indicated a negligible ohmic drop. A decrease of the Tafel slopes from 120 to 80 mV during productive periods of MFCs followed the biological activity in the whole MFC system. A high PTFE content in the cathode showed a detrimental effect on the MFC productivity, acting as an inhibitor of ORR electrocatalysis in the triple contact zone.

  14. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  15. S- and N-Doped Graphene Nanomaterials for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Luis Miguel Rivera

    2017-09-01

    Full Text Available In the current work, heteroatom-doped graphene materials containing different atomic ratios of nitrogen and sulphur were employed as electrocatalysts for the oxygen reduction reaction (ORR in acidic and alkaline media. To this end, the hydrothermal route and different chemical reducing agents were employed to synthesize the catalytic materials. The physicochemical characterization of the catalysts was performed by several techniques, such as X-ray diffraction, Raman spectroscopy and elemental analysis; meanwhile, the electrochemical performance of the materials toward the ORR was analyzed by linear sweep voltammetry (LSV, rotating disk electrode (RDE and rotating ring-disk electrode (RRDE techniques. The main results indicate that the ORR using heteroatom-doped graphene is a direct four-electron pathway, for which the catalytic activity is higher in alkaline than in acidic media. Indeed, a change of the reaction mechanism was observed with the insertion of N into the graphenic network, by the rate determining step changes from the first electrochemical step (formation of adsorbed OOH on glassy carbon to the removal of adsorbed O (Oad from the N-graphene surface. Moreover, the addition of sulphur atoms into the N-graphene structure increases the catalytic activity toward the ORR, as the desorption of Oad is accelerated.

  16. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  17. Microwave Assisted Synthesis of Osmium Electrocatalysts for the Oxygen Reduction Reaction in the Absence and Presence of Aqueous Methanol

    Directory of Open Access Journals (Sweden)

    Edgar Borja-Arco

    2011-01-01

    Full Text Available Osmium electrocatalysts for the oxygen reduction reaction (ORR were prepared by microwave irradiation of Os3(CO12 at different experimental conditions. The materials obtained were structurally characterized by FT-IR, micro-Raman spectroscopy and X-ray diffraction. Their chemical compositions were obtained by EDS. The electrocatalytic properties for the oxygen reduction reaction were evaluated by rotating disk electrode measurements in 0.5 mol L-1 H2SO4, in the absence and presence of aqueous methanol. The kinetic parameters, such as Tafel slope, exchange current density, and charge transfer coefficient are reported.

  18. Kinetics of several oxygenated carbon-centered free radical reactions with NO2.

    Science.gov (United States)

    Rissanen, Matti P; Arppe, Suula L; Timonen, Raimo S

    2013-05-16

    Five oxygenated carbon-centered free radical reactions with nitrogen dioxide (NO2) have been studied in direct time-resolved measurements. Experiments were conducted in a temperature-controlled flow tube reactor coupled to a 193 nm exciplex laser photolysis and a resonance gas lamp photoionization mass spectrometer. Reactions were investigated under pseudofirst-order conditions, with the NO2 concentrations of the experiments in great excess over the initial radical concentrations ([R]0 CH3CO radical reactions with NO2 and, hence, includes the three smallest hydroxyalkyl radical species (CH2OH, CH2CH2OH, and CH3CHOH). The obtained rate coefficients are high with the temperature-dependent rate coefficients given by a formula k(T) = k300K × (T/300 K)(-n) as (in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO2) = (8.95 ± 2.70) × 10(-11) × (T/300 K)(-0.54±0.27) (T = 298-363 K), k(CH2CH2OH + NO2) = (5.99 ± 1.80) × 10(-11) × (T/300 K)(-1.49±0.45)(T = 241-363 K), k(CH3CHOH + NO2) = (7.48 ± 2.24) × 10(-11) × (T/300 K)(-1.36±0.41) (T = 266-363 K), k(CH3OCH2 + NO2) = (7.85 ± 2.36) × 10(-11) × (T/300 K)(-0.93±0.28) (T = 243-363 K), and k(CH3CO + NO2) = (2.87 ± 0.57) × 10(-11) × (T/300 K)(-2.45±0.49) (T = 241-363 K), where the uncertainties refer to the estimated overall uncertainties of the values obtained. The determined rate coefficients show negative temperature dependence with no apparent bath gas pressure dependence under the current experimental conditions (241-363 K and about 1-3 Torr helium). This behavior is typical for a radical-radical addition mechanism with no potential energy barrier above the energy of the separated reactants in the entrance channel of the reaction. Unfortunately the absence of detected product signals prevented gaining deeper insight into the reaction mechanism.

  19. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  20. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

    Science.gov (United States)

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  1. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

  2. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  3. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  4. Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction

    Science.gov (United States)

    Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Zheng, Gengfeng

    2015-08-01

    A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE.A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific

  5. Ultrafine Iridium Oxide Nanorods Synthesized by Molten Salt Method toward Electrocatalytic Oxygen and Hydrogen Evolution Reactions

    International Nuclear Information System (INIS)

    Ahmed, Jahangeer; Mao, Yuanbing

    2016-01-01

    Highlights: • Ultrafine iridium oxide nanorods were synthesized by a molten salt method at 650 °C. • They show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions. • These results are comparable with, and in most cases, higher than reported data in the literature. • This study reports a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure. • These IrO_2 NRs are expected to serve as a benchmark to develop active electrocatalysts. - Abstract: Ultrafine iridium oxide nanorods (IrO_2 NRs) were successfully synthesized using a molten salt method at 650 °C. The structural and morphological characterizations of these IrO_2 NRs were carried out by powder X-ray diffraction, Raman spectroscopy and electron microscopic techniques. Compared to commercial IrO_2 nanoparticles (IrO_2 NPs) and previous reports, these IrO_2 NRs show enhanced electrocatalytic activity to oxygen and hydrogen evolution reactions by passing either N_2 or O_2 gas in a 0.5 M KOH electrolyte before electrochemical measurements, including cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Specifically, the current densities from the as-synthesized IrO_2 NRs and commercial IrO_2 NPs were measured in 0.5 M KOH electrolyte to be 70 and 58 (OER, deaerated, at 0.6 V versus Ag/AgCl), 71 and 61 (OER, O_2, from −0.10 to 1.0 V versus Ag/AgCl at 50 mV/s), and 25 and 14 (HER, deaerated, at −1.4 V versus Ag/AgCl) mA/cm"2, respectively. These results are comparable with, and in most cases, higher than reported data in the literature. Therefore, the current study reports not only a novel synthetic process for IrO_2 but also a high efficient IrO_2 nanostructure, and it is expected that these IrO_2 NRs can serve as a benchmark in the development of active OER and HER (photo)electrocatalysts for various applications.

  6. Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

    Directory of Open Access Journals (Sweden)

    Jakšić Jelena M.

    2012-01-01

    Full Text Available Altervalent hypo-d-oxides of transition metal series impose spontaneous dissociative adsorption of water molecules and pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic, and/or its hydrated state (Pt/W(OH6 responsible for the primary oxide (Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3 Pt/W(OH6, and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. As the consequence, the new striking and unpredictable prospects both in law and medium temperature proton exchange membrane fuell cell (L&MT PEMFC and water electrolysis (WE have been opened by the interactive supported individual (Pt, Pd, Ni or prevailing hyper-d-electronic nanostructured intermetallic phase clusters (WPt3, NbPt3, HfPd3, ZrNi3, grafted upon and within high altervalent capacity hypo-d-oxides (WO3, Nb2O5, Ta2O5, TiO2 and their proper mixed valence compounds, to create a novel type of alterpolar interchangeable composite electrocatalysts for hydrogen and oxygen electrode reactions. Whereas in aqueous media Pt (Pt/C features either chemisorbed catalytic surface properties of H-adatoms (Pt-H, or surface oxide (Pt=O, missing any effusion of other interacting species, new generation and selection of composite and interactive strong metal-support interaction (SMSI electrocatalysts in condensed wet state primarily characterizes interchangeable extremely fast reversible spillover of either H-adatoms, or the primary oxides (Pt-OH, Au-OH, or the invertible bronze type behavior of these significant interactive electrocatalytic ingredients. Such nanostructured type electrocatalysts, even of mixed hypo-d-oxide structure (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron

  7. Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

    Science.gov (United States)

    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

  8. Development of Refractory Ceramics for The Oxygen Evolution Reaction (OER) Electrocatalyst Support for Water Electrolysis at elevated temperatures

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Prag, Carsten Brorson; Polonsky, J.

    2012-01-01

    Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis...

  9. Oxygen reduction reaction on a highly-alloyed Pt-Ni supported carbon electrocatalyst in acid solution

    CSIR Research Space (South Africa)

    Zheng, H

    2010-08-31

    Full Text Available Alloyed electrocatalysts such as PtNi/C[1-2], PtCo/C[3], PtCr/C[4], PtFe/C [5-6], and non-alloyed Pt-TiO2/C were reportedly investigated for methanol tolerance during Oxygen reduction reaction (ORR). The high methanol tolerance...

  10. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.

    2013-11-13

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine oxide nanoparticles exhibited a distinctively high onset potential different from that of the bulky oxide particles.

  11. Charged particle spectra in oxygen-induced reactions at 14. 6 and 60 GeV/Nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Adamovich, M I; Aggarwal, M M; Arora, R; Alexandrov, Y A; Azimov, S A; Badyal, S K; Basova, E; Bhalla, K B; Bahsin, A; Bhatia, V S; Bomdarenko, R A; Burnett, T H; Cai, X; Chernova, L P; Chernyavski, M M; Dressel, B; Friedlander, E M; Gadzhieva, S I; Ganssauge, E R; Garpman, S; Gerassimov, S G; Gill, A; Grote, J; Gulamov, K G; Gulyamov, V G; Gupta, V K; Hackel, S; Heckman, H H; Jakobsson, B; Judek, B; Katroo, S; Kadyrov, F G; Kallies, H; Karlsson, L; Kaul, G L; Kaur, M; Kharlamov, S P; Kohli, J; Kumar, V; Lal, P; Larionova, V G; Lindstrom, P J; Liu, L S; Lokanathan, S; Lord, J; Lukicheva, N S; Mangotra, L K; Maslennikova, N V; Mitta, I S; Monnand, E; Mookerjee, S; Mueller, C; Nasyrov, S H; Nvtny, V S; Orlova, G I; Otterlund, I; Peresadko, N G; Persson, S; Petrov, N V; Qian, W Y; Raniwala, R; Raniwala, S; Rao, N K; Rhee, J Y; Shaidkhanov, N; Salmanova, N G; Schulz, W; Schussler, F; Shukla, V S; Skelding, D; Soederstroe,

    1989-10-01

    Multiplicity distributions and pseudo-rapidity distributions of charged particles from oxygen-induced nuclear reactions at 14.6 and 60 GeV/nucleon are presented. The data were taken from the EMU{minus}01 emulsion stacks and compared to simulations from the Lund Monte Carlo Model (FRITIOF).

  12. Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-05-01

    Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...

  13. Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

    Science.gov (United States)

    Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

    2015-06-11

    A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

  14. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2015-01-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors

  15. Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

    Science.gov (United States)

    Stecura, S.

    1976-01-01

    Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

  16. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk

    2014-12-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  17. Effect of pH and Water Structure on the Oxygen Reduction Reaction on platinum electrodes

    International Nuclear Information System (INIS)

    Briega-Martos, Valentín; Herrero, Enrique; Feliu, Juan M.

    2017-01-01

    The oxygen reduction reaction (ORR) at different pH values has been studied at platinum single crystal electrodes using the hanging meniscus rotating disk electrode (HMRDE) configuration. The use of NaF/HClO 4 mixtures allows investigating the reaction up to pH = 6 in solutions with enough buffering capacity and in the absence of anion specific adsorption. The analysis of the currents shows that the kinetic current density measured at 0.85 V for the Pt(111) electrode follows a volcano curve with the maximum located around pH = 9. This maximum activity for pH = 9 can be related to the effects of the electrode charge and/or water structure in the ORR. On the other hand, the catalytic activity for the other basal planes shows a monotonic behavior with a small dependence of the activity with pH. For stepped surfaces with (111) terraces, the behavior with pH changes gets closer to that of the Pt(111) surface as the terrace length increases. Additionally, the ORR curves show a dependence of the limiting diffusion current with pH. It is observed that the limiting current density diminishes as the pH increases in a potential region where hydrogen peroxide is readily reduced. These results suggest the existence of a bifurcation point in the mechanism previous to peroxide formation, in which OOH • is proposed as the bifurcation intermediate. The reduction of OOH • requires proton addition and would be more difficult at neutral pH values, justifying the diminution of the limiting currents.

  18. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk; Anjum, Dalaver H.; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  19. Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

    2018-05-01

    The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

  20. Scalable preparation of sized-controlled Co-N-C electrocatalyst for efficient oxygen reduction reaction

    Science.gov (United States)

    Ai, Kelong; Li, Zelun; Cui, Xiaoqiang

    2017-11-01

    Heat-treated metal-nitrogen-carbon (M-N-C) materials are emerging as promising non-precious catalysts to replace expensive Pt-based materials for oxygen reduction reaction (ORR) in energy conversion and storage devices. Despite recent progress, their activity and durability are still far from satisfactory. The activity site and particle size are among the most important factors for the ORR activity of M-N-C catalysts. Extensive efforts have been made to reveal the correlation of active site and activity. However, it remains unclear to what extent the particle size will influence the ORR activity of M-N-C materials. Moreover, to the best of our knowledge, controllable synthesis of M-N-C catalysts with high-density activity sites remains elusive. Herein, we develop a straightforward method to produce a monodisperse and size-controlled Co-N-C (Nano-P-ZIF-67) electrocatalyst, and systemically investigate its catalytic mechanisms. Only by optimizing the particle size, Nano-P-ZIF-67 outperforms the commercial 20 wt% Pt/C regarding all evaluating indicators for ORR catalysts in alkaline media including higher catalytic activity, durability, and stronger methanol tolerance. Nano-P-ZIF-67 is assembled into a cell, and the cell shows a power density of 45.5 mW/cm2, which is the highest value among currently studied cathode catalysts. We expect Nano-P-ZIF-67 to be a highly interesting candidate for the next generation of ORR catalysts.

  1. Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

    Science.gov (United States)

    Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

    2018-03-01

    Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

  2. Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

    International Nuclear Information System (INIS)

    Feng Yongjun; He Ting; Alonso-Vante, Nicolas

    2009-01-01

    We investigated the effect of CoSe 2 /C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H 2 O 2 production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe 2 nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H 2 O 2 production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe 2 loading on the disk electrode. H 2 O 2 production also decreased with increasing catalytic site density, a phenomenon related to the CoSe 2 loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe 2 /C nanoparticles at 22 μg cm -2 , we determined that the transfer process involves about 3.5 electrons.

  3. Organodioxygen complexes of some heavy metal ions and their oxygen transfer reactions

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Mei Ling; Gino Mariotto

    2003-09-01

    Several novel organodioxygen complexes of lanthanide ions, viz., lanthanum(m) and cerium(IV) have been synthesized containing a number of organic co- ligands. The complexes characterized were, [La(0 2 )(det)(N0 3 ) 2 ] (1), [La(O 2 )(tet)(NO 3 ) 2 ] (2), [La(O 2 )(C 5 H 5 N)2NO 3 ] (3), [La(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 2 ] (4), [La(0 2 )(OPPh 3 ) 2 (N0 3 ) 2 ] (5), [La(O 2 ) 2 (NH 2 CH 2 CH 2 NH 2 ) 2 NO 3 ] (6), [La(O 2 )(PPh 3 ) 2 (NO 3 ) 2 ] (7) and [Ce(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 3 ] (8). IR and Raman spectra revealed that (3) was a peroxo complex while the others were, in particular, superoxo type. The IR spectrum of (3) gives V 1 (O-O) at 851 cm -1 while the Raman spectra of (4), (5), (7) and (8) give V 1 (O 2 ) bands at 1046 cm -1 , 1032 cm 1 , 1100 cm -1 and 1046 cm -1 , respectively. The oxygen transfer reactions of two selected complexes were carried out under stoichiometric conditions. The complex containing a bidentate ligand, (6), was found to oxidize triphenylphosphine and trans-stilbene to their oxides while the complex containing tridentate ligand (1) was stable and inert towards oxidation. (author)

  4. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

    International Nuclear Information System (INIS)

    Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

  5. A Pt-free Electrocatalyst Based on Pyrolized Vinazene-Carbon Composite for Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Akinpelu, Akeem; Merzougui, Belabbes; Bukola, Saheed; Azad, Abdul-Majeed; Basheer, Rafil A.; Swain, Greg M.; Chang, Qiaowan; Shao, Minhua

    2015-01-01

    The 2-vinyl-4, 5-dicyanoimidazole (Vinazene) was used as a nitrogen precursor to synthesize a promising non-precious metal (NPM) catalyst for oxygen reduction reaction (ORR). Vinazene together with an iron source was impregnated into a carbon matrix and pyrolyzed at 900 °C in N 2 atmosphere. The structure of the resulting Fe–N–C nanocomposite was analyzed by X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction. Both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) experiments showed excellent ORR activity for the obtained catalyst with low H 2 O 2 formation (∼3.0%) in 0.1 M KOH. The catalyst was found to be rich in mesoporous structure along with high percentage of pyrrolic-N function with surface area of about 673 m 2 g −1 and pore size of 4.2 nm. In addition to its excellent ORR activity, the catalyst showed remarkable tolerance towards methanol oxidation and demonstrates good stability over 10,000 potential cycles (0.6–1.0 V Vs RHE). We believe that this N-rich Vinazene molecule will be beneficial to further development of nitrogen doped carbon electrocatalysts

  6. Investigations of Pd-Cu electrocatalyst for oxygen reduction reaction in acidic media with RDE method

    Energy Technology Data Exchange (ETDEWEB)

    Fouda-Onana, F.; Bah, S.; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

    2008-07-01

    The kinetics of the oxygen reduction reaction (ORR) has been studied extensively with different platinum bi-metallic alloys such as Pt-Fe, Pt-Ni, Pt-Co. However, palladium-based bi-metallic alloys are being considered as a substitute for platinum in electrocatalysts. This paper reported on a study that investigated the ORR on bi-metallic Pd-Cu electrocatalyst. Different contents in Cu were analyzed and an optimal Cu composition leading to the highest ORR activity was found. A mechanism of the ORR kinetics for this catalyst was introduced based on the value of the Tafel slope. A smooth increase in surface area up to 50 per cent Cu was observed to a constant value of 23 cm{sup 2}. Such behaviour was due to the high dispersion of Pd as Cu increased and segregated. A volcano-shape was found between the kinetic current, activation energy and the Cu composition. The maximum exchange current density and the lowest activation energy were found for Pd50Cu50, which corresponded to the highest surface area. All Pd-Cu alloys presented a higher kinetic current than Pd alone. 3 refs., 1 tab., 3 figs.

  7. Ordered hierarchically porous carbon codoped with iron and nitrogen as electrocatalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Yao, Lan; Liu, Sisi; Xu, Zhuang; Zhang, Huamin

    2014-12-01

    N-doped carbon catalysts have attracted great attention as potential alternatives to expensive Pt-based catalysts used in fuel cells. Herein, an ordered hierarchically porous carbon codoped with N and Fe (Fe-NOHPC) is prepared by an evaporation-induced self-assembly process followed by carbonization under ammonia. The soft template and Fe species promote the formation of the porous structure and facilitate the oxygen reduction reaction (ORR).The catalyst possesses an ordered hierarchically porous structure with a large surface area (1172.5 m(2) g(-1) ) and pore volume of 1.03 cm(3) g(-1) . Compared to commercial 20% Pt/C, it exhibits better ORR catalytic activity and higher stability as well as higher methanol tolerance in an alkaline electrolyte, which demonstrates its potential use in fuel cells as a nonprecious cathode catalyst. The N configuration, Fe species, and pore structure of the catalysts are believed to correlate with its high catalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

    2018-06-26

    It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

  9. Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

    Science.gov (United States)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

    2018-01-01

    Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

  10. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    Science.gov (United States)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  11. Electrocatalytic performance evaluation of cobalt hydroxide and cobalt oxide thin films for oxygen evolution reaction

    Science.gov (United States)

    Babar, P. T.; Lokhande, A. C.; Pawar, B. S.; Gang, M. G.; Jo, Eunjin; Go, Changsik; Suryawanshi, M. P.; Pawar, S. M.; Kim, Jin Hyeok

    2018-01-01

    The development of an inexpensive, stable, and highly active electrocatalyst for oxygen evolution reaction (OER) is essential for the practical application of water splitting. Herein, we have synthesized an electrodeposited cobalt hydroxide on nickel foam and subsequently annealed in an air atmosphere at 400 °C for 2 h. In-depth characterization of all the films using X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) techniques, which reveals major changes for their structural, morphological, compositional and electrochemical properties, respectively. The cobalt hydroxide nanosheet film shows high catalytic activity with 290 mV overpotential at 10 mA cm-2 and 91 mV dec-1 Tafel slope and robust stability (24 h) for OER in 1 M KOH electrolyte compared to cobalt oxide (340 mV). The better OER activity of cobalt hydroxide in comparison to cobalt oxide originated from high active sites, enhanced surface, and charge transport capability.

  12. Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction.

    Science.gov (United States)

    Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M; Elzatahry, Ahmed A; Zheng, Gengfeng

    2015-09-14

    A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g(-1), with excellent capacitance retention (>90%) at 10 A g(-1) for over 10,000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm(-2) at 1.65 V vs. the RHE.

  13. Theoretical predictions for hexagonal BN based nanomaterials as electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Lyalin, Andrey; Nakayama, Akira; Uosaki, Kohei; Taketsugu, Tetsuya

    2013-02-28

    The catalytic activity for the oxygen reduction reaction (ORR) of both the pristine and defect-possessing hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O(2), O, OH, OOH, and H(2)O on N atom impurities in the h-BN monolayer (N(B)@h-BN) is quite similar to that known for a Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N(B)@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that a N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under the condition that electron transport to the catalytically active center is provided.

  14. High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

    2017-08-17

    Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

  15. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  16. Synthesis and characterization of Pd-Ni nanoalloy electrocatalysts for oxygen reduction reaction in fuel cells

    International Nuclear Information System (INIS)

    Zhao, Juan; Sarkar, Arindam; Manthiram, Arumugam

    2010-01-01

    Carbon-supported Pd-Ni nanoalloy electrocatalysts with different Pd/Ni atomic ratios have been synthesized by a modified polyol method, followed by heat treatment in a reducing atmosphere at 500-900 deg. C. The samples have been characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), rotating disk electrode (RDE) measurements, and single-cell proton exchange membrane fuel cell (PEMFC) tests for oxygen reduction reaction (ORR). XRD and TEM data reveal an increase in the degree of alloying and particle size with increasing heat-treatment temperature. XPS data indicate surface segregation with Pd enrichment on the surface of Pd 80 Ni 20 after heat treatment at ≥500 deg. C, suggesting possible lattice strains in the outermost layers. Electrochemical data based on CV, RDE, and single-cell PEMFC measurement show that Pd 80 Ni 20 heated at 500 deg. C has the highest mass catalytic activity for ORR among the Pd-Ni samples investigated, with stability and catalytic activity significantly higher than that found with Pd. With a lower cost, the Pd-Ni catalysts exhibit higher tolerance to methanol than Pt, offering an added advantage in direct methanol fuel cells (DMFC).

  17. Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Salomé, Sónia; Rego, Rosa; Oliveira, M. Cristina, E-mail: mcris@utad.pt

    2013-12-16

    Silver-gas diffusion electrodes (Ag-GDE) were prepared by direct deposition of the catalyst onto a carbon paper support by electrodeposition. This deposition technique, under potentiostatic and galvanostatic mode, allows the production of well dispersed ultra-low Ag loading levels. The catalytic activity of the prepared materials towards the oxygen reduction reaction (ORR) was investigated in the alkaline solution and its tolerance to methanol was evaluated. Based on an Ag-ink prepared from the electrodeposit material and RDE experiments, it was concluded that the ORR occurs via a four-electron pathway on the Ag electrodeposit. The combination of reasonably high catalytic activity, efficiency, low price, facile and green synthesis makes the electrodeposited Ag-GDE attractive for the ORR in alkaline fuel cells. - Highlights: • A facile and simple way to successfully prepare catalyzed gas diffusion electrodes. • Ultra-low loadings of Ag-GDEs can be achieved. • Good tolerance to methanol and a high mass activity (3.14 mA{sub Ag} mg{sup −1}). • ORR occurs via a four-electron pathway.

  18. High Oxygen Reduction Reaction Performances of Cathode Materials Combining Polyoxometalates, Coordination Complexes, and Carboneous Supports.

    Science.gov (United States)

    Zhang, Shuangshuang; Oms, Olivier; Hao, Long; Liu, Rongji; Wang, Meng; Zhang, Yaqin; He, Hong-Yan; Dolbecq, Anne; Marrot, Jérôme; Keita, Bineta; Zhi, Linjie; Mialane, Pierre; Li, Bin; Zhang, Guangjin

    2017-11-08

    A series of carbonaceous-supported precious-metal-free polyoxometalate (POM)-based composites which can be easily synthesized on a large scale was shown to act as efficient cathode materials for the oxygen reduction reaction (ORR) in neutral or basic media via a four-electron mechanism with high durability. Moreover, exploiting the versatility of the considered system, its activity was optimized by the judicious choice of the 3d metals incorporated in the {(PW 9 ) 2 M 7 } (M = Co, Ni) POM core, the POM counterions and the support (thermalized triazine-based frameworks (TTFs), fluorine-doped TTF (TTF-F), reduced graphene oxide, or carbon Vulcan XC-72. In particular, for {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F, the overpotential required to drive the ORR compared well with those of Pt/C. This outstanding ORR electrocatalytic activity is linked with two synergistic effects due to the binary combination of the Cu and Ni centers and the strong interaction between the POM molecules and the porous and highly conducting TTF-F framework. To our knowledge, {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F represents the first example of POM-based noble-metal-free ORR electrocatalyst possessing both comparable ORR electrocatalytic activity and much higher stability than that of Pt/C in neutral medium.

  19. A study on rare gas - oxygen reactions excited by low temperature plasma

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Hiroaki; Kiuchi, Kiyoshi; Saburi, Tei; Fukaya, Kiyoshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2001-03-01

    The concentration of radioactive rare gases like Xe and Kr in nuclear fuels on PWRs and BWRs increases promptly with dependent on the burn-up ratio. These gases are affect to the long performance of nuclear fuel elements due to accumulate in gap between cladding and fuel, because it has the low thermal conductivity. It is also required to develop the practical means to correct these gases including in the off-gas in nuclear plants for inhibiting the environmental pollution. On the present study, we carried out the fundamental research to evaluate the chemical reactivity of these gases under heavy irradiation. We proposed the new excitation mechanism of these gases by expecting the formation of low energy plasma under irradiation. The chemical reactivity on rare gas-oxygen system was examined by using the low energy plasma driven reaction apparatus installed the RF excitation source. The density of electrons and lower pressure limit for the RF excitation was depended on the ionization energy of each gas. It is clarified that Xe is easy to form gaseous oxide due to the high excitation efficiency in low energy plasma. (author)

  20. Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Zhipeng Yu

    2017-02-01

    Full Text Available 2D nitrogen-doped mesoporous carbon (NMC is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR. The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM, nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS, cyclic voltammetry (CV, and rotating disk electrode measurements (RDE. The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells.

  1. Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction

    Science.gov (United States)

    Kang, SungYeon; Kim, HuiJung; Chung, Yong-Ho

    2018-04-01

    Developments of high efficient materials for electrocatalyst are significant topics of numerous researches since a few decades. Recent global interests related with energy conversion and storage lead to the expansion of efforts to find cost-effective catalysts that can substitute conventional catalytic materials. Especially, in the field of fuel cell, novel materials for oxygen reduction reaction (ORR) have been noticed to overcome disadvantages of conventional platinum-based catalysts. Various approaching methods have been attempted to achieve low cost and high electrochemical activity comparable with Pt-based catalysts, including reducing Pt consumption by the formation of hybrid materials, Pt-based alloys, and not-Pt metal or carbon based materials. To enhance catalytic performance and stability, numerous methods such as structural modifications and complex formations with other functional materials are proposed, and they are basically based on well-defined and well-ordered catalytic active sites by exquisite control at nanoscale. In this review, we highlight the development of nano-structured catalytic materials for ORR based on recent findings, and discuss about an outlook for the direction of future researches.

  2. Kinetics of Several Oxygen-Containing Carbon-Centered Free Radical Reactions with Nitric Oxide.

    Science.gov (United States)

    Rissanen, Matti P; Ihlenborg, Marvin; Pekkanen, Timo T; Timonen, Raimo S

    2015-07-16

    Kinetics of four carbon-centered, oxygen-containing free radical reactions with nitric oxide (NO) were investigated as a function of temperature at a few Torr pressure of helium, employing flow tube reactors coupled to a laser-photolysis/resonance-gas-discharge-lamp photoionization mass spectrometer (LP-RPIMS). Rate coefficients were directly determined from radical (R) decay signals under pseudo-first-order conditions ([R]0 ≪ [NO]). The obtained rate coefficients showed negative temperature dependences, typical for a radical-radical association process, and can be represented by the following parametrizations (all in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO) = (4.76 × 10(-21)) × (T/300 K)(15.92) × exp[50700/(RT)] (T = 266-363 K, p = 0.79-3.44 Torr); k(CH3CHOH + NO) = (1.27 × 10(-16)) × (T/300 K)(6.81) × exp[28700/(RT)] (T = 241-363 K, p = 0.52-3.43 Torr); k(CH3OCH2 + NO) = (3.58 ± 0.12) × 10(-12) × (T/300 K)(-3.17±0.14) (T = 221-363 K, p = 0.50-0.80 Torr); k(T)3 = 9.62 × 10(-11) × (T/300 K)(-5.99) × exp[-7100/(RT)] (T = 221-473 K, p = 1.41-2.95 Torr), with the uncertainties given as standard errors of the fits and the overall uncertainties estimated as ±20%. The rate of CH3OCH2 + NO reaction was measured in two density ranges due to its observed considerable pressure dependence, which was not found in the studied hydroxyalkyl reactions. In addition, the CH3CO + NO rate coefficient was determined at two temperatures resulting in k298K(CH3CO + NO) = (5.6 ± 2.8) × 10(-13) cm(3) molecule(-1) s(-1). No products were found during these experiments, reasons for which are briefly discussed.

  3. Improvement of attention span and reaction time with hyperbaric oxygen treatment in patients with toxic injury due to mold exposure.

    Science.gov (United States)

    Ezra, N; Dang, K; Heuser, G

    2011-01-01

    It is, by now, well established that mold toxins (mycotoxins) can cause significant adverse health effects. In this study, 15 subjects who developed an attention deficit disorder (ADD) and slowing of reaction time at the time of exposure to mold toxins were identified. Deficits in attention span and reaction time were documented not only by taking a careful history, but also by performing a Test of Variables of Attention (TOVA). The TOVA test provides an objective measure of these two variables. It was found that mold-exposed subjects show statistically significant decreases in attention span and significant increases in reaction time to stimuli compared to controls. After ten sessions of hyperbaric oxygen treatment (HBOT), a statistically significant improvement was seen in both measures. This preliminary study suggests promising outcomes in treating mold-exposed patients with hyperbaric oxygen.

  4. Facilitated Oxygen Chemisorption in Heteroatom-Doped Carbon for Improved Oxygen Reaction Activity in All-Solid-State Zinc-Air Batteries.

    Science.gov (United States)

    Liu, Sisi; Wang, Mengfan; Sun, Xinyi; Xu, Na; Liu, Jie; Wang, Yuzhou; Qian, Tao; Yan, Chenglin

    2018-01-01

    Driven by the intensified demand for energy storage systems with high-power density and safety, all-solid-state zinc-air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc-air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X-ray diffraction and Raman spectroscopy, of a heteroatom-doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen-containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc-air batteries. As expected, solid-state zinc-air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom-doped carbon materials in zinc-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. The synthesis of PdPt/carbon paper via surface limited redox replacement reactions for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Motsoeneng, RG

    2015-09-01

    Full Text Available Surface-limited redox replacement reactions using the electrochemical atomic layer deposition (EC-ALD) technique were used to synthesize PdPt bimetallic electrocatalysts on carbon paper substrate. Electrocatalysts having different Pd:Pt ratio were...

  6. Obtaining of platinum-titanium alloys by sol-gel and their performance for the detachment reactions and oxygen reduction

    International Nuclear Information System (INIS)

    Regueira R, B. I.

    2011-01-01

    In the present work, platinum-titanium (Pt-Ti) alloys were prepared, characterized and evaluated in acid media as bifunctional electrocatalysts for the oxygen evolution reaction (Oer) and oxygen reduction reactions (Orr) in acid media. The alloys were synthesized by sol-gel method, heating the gel at temperatures of 400 and 600 C. The alloys characterization was realized by X-ray diffraction, scanning electron microscopy and EDS. Both alloys were formed by agglomerates of nanometer particles. The particle sizes were lower for the alloy obtained at 400 C (120 nm to 257 nm) compared to the alloy prepared at 600 C (555 nm to 833 nm). Cyclic and linear voltammetry techniques were used for the electrochemical evaluation of the alloy obtained at both temperatures for the Oer and Orr, in a 0.5 M sulfuric acid solution. The materials have response for both electrochemical reactions, therefore the best performance was for the Pt-Ti alloy, obtained at 400 C and it was stable for the oxygen evolution reaction. The alloy obtained at 400 C presents satisfactory electrocatalytic characteristics to be used as bifunctional material in a unified regenerative fuel cell. (Author)

  7. Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

    Directory of Open Access Journals (Sweden)

    Georgios D. Papakonstantinou

    2011-01-01

    striking target issue of the present paper, has been shown to be the superior for substantiation of the revertible cell assembly for spontaneous reversible alterpolar interchanges between PEMFC and WE. The main target of the present thorough review study has been to throw some specific insight light on the overall spillover phenomena and their effects in electrocatalysis of oxygen and hydrogen electrode reactions from diverse angles of view and broad contemporary experimental methods and approaches (XPS, FTIR, DRIFT, XRD, potentiodynamic spectra, UHRTEM.

  8. Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

    2011-06-30

    Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

  9. Preparation of graphene/nile blue nanocomposite: Application for oxygen reduction reaction and biosensing

    International Nuclear Information System (INIS)

    Shervedani, Reza Karimi; Amini, Akbar

    2015-01-01

    Highlights: •New nanocomposite is synthesized by electrochemical polymerization of Nile blue and reduction of GO on GCE. •The nanocomposite is characterized by SEM, UV–vis and electrochemical methods. •High electrocatalytic activity was observed for O 2 reduction on GNs-NB nanocomposite. •GCE-GNs-NB poly was tested successfully for immobilization of GOx and detection of glucose. -- Abstract: Nile blue/graphene (NB-GNs) nanocomposite was synthesized for the first time via a green and effective one-step electrochemical method, allowing to reduce graphene oxide (GO) and NB on the glassy carbon electrode (GCE) simultaneously and construct GCE-GNs-NB poly composite. The composite was characterized by scanning electron microscopy (SEM), UV–Vis spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrochemical results obtained in the absence of any redox probe, where NB was active, allowed to trace step-by-step addition of the NB-GNs nanocomposite onto the GCE electrode surface, supporting formation of the GCE-GNs-NB poly composite. The electrocatalytic activity of the as-prepared GCE-GNs-NB poly towards O 2 reduction was studied in neutral medium. The results revealed excellent electrocatalytic performance for two-electron reduction of oxygen, suggesting its potential application as metal-free electrocatalysts for O 2 reduction reaction. Application of the GCE-GNs-NB poly in electrochemical biosensing was demonstrated by immobilization of glucose oxidase (GOx) on the surface of GCE-GNs-NB poly , and then, using it for sensing of glucose. The biosensor exhibited a linear response, from 0.2 to 2.0 mM glucose, with a low detection limit, 2.1 μM, and high sensitivity, 67.0 μA mM −1 cm −2 , obtained by cyclic voltammetry method. The proposed biosensor was successfully tested for determination of glucose in blood serum samples

  10. Structure Effects of 2D Materials on α-Nickel Hydroxide for Oxygen Evolution Reaction.

    Science.gov (United States)

    Luan, Chenglong; Liu, Guangli; Liu, Yujie; Yu, Lei; Wang, Yao; Xiao, Yun; Qiao, Hongyan; Dai, Xiaoping; Zhang, Xin

    2018-04-24

    To engineer low-cost, high-efficiency, and stable oxygen evolution reaction (OER) catalysts, structure effects should be primarily understood. Focusing on this, we systematically investigated the relationship between structures of materials and their OER performances by taking four 2D α-Ni(OH) 2 as model materials, including layer-stacked bud-like Ni(OH) 2 -NB, flower-like Ni(OH) 2 -NF, and petal-like Ni(OH) 2 -NP as well as the ultralarge sheet-like Ni(OH) 2 -NS. For the first three (layer-stacking) catalysts, with the decrease of stacked layers, their accessible surface areas, abilities to adsorb OH - , diffusion properties, and the intrinsic activities of active sites increase, which accounts for their steadily enhanced activity. As expected, Ni(OH) 2 -NP shows the lowest overpotential (260 mV at 10 mA cm -2 ) and Tafel slope (78.6 mV dec -1 ) with a robust stability over 10 h among the samples, which also outperforms the benchmark IrO 2 (360 mV and 115.8 mV dec -1 ) catalyst. Interestingly, Ni(OH) 2 -NS relative to Ni(OH) 2 -NP exhibits even faster substance diffusion due to the sheet-like structure, but shows inferior OER activity, which is mainly because the Ni(OH) 2 -NP with a smaller size possesses more active boundary sites (higher reactivity of active sites) than Ni(OH) 2 -NS, considering the adsorption properties and accessible surface areas of the two samples are quite similar. By comparing the different structures and their OER behaviors of four α-Ni(OH) 2 samples, our work may shed some light on the structure effect of 2D materials and accelerate the development of efficient OER catalysts.

  11. Laser Doppler imaging, thermographic imaging, and tissue oxygen saturation measurements detect early skin reactions during breast radiotherapy

    Science.gov (United States)

    Harrison, David K.; Harrison, Eileen M.; Newton, David J.; Windsor, Phyllis M.

    2001-05-01

    A range of acute skin reactions, ranging from mild erythema to moist desquamation, can be seen in patients receiving standard fractionated radiotherapy to the breast for conservation therapy of breast carcinoma. In a number of cases these reactions can cause considerable discomfort and seriously affect the patient's quality of life. In previous studies we have used the techniques of laser Doppler imaging, digital thermographic imaging and lightguide spectrophotometry to study oxygen supply and blood flow in inflammatory reactions induced experimentally in forearm skin. The present study is an attempt to use the same techniques to investigate whether any or all of them can detect changes in breast skin very early on in the course of radiotherapy treatment. A further aim of the longer term study is to investigate to what extent these early changes may be able to predict the occurrence later of severe acute or delayed reactions.

  12. Quasifree (p, 2p) Reactions on Oxygen Isotopes: Observation of Isospin Independence of the Reduced Single-Particle Strength.

    Science.gov (United States)

    Atar, L; Paschalis, S; Barbieri, C; Bertulani, C A; Díaz Fernández, P; Holl, M; Najafi, M A; Panin, V; Alvarez-Pol, H; Aumann, T; Avdeichikov, V; Beceiro-Novo, S; Bemmerer, D; Benlliure, J; Boillos, J M; Boretzky, K; Borge, M J G; Caamaño, M; Caesar, C; Casarejos, E; Catford, W; Cederkall, J; Chartier, M; Chulkov, L; Cortina-Gil, D; Cravo, E; Crespo, R; Dillmann, I; Elekes, Z; Enders, J; Ershova, O; Estrade, A; Farinon, F; Fraile, L M; Freer, M; Galaviz Redondo, D; Geissel, H; Gernhäuser, R; Golubev, P; Göbel, K; Hagdahl, J; Heftrich, T; Heil, M; Heine, M; Heinz, A; Henriques, A; Hufnagel, A; Ignatov, A; Johansson, H T; Jonson, B; Kahlbow, J; Kalantar-Nayestanaki, N; Kanungo, R; Kelic-Heil, A; Knyazev, A; Kröll, T; Kurz, N; Labiche, M; Langer, C; Le Bleis, T; Lemmon, R; Lindberg, S; Machado, J; Marganiec-Gałązka, J; Movsesyan, A; Nacher, E; Nikolskii, E Y; Nilsson, T; Nociforo, C; Perea, A; Petri, M; Pietri, S; Plag, R; Reifarth, R; Ribeiro, G; Rigollet, C; Rossi, D M; Röder, M; Savran, D; Scheit, H; Simon, H; Sorlin, O; Syndikus, I; Taylor, J T; Tengblad, O; Thies, R; Togano, Y; Vandebrouck, M; Velho, P; Volkov, V; Wagner, A; Wamers, F; Weick, H; Wheldon, C; Wilson, G L; Winfield, J S; Woods, P; Yakorev, D; Zhukov, M; Zilges, A; Zuber, K

    2018-02-02

    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R^{3}B/LAND setup with incident beam energies in the range of 300-450  MeV/u. The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type ^{A}O(p,2p)^{A-1}N have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  13. Oxygen 18 concentration profile measurements near the surface by 18O(p,α)15N resonance reaction

    International Nuclear Information System (INIS)

    Amsel, G.; David, D.

    1975-01-01

    The method of spectrum reduction in nuclear reaction microanalysis does not allow to obtain depth resolutions better than the order of 2000A. Resolutions of the order of 200A may be obtained by using the narrow resonance technique, when applied to thin films. The latter technique was extended to thick targets, with deep concentration profiles presenting a sharp gradient near the surface. This method is presented and illustrated by the study of 18 O profiles in oxygen diffusion measurements in growing ZrO 2 , using the 629keV resonance of the reaction 18 O(p,α) 15 N [fr

  14. A survey of the reaction rate constants for the thermal dissociation and recombination of nitrogen and oxygen

    Science.gov (United States)

    Marraffa, Lionel; Dulikravich, George S.; Keeney, Timothy C.; Deiwert, George S.

    1988-01-01

    The objective of the present report is to survey the various values of forward and backward reaction rate constants used by investigators in the field of high-temperature (T greater than 2000 K) gas reactions involving nitrogen and oxygen only. The objective is to find those values that correlate well so that they can be used for the studies of hypersonic flow and supersonic combustion with reasonable confidence. Relatively good agreement among these various values is observed for temperatures lower than 10,000 K.

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

    DEFF Research Database (Denmark)

    Hu, Yang; Zhu, Jianbin; Lv, Qing

    2015-01-01

    Cost-effective, active and stable electrocatalysts for the oxygen reduction reaction (ORR) are highly desirable for the wide-spread adoption of technologies such as fuel cells and metal-air batteries. Among the already reported non-precious metal catalysts, carbon-supported transition metal...... to that for the undoped Fe-N/C catalyst. The activity and durability of the catalysts are demonstrated in direct methanol fuel cells....

  16. Electrocatalytic activity of silver decorated ceria microspheres for the oxygen reduction reaction and their application in aluminium-air batteries.

    Science.gov (United States)

    Sun, Shanshan; Xue, Yejian; Wang, Qin; Li, Shihua; Huang, Heran; Miao, He; Liu, Zhaoping

    2017-07-11

    Nanosheet-constructing porous CeO 2 microspheres with silver nanoparticles anchored on the surface were developed as a highly efficient oxygen reduction reaction (ORR) catalyst. The aluminum-air batteries applying Ag-CeO 2 as the ORR catalyst exhibit a high output power density and low degradation rate of 345 mW cm -2 and 2.6% per 100 h, respectively.

  17. Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2008-01-01

    Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

  18. Reaction analogues in the radiation-induced deamination and dephosphorylation of bio-organic molecules 2: Oxygenated solutions

    International Nuclear Information System (INIS)

    Garrison, W.M.

    1988-02-01

    The OH-induced deamination and dephosphorylation of simple peptides and phosphate esters in oxygenated solutions involve the fomation and subsequent degradation of the perodyl radicals RCONHC(/dot O/)R 2 and /bigcirc P/ OC(/dot O/ 2 )R 2 respectively. Reaction analogues in the degradation of peroxyl and alkoxyl radicals in these two systems are evaluated with reference to the OH-induced main-chain cleavage of protein and DNA. 25 refs

  19. The Reduction Reaction of Dissolved Oxygen in Water by Hydrazine over Platinum Catalyst Supported on Activated Carbon Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Park, K.K.; Moon, J.S. [Korea Electric Power Research Institute, Taejon (Korea)

    1999-07-01

    The reduction reaction of dissolved oxygen (DO) by hydrazine was investigated on activated carbon fiber (ACF) and Pt/ACF catalysts using a batch reactor with an external circulating loop. The ACF itself showed catalytic activity and this was further improved by supporting platinum on ACF. The catalytic role platinum is ascribed to its acceleration of hydrazine decomposition, based on electric potential and current measurements as well as the kinetic study. (author). 15 refs., 13 figs.

  20. An investigation on the electrocatalytic properties of polypyrrole films on the kinetics of oxygen reduction reaction in PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Saremi, M.; Sharifi Asl, S.; Kazemi, Sh. [Tehran Univ., Tehran (Iran, Islamic Republic of). School of Metallurgy and Material Science Engineering

    2008-07-01

    A proton exchange membrane (PEM) fuel cell has high power density, low weight, very short start-up time and no leakage of electrolytes. However, there are some disadvantages when operating the PEM fuel cell at room temperature. Many studies involving the widespread commercial use of Pt-based electrocatalysts search for low-cost electrocatalysts for the oxygen reduction reaction. In recent years, much attention has been placed on the use of electrocatalysis for the conducting polymer electrode. Polypyrrole has attracted much attention as an advanced conducting material because of its good environmental stability, easy synthesis and high conductivity. This study examined the effect of the polypyrrole catalyst in a PEMFC cathode. The electropolymerization of pyrrole was carried out in a 3-electrode cell using pure hydrogen and oxygen as the reactants. Tests were carried out at room temperature and cell impedance was measured. The polymer was formed galvanostatically in a 0.1 M pyrrole with a 0.15 KCl aqueous solution with a 20 mA/cm{sup 2} current density. The effect of operating voltage and oxygen mass transport was examined by EIS method, which separates these two phenomena. The study showed that polypyrrole has a catalytic effect for oxygen reduction reaction in PEMFC comparable to a Pt catalyzed electrode. Although the cell potential with polypyrrole was slightly lower than a Pt coated cell, it was found to be more economical. 8 refs., 2 figs.

  1. Characterization of reaction products in sodium-oxygen batteries : An electrolyte concentration study

    OpenAIRE

    Hedman, Jonas

    2017-01-01

    In this thesis, the discharge products formed at the cathode and the performance and cell chemistry of sodium-oxygen batteries have been studied. This was carried out using different NaOTf salt concentrations. The influence of different salt concentrations on sodium-oxygen batteries was investigated since it has been shown that increasing the salt concentration beyond conventional concentrations could result in advantages such as increased stability of the electrolytes towards decomposition, ...

  2. Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

    2014-01-01

    Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

  3. Influence of Micropore and Mesoporous in Activated Carbon Air-cathode Catalysts on Oxygen Reduction Reaction in Microbial Fuel Cells

    International Nuclear Information System (INIS)

    Liu, Yi; Li, Kexun; Ge, Baochao; Pu, Liangtao; Liu, Ziqi

    2016-01-01

    In this study, carbon samples with different micropore and mesoporous structures are prepared as air-cathode catalyst layer to explore the role of pore structure on oxygen reduction reaction. The results of linear sweep voltammetry and power density show that the commercially-produced activated carbon (CAC) has the best electrochemical performance, and carbon samples with only micropore or mesoporous show lower performance than CAC. Nitrogen adsorption-desorption isotherms analysis confirm that CAC has highest surface area (1616 m 2 g −1 ) and a certain amount of micropore and mesoporous. According to Tafel plot and rotating disk electrode, CAC behaves the highest kinetic activity and electron transfer number, leading to the improvement of oxygen reduction reaction. The air permeability test proves that mesoporous structure enhance oxygen permeation. Carbon materials are also analyzed by In situ Fourier Transform Infrared Spectroscopy and H 2 temperature programmed reduction, which indicate that micropore provide active sites for catalysis. In a word, micropore and mesoporous together would improve the electrochemical performance of carbon materials.

  4. One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

    KAUST Repository

    Varga, Tamás

    2018-03-14

    Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close to the ideal particle size for oxygen reduction reaction (ORR) were formed, i.e., with diameter of 3–4 nm (500 and 600 °C) and 6 nm (700 °C). X-ray photoelectron spectroscopy confirmed the successful introduction of both pyridinic and pyrrolic type nitrogen moieties into the graphene layers, which indicates a strong interaction between the nanoparticles and the graphene layers. The electrocatalytic activity of glassy carbon electrodes (GCE) modified with the synthesized Pt/NG samples for oxygen reduction was compared to that of a platinum/carbon black catalyst modified electrode in acidic and alkaline media. Based on the measured limiting current densities and calculated electron transfer number, the highest activity was measured in acidic and alkaline media on the samples annealed at 600 and 700 °C, respectively.

  5. Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císařová, I.; Klepetářová, Blanka; Jones, P. G.; Jahn, Ullrich

    2015-01-01

    Roč. 21, č. 27 (2015), s. 9877-9888 ISSN 0947-6539 R&D Projects: GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : cyclization * domino reactions * electron transfer * Michael addition * radical reactions Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

  6. Study of reactions between nuclear fuel and cladding (316 stainless steel) in reactors. Influence of oxygen

    International Nuclear Information System (INIS)

    Otter, Monique.

    1980-12-01

    We have studied oxidation of 316 steel in close contact with oxides (Usub(0,74)Pusub(0,26)O 2 or UO 2 ), the stoichiometry of oxygen ranging from 2.00 to 2.5. Experiments are carried out either in a closed isothermal system or in an opened isothermal system with a fixed oxygen potential of uranium oxide. We have realized a potentiostatic device using a solid state electrotyte galvanic cell. In a closed system, the sensitized austenitic steel shows intergranular and volume oxidation probably enhanced by migration of steel components towards the fuel. Evidence of the usefulness of passivation have been obtained. We conclude that in a fast reactor sensitized cladding steel is oxydized by the constant potential of oxygen of UPuO 2 . Deposits observed in fuel can be explain by evaporation and cyclic transport phenomena that can be differents from VAN-ARKEL mechanism taking place through fission products [fr

  7. Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

    2017-04-15

    We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

  8. Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

    International Nuclear Information System (INIS)

    Chisaka, Mitsuharu; Itagaki, Noriaki

    2016-01-01

    Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

  9. Inactivation of Neurospora crassa conidia by singlet molecular oxygen generated by a photosensitized reaction

    International Nuclear Information System (INIS)

    Shimizu, M.; Egashira, T.; Takahama, U.

    1979-01-01

    Photodynamic damage of Neurospora crassa conidia was studied in the presence of the photosensitizing dye, toluidine blue O. Conidia which germinated to form colonies decreased in number as irradiation time became longer. The photoinactivation of conidia was suppressed by azide, bovine serum albumin, and histidine, and was stimulated in deuterium oxide. Wild-type conidia were less sensitive to the irradiation that albino conidia. In the wild type, carotenoid-enriched conidia were more resistant against the lethal damage than the conidia which contained small amounts of carotenoids. These results suggest that singlet molecular oxygen causes photodynamic lethal damage to N. crassa conidia and that singlet molecular oxygen is quenched by endogenous carotenoids

  10. Oxygen determination in materials by {sup 18}O(p,αγ){sup 15}N nuclear reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Sanjiv, E-mail: sanjucccm@rediffmail.com [National Centre for Compositional Characterization of Materials, BARC, ECIL Post, Hyderabad 500062 (India); Sunitha, Y.; Reddy, G.L.N.; Sukumar, A.A.; Ramana, J.V.; Sarkar, A. [National Centre for Compositional Characterization of Materials, BARC, ECIL Post, Hyderabad 500062 (India); Verma, Rakesh [Analytical Chemistry Division, BARC, Mumbai 400085 (India)

    2016-07-01

    The paper presents a proton induced γ-ray emission method based on {sup 18}O(p,αγ){sup 15}N nuclear reaction to determine bulk oxygen in materials. The determination involves the measurement of 5.27 MeV γ-rays emitted following the de-excitation of {sup 15}N nuclei. A description of the energetics of the reaction is given to provide an insight into the origin of 5.27 MeV γ-rays. In addition, thick target γ-ray yields and the limits of detection are measured to ascertain the analytical potential of the reaction. The thick-target γ-ray yields are measured with a high purity germanium detector and a bismuth germanate detector at 0° as well as 90° angles in 3.0–4.2 MeV proton energy region. The best limit of detection of about 1.3 at.% is achieved at 4.2 MeV proton energy for measurements at 0° as well 90° angles with the bismuth germanate detector while the uncertainty in quantitative analysis is <8%. The reaction has a probing depth of several tens of microns. Interferences can arise from fluorine due to the occurrence of {sup 19}F(p,αγ){sup 16}O reaction that emits 6–7 MeV γ-rays. The analytical potential of the methodology is demonstrated by determining oxygen in several oxide as well as non-oxide materials.

  11. Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Lukasz JOZWIAK

    2017-02-01

    Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

  12. 1,5-Asymmetric induction in the boron-mediated aldol reaction of β-oxygenated methyl ketones

    International Nuclear Information System (INIS)

    Dias, Luiz C.

    2007-01-01

    High levels of substrate-based 1,5-stereo induction are obtained in the boron-mediated aldol reactions of β-oxygenated methyl ketones with achiral and chiral aldehydes. Remote induction from the boron enolates gives the 1,5-anti adducts, with the enolate pi-facial selectivity critically dependent upon the nature of the beta-alkoxy protecting group. This 1,5-anti aldol methodology has been strategically employed in the total synthesis of several natural products. At present, the origin of the high level of 1,5-anti induction obtained with the boron enolates is unclear, although a model based on a hydrogen bonding between the alkoxy oxygen and the formyl hydrogen has been recently proposed. (author)

  13. Studies on the heterogeneous electron transport and oxygen reduction reaction at metal (Co, Fe) octabutylsulphonylphthalocyanines supported on multi-walled carbon nanotube modified graphite electrode

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-09-01

    Full Text Available Heterogeneous electron transfer dynamics and oxygen reduction reaction (ORR) activities using octabutylsulphonylphthalocyanine complexes of iron (FeOBSPc) and cobalt (CoOBSPc) supported on multi-walled carbon nanotube (MWCNT) platforms have been...

  14. Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium

    CSIR Research Space (South Africa)

    Mamuru, SA

    2010-11-01

    Full Text Available Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron...

  15. Oxygen reduction reaction at MWCNT-modified nanoscale iron(II) tetrasulfophthalocyanine: remarkable performance over platinum and tolerance toward methanol in alkaline medium

    CSIR Research Space (South Africa)

    Fashedemi, OO

    2015-04-01

    Full Text Available A nanoscale iron(II) tetrasulfophthalocyanine (nanoFeTSPc) catalyst obtained by co-ordinating with hexadecyltrimethylammonium bromide and subsequently anchored onto multi-walled carbon nanotubes (MWCNTs) for oxygen reduction reaction (ORR) has been...

  16. Oxygen dependency of neutrophilic Fe(II) oxidation by Leptothrix differs from abiotic reaction

    NARCIS (Netherlands)

    Vollrath, S.; Behrends, T.; Van Cappellen, P.

    2012-01-01

    Neutrophilic Fe(II) oxidizing microorganisms are found in many natural environments. It has been hypothesized that, at low oxygen concentrations, microbial iron oxidation is favored over abiotic oxidation. Here, we compare the kinetics of abiotic Fe(II) oxidation to oxidation in the presence of

  17. Three-dimensional iron, nitrogen-doped carbon foams as efficient electrocatalysts for oxygen reduction reaction in alkaline solution

    International Nuclear Information System (INIS)

    Ma, Yanjiao; Wang, Hui; Feng, Hanqing; Ji, Shan; Mao, Xuefeng; Wang, Rongfang

    2014-01-01

    Graphical abstract: Three-dimentional Fe, N-doped carbon foams prepared by two steps exhibited comparable catalytic activity for oxygen reduction reaction to commercial Pt/C due to the unique structure and the synergistic effect of Fe and N atoms. - Highlights: • Three-dimensional Fe, N-doped carbon foam (3D-CF) were prepared. • 3D-CF exhibits comparable catalytic activity to Pt/C for oxygen reduction reaction. • The enhanced activity of 3D-CF results of its unique structure. - Abstract: Three-dimensional (3D) Fe, N-doped carbon foams (3D-CF) as efficient cathode catalysts for the oxygen reduction reaction (ORR) in alkaline solution are reported. The 3D-CF exhibit interconnected hierarchical pore structure. In addition, Fe, N-doped carbon without porous strucuture (Fe-N-C) and 3D N-doped carbon without Fe (3D-CF’) are prepared to verify the electrocatalytic activity of 3D-CF. The electrocatalytic performance of as-prepared 3D-CF for ORR shows that the onset potential on 3D-CF electrode positively shifts about 41 mV than those of 3D-CF’ and Fe-N-C respectively. In addition, the onset potential on 3D-CF electrode for ORR is about 27 mV more negative than that on commercial Pt/C electrode. 3D-CF also show better methanol tolerance and durability than commercial Pt/C catalyst. These results show that to synthesize 3D hierarchical pores with high specific surface area is an efficient way to improve the ORR performance

  18. Optimization of the Pd-Fe-Mo Catalysts for Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

    International Nuclear Information System (INIS)

    Lee, Yeayeon; Jang, Jeongseok; Lee, Jin Goo; Jeon, Ok Sung; Kim, Hyeong Su; Hwang, Ho Jung; Shul, Yong Gun

    2016-01-01

    Highlights: • Pd-Mo-Fe catalysts show high catalytic activity and stability for oxygen-reduction reactions in acid media. • The optimum compositions were 7.5:1.5:1.0 for Pd-Fe-Mo, and the optimum temperatures were 500 °C. • The Pd-Fe-Mo catalysts were successfully applied to the PEMFC cathode, showing ∼500 mA cm −1 at 0.6 V. • The lattice constant was strongly related to the activity and stability of the catalysts for oxygen-reduction reactions. - Abstract: Highly active and durable non-platinum catalysts for oxygen-reduction reaction (ORR) have been developed for energy conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this study, Pd-Fe-Mo catalyst is reported as a non-platinum catalyst for ORR. The atomic ratio and annealing temperatures are controlled on the catalysts to understand interplay between their physical and chemical properties and electrochemical activities. The Pd-Fe-Mo catalyst optimized with 7.5:1.5:1.0 of the atomic ratio and 500 °C of the annealing temperature shows 32.18 mA mg −1 PGM (PGM: platinum group metal) of the kinetic current density at 0.9 V for ORR, which is comparable to that of commercial Pt/C catalyst. The current density is degraded to 6.20 mA mg −1 PGM after 3000 cycling of cyclic voltammetry, but it is greatly enhanced value compared to other non-platinum catalysts. In actual application to PEMFCs, the 20% Pd-Fe-Mo catalyst supported on carbons exhibits a high performance of 506 mA cm −2 at 0.6 V. The results suggest that the Pd-Fe-Mo catalyst can be a good candidate for non-platinum ORR catalysts.

  19. In Operando Self-Healing of Perovskite Electrocatalysts: A Case Study of SrCoO3 for the Oxygen Evolution Reaction

    KAUST Repository

    Tahini, Hassan A.

    2017-01-24

    Perovskites are promising catalysts for oxygen evolution reactions (OER); among them, SrCoO3 is one of the best for these reactions. We study the O* intermediates and the role of surface oxygen vacancies of SrCoO3 during OER. A self-healing mechanism is proposed in which O* are incorporated into the surface to recover the redox capabilities of the material.

  20. In Operando Self-Healing of Perovskite Electrocatalysts: A Case Study of SrCoO3 for the Oxygen Evolution Reaction

    KAUST Repository

    Tahini, Hassan A.; Tan, Xin; Schwingenschlö gl, Udo; Smith, Sean C.

    2017-01-01

    Perovskites are promising catalysts for oxygen evolution reactions (OER); among them, SrCoO3 is one of the best for these reactions. We study the O* intermediates and the role of surface oxygen vacancies of SrCoO3 during OER. A self-healing mechanism is proposed in which O* are incorporated into the surface to recover the redox capabilities of the material.

  1. A Theoretical Analysis of the Reaction Between Ethyl and Molecular Oxygen

    National Research Council Canada - National Science Library

    Miller, James A; Klippenstein, Stephen J; Robertson, Struan H

    2000-01-01

    Using a combination of electronic-structure theory, variational transition-state theory, and solutions to the time-dependent master equation, we have studied the kinetics of the reaction between ethyl...

  2. Operando investigation of Au-MnOx thin films with improved activity for the oxygen evolution reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Seitz, Linsey C.; Sokaras, Dimosthenis

    2017-01-01

    The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen...... improvement over pure MnOx. These films are characterized with operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. The magnitude of the enhancement is correlated to the size of the Au domains, where larger domains...

  3. A cell for extended x-ray absorption fine structure studies of oxygen sensitive products of redox reactions

    International Nuclear Information System (INIS)

    Furenlid, L.R.; Renner, M.W.; Fajer, J.

    1990-01-01

    We describe a cell suitable for extended x-ray absorption fine structure (EXAFS) studies of oxygen and/or water sensitive products of redox reactions. The cell utilizes aluminized Mylar windows that are transparent to x rays, provide low gas permeability, and allow vacuum to be maintained in the cell. The windows are attached to the glassware with an epoxy that resists attack by common organic solvents. Additional side arms allow multiple spectroscopic probes of the same sample under anaerobic and anhydrous conditions

  4. Nitrogen and Fluorine-Codoped Carbon Nanowire Aerogels as Metal-Free Electrocatalysts for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Zhu, Chengzhou [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Song, Junhua [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Xiao, Biwei [Energy and Environmental Directory, Pacific Northwest National Laboratory, Richland WA 99352 USA; Du, Dan [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA; Lin, Yuehe [School of Mechanical and Materials Engineering, Washington State University, Pullman, WA 99164 USA

    2017-07-11

    The development of active, durable, and low-cost catalysts to replace noble metal-based materials is highly desirable to promote the sluggish oxygen reduction reaction in fuel cells. Herein, nitrogen and fluorine-codoped three-dimensional carbon nanowire aerogels, composed of interconnected carbon nanowires, were synthesized for the first time by a hydrothermal carbonization process. Owing to their porous nanostructures and heteroatom-doping, the as-prepared carbon nanowire aerogels, with optimized composition, present excellent electrocatalytic activity that is comparable to commercial Pt/C. Remarkably, the aerogels also exhibit superior stability and methanol tolerance. This synthesis procedure paves a new way to design novel heteroatomdoped catalysts.

  5. A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

    Science.gov (United States)

    Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

    2015-04-30

    Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

  6. Use of nuclear reactions to trace the source of oxygen in anodization

    International Nuclear Information System (INIS)

    Lewis, M.B.; Perkins, R.A.

    1978-01-01

    In cases where the anodization of metals involves the use of chemical solutions, the oxidation mechanism is frequently uncertain. In such cases it is usually possible to make oxygen bearing solutes from oxgen which is enriched in isotope-18. After use in anodization, the oxide films can be analyzed by the method of nuclear microanalysis which separately profiles the 18 O and 16 O. In this way the depth distribution of the 18 O can be compared quantitatively with that of the 16 O arising from all other oxygen bearing chemicals in solution. This method was applied to the case of the anodization of vanadium and zirconium. The results indicate an unconventional anodization mechanism for the vanadium case

  7. Electrocatalysis of oxygen electrode reactions by some perovskite oxides based on lanthanum manganate

    International Nuclear Information System (INIS)

    Raj, I.A.; Rao, K.V.; Venkatesan, V.K.

    1984-01-01

    In recent years, several electrocatalyst materials based on platinum, silver, tungsten bronzes, spinels, metal chelates, etc., have been studied for use as oxygen diffusion electrodes in alkaline fuel cells, secondary metal-air batteries, and water electrolyzers. However, virtually all catalysts of commercial importance are semiconducting transition metal oxides. The various oxide catalysts that have been studied can be grouped under mixed oxides, spinels, and perovskites

  8. First-principles study of oxygen evolution reaction on Co doped NiFe-layered double hydroxides

    Science.gov (United States)

    Yu, Jie; Perdew, John; Yan, Qimin

    The conversion of solar energy to renewable fuels is a grand challenge. One of the crucial steps for this energy conversion process is the discovery of efficient catalysts with lower overpotential for the oxygen evolution reaction (OER). Layered double hydroxides (LDH) with earth abundant elements such as Ni and Fe have been found as promising OER catalysts and shown to be active for water oxidation. Doping is one of the feasible ways to even lower the overpotential of host materials and breaks the linear scaling law. In this talk we'll present our study on the reaction mechanism of OER on pure and Co-doped NiFe-LDH systems in alkaline solution. We study the absorption energetics of reaction intermediate states and calculate the thermodynamic reaction energy using density functional theory with the PBE +U and the newly developed SCAN functionals. It is shown that the NiFe-LDH system with Co dopants has lower overpotential and higher activity compared with the undoped system. The improvement in activity is related to the presence of Co states in the electronic structure. The work provides a clear clue for the further improvement of the OER activity of LDH systems by chemical doping. The work was supported as part of the Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science.

  9. Dependence of size and size distribution on reactivity of aluminum nanoparticles in reactions with oxygen and MoO3

    International Nuclear Information System (INIS)

    Sun, Juan; Pantoya, Michelle L.; Simon, Sindee L.

    2006-01-01

    The oxidation reaction of aluminum nanoparticles with oxygen gas and the thermal behavior of a metastable intermolecular composite (MIC) composed of the aluminum nanoparticles and molybdenum trioxide are studied with differential scanning calorimetry (DSC) as a function of the size and size distribution of the aluminum particles. Both broad and narrow size distributions have been investigated with aluminum particle sizes ranging from 30 to 160 nm; comparisons are also made to the behavior of micrometer-size particles. Several parameters have been used to characterize the reactivity of aluminum nanoparticles, including the fraction of aluminum that reacts prior to aluminum melting, heat of reaction, onset and peak temperatures, and maximum reaction rates. The results indicate that the reactivity of aluminum nanoparticles is significantly higher than that of the micrometer-size samples, but depending on the measure of reactivity, it may also depend strongly on the size distribution. The isoconversional method was used to calculate the apparent activation energy, and the values obtained for both the Al/O 2 and Al/MoO 3 reaction are in the range of 200-300 kJ/mol

  10. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  11. Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries

    International Nuclear Information System (INIS)

    Li Xiaoxia; Zhu, Aaron Li; Qu Wei; Wang Haijiang; Hui, Rob; Zhang Lei; Zhang Jiujun

    2010-01-01

    In this paper, Magneli phase Ti 4 O 7 was successfully synthesized using a TiO 2 reduction method, and characterized using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The electrode coated with this Ti 4 O 7 material showed activities for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). For the ORR, several parameters, including overall electron transfer number, kinetic constants, electron transfer coefficient, and percentage H 2 O 2 production, were obtained using the rotating ring-disk electrode (RRDE) technique and the Koutecky-Levich theory. The overall electron transfer number was found to be between 2.3 and 2.9 in 1, 4, and 6 M KOH electrolytes, suggesting that the ORR process on the Ti 4 O 7 electrode was a mixed process of 2- and 4-electron transfer pathways. Electrochemical durability tests, carried out in highly concentrated KOH electrolyte, confirmed that this Ti 4 O 7 is a stable electrode material, suggesting that it should be a feasible candidate for the air-cathodes of zinc-air batteries. To understand the stability of this material, Raman and XPS spectra were also collected for the Ti 4 O 7 samples before and after the stability tests. The results and analysis revealed that a thin layer of TiO 2 formed on the Ti 4 O 7 surface, which may have prevented further oxidation into the bulk of the Ti 4 O 7 electrode.

  12. O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts.

    Science.gov (United States)

    Yang, Yang; Mao, Kaitian; Gao, Shiqi; Huang, Hao; Xia, Guoliang; Lin, Zhiyu; Jiang, Peng; Wang, Changlai; Wang, Hui; Chen, Qianwang

    2018-05-28

    Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese-containing enzymes can catalyze oxygen-evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme-copper oxidases superfamily. Unlike previous single-metal catalysts with general M-N-C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc-air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn-N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Jiashen Meng; Chaojiang Niu; Xiong Liu; Ziang Liu; Hongliang Chen; Xuanpeng Wang; Jiantao Li

    2016-01-01

    Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis,chemical sensing,drug delivery,and energy storage.However,the controlled synthesis of multilevel nanotubes remains a great challenge.Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment.This versatile strategy can be effectively applied to fabricate wire-in-tube and tubein-tube nanotubes of various metal oxides.These multilevel nanotubes possess a large specific surface area,fast mass transport,good strain accommodation,and high packing density,which are advantageous for lithium-ion batteries (LIBs)and the oxygen reduction reaction (ORR).Specifically,shrinkable CoMn2O4 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of ~565 mAh.g-1 at a high rate of 2 A.g-1,maintaining 89% of the latter after 500 cycles.Further,as an oxygen reduction reaction catalyst,these nanotubes also exhibit excellent stability with about 92% current retention after 30,000 s,which is higher than that of commercial Pt/C (81%).Therefore,this feasible method may push the rapid development of one-dimensional (1D) nanomaterials.These multifunctional nanotubes have great potential in many frontier fields.

  14. Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

    Science.gov (United States)

    Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

    2018-03-01

    We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

  15. Proton conductive Pt-Co nanoparticles anchoring on citric acid functionalized graphene for efficient oxygen reduction reaction

    Science.gov (United States)

    Zhao, Yige; Liu, Jingjun; Wu, Yijun; Wang, Feng

    2017-08-01

    Designing highly efficient electro-catalysts for the oxygen reduction reaction (ORR) has been regarded as a demanding task in the development of renewable energy sources. However, little attention has been paid on improving Pt-based catalysts by promoting proton transfer from the electrolyte solutions to the catalyst layer at the cathode. Herein, we design proton conductive Pt-Co alloy nanoparticles anchoring on citric acid functionalized graphene (Pt-Co/CA-G) catalysts for efficient ORR. The facile modification approach for graphene can introduce oxygenated functional groups on the graphene surface to promote proton transfer as well as keeping the high electron conductivity without destroying the graphene original structure. The electrochemical results show that the Pt-Co/CA-G catalyst exhibits more excellent ORR activity and stability than the commercial Pt/C catalyst, which can be attributed to its improved proton transfer ability. The fast proton transfer comes from the hydrogen-bonding networks formed by the interaction between the oxygenated functional groups and water molecules. This work provides not only a novel and simple approach to modify graphene but also an effective strategy to improve Pt-based catalysts for the ORR.

  16. Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution

    Science.gov (United States)

    Suo, Ni; Huang, Hao; Wu, Aimin; Cao, Guozhong; Hou, Xiaoduo; Zhang, Guifeng

    2018-05-01

    Porous boron doped diamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the boron doped diamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous boron doped diamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

  17. Nuclear stopping in oxygen-induced reactions at 200 A GeV

    International Nuclear Information System (INIS)

    Obenshain, F.E.; Albrecht, R.; Awes, T.C.

    1988-01-01

    A primary goal of relativistic heavy-ion studies is to verify the existence of the postulated quark-gluon plasma (QGP). Since most of the possible plasma signatures are indistinguishable from background created by nonplasma events. Thorough understanding of reaction mechanisms is an important prerequisite in any QGP search. To isolate collective features of nucleus-nucleus collisions from those that may be expected on the basis of linear superposition of nucleon-nucleus collisions, we compare measured quantities with calculations that reproduce data from nucleon-induced reactions and that make predictions for nucleus-nucleus reactions. Here we discuss the data obtained from our Zero-Degree Calorimeter (ZDC) and the transverse energy obtained from the Mid-Rapidity Calorimeter (MIRAC). The primary reactions considered are: 16 O + 16 C and 16 O + 197 Au. The measurements show a high degree of nuclear stopping and the energy densities may be large enough to produce a transition to the quark-gluon plasma. 10 refs., 5 figs

  18. Activation pathways taking place at molecular copper precatalysts for the oxygen evolution reaction

    NARCIS (Netherlands)

    van der Ham, C.J.M.; Işık, F.; Verhoeven, T.W.G.M.; Niemantsverdriet, J.W.; Hetterscheid, D.G.H.

    2017-01-01

    The activation processes of [CuII(bdmpza)2] in the water oxidation reaction were investigated using cyclic voltammetry and chronoamperometry. Two different paths wherein CuO is formed were distinguished. [CuII(bdmpza)2] can be oxidized at high potentials to form CuO, which was observed by a slight

  19. Fundamental understanding of oxygen reduction and reaction behavior and developing high performance and stable hetero-structured cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xingbo [West Virginia Univ., Morgantown, WV (United States)

    2016-11-14

    New unique hetero-structured cathode has been developed in this project. La2NiO4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ (LSCF) cathode to enhance the surface-limited ORR kinetics on SOFC cathode. Furthermore, the hetero-structured cathode surface maintains high activity under electrode polarization with much less negative effects from surface cation segregation of Sr, which is known to cause degradation issues for conventional LSCF and LSC cathodes, thus improving the cathode long-term stability. The interface chemistry distribution and oxygen transport properties have been studied to prove the enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO2 & La2-xNiO4+δ (x=0-0.2) co-infiltration is a simple and cost-effective method to improve both performance and stability of LSCF cathode by limiting nano-particles growth/delamination and further improve the surface stability. For the first time, a physical model is proposed to illustrate how unique interstitial species on hetero-structured cathode surface work to regulate the exchange rate of the incorporation reaction. Meanwhile, fundamental investigation of the surface oxygen exchange and bulk oxygen transport properties under over-potential conditions across cathode materials have been carried out in this project, which were discussed and compared to the Nernst equation that is generally applied to treat any oxide electrodes under equilibrium.

  20. Reaction of Oxygen with Chromium and Chromium Carbide at Low O2 Pressures and High Temperatures

    International Nuclear Information System (INIS)

    Hur, Dong O.; Kang, Sung G.; Paik, Young N.

    1984-01-01

    The oxidation rate of chromium carbide has been measured continuously using thermogravimetric analysis at different oxygen pressures ranging from 1.33x10 -2 to 2.67x10 -1 Pa O 2 at 1000-1300 .deg. C. The oxidation of pure chromium has also been studied between 1000-1300 .deg. C under 6.67x10 -2 Pa O 2 and compared with that of chromium carbide. The oxidation of chromium carbide showed a linear behavior which was different from that of chromium. The oxidation rate of chromium carbide increased with increasing temperature and oxygen pressure was lower than of pure chromium. Above 1200 .deg. C, the volatile oxide was formed and evaporated causing a weight loss. The compositions and morphology of the oxide were studied with X-ray diffractometer and scanning electron microscope, respectively. The morphology of oxide changed with varying temperature and pressure. The oxide scale was consisted of mainly two different layers of Cr 2 O 3 and CrO, and the properties of oxide scale were correlated with oxidation behavior. The oxide film formed in the above test condition has been detached from the carbide surface. The crack and pore were thought to be from CO gas evolving at the interface of chromium carbide and its oxide and the major factor of the linear behavior of chromium carbide

  1. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

    Science.gov (United States)

    Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

    2017-10-16

    Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

  2. ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua; He, Xiao-Bo; Lv, Peng-Liang; Ye, Cai-Yun; Liu, Di-Jia

    2017-05-01

    Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

  3. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  4. Mechanochemical synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen reduction reaction

    International Nuclear Information System (INIS)

    Flores-Rojas, E.; Cabañas-Moreno, J.G.; Pérez-Robles, J.F.; Solorza-Feria, O.

    2016-01-01

    High energy milling in combination with galvanic displacement were used for the preparation of bimetallic nanocatalysts. Co and Ni monometallic powders milled for 30 and 20 h, respectively were both produced in air atmosphere and used as precursors for the preparation of M-Pt (M = Co,Ni) compounds. Nanosized monometallic powders were physically supported on Vulcan carbon, and covered with 20 wt%Pt through a Galvanic Displacement Reaction (GDR) to produce Co-20Pt/C and Ni-20Pt/C electrocatalysts. XRD was used for phase identification on milled powders and for demonstrating structural transformations of Co powders during milling. Results on unmilled metallic Co powder show a predominant HCP structure modifying to a FCC structure after milling. Ni powders maintain their same FCC structure. Energy Dispersive X-Ray Spectometry (EDX) was used for chemical composition analysis on milled powders at several milling times. Scanning Transmission Electron Microscopy (STEM) show the formation of heterogeneous particle with ∼10 nm in size for both electrocatalysts. The electrocatalytic activity was evaluated by Cyclic Voltammetry (CV) and steady state Rotating Disk Electrode (RDE) for the Oxygen Reduction Reaction (ORR) in 0.1 M HClO_4. The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the cathodic reaction. - Highlights: • Monometallic powders of Co, and Ni were used as precursors for the preparation of M-Pt (M = Co,Ni) electrocatalysts. • Nanosized monometallic powders were decorated with Pt by a Galvanic Displacement Reaction. • The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the ORR reaction.

  5. Mechanochemical synthesis of Co and Ni decorated with chemically deposited Pt as electrocatalysts for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Flores-Rojas, E.; Cabañas-Moreno, J.G. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Pérez-Robles, J.F. [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Dpto. Ciencia de los Materiales, CINVESTAV-IPN Unidad Queretaro, Libramiento Norponiente No. 2000 Fracc. Real de Juriquilla, 76230, Queretaro (Mexico); Solorza-Feria, O., E-mail: osolorza@cinvestav.mx [Programa de Nanociencias y Nanotecnología, Centro de Investigación y de Estudios Avanzados, CINVESTAV-IPN, Av. Instituto Politécnico Nacional 2508, Col. Zacatenco, 07360 Mexico City (Mexico); Depto. Química, CINVESTAV-IPN, 07360, México City (Mexico)

    2016-11-01

    High energy milling in combination with galvanic displacement were used for the preparation of bimetallic nanocatalysts. Co and Ni monometallic powders milled for 30 and 20 h, respectively were both produced in air atmosphere and used as precursors for the preparation of M-Pt (M = Co,Ni) compounds. Nanosized monometallic powders were physically supported on Vulcan carbon, and covered with 20 wt%Pt through a Galvanic Displacement Reaction (GDR) to produce Co-20Pt/C and Ni-20Pt/C electrocatalysts. XRD was used for phase identification on milled powders and for demonstrating structural transformations of Co powders during milling. Results on unmilled metallic Co powder show a predominant HCP structure modifying to a FCC structure after milling. Ni powders maintain their same FCC structure. Energy Dispersive X-Ray Spectometry (EDX) was used for chemical composition analysis on milled powders at several milling times. Scanning Transmission Electron Microscopy (STEM) show the formation of heterogeneous particle with ∼10 nm in size for both electrocatalysts. The electrocatalytic activity was evaluated by Cyclic Voltammetry (CV) and steady state Rotating Disk Electrode (RDE) for the Oxygen Reduction Reaction (ORR) in 0.1 M HClO{sub 4}. The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the cathodic reaction. - Highlights: • Monometallic powders of Co, and Ni were used as precursors for the preparation of M-Pt (M = Co,Ni) electrocatalysts. • Nanosized monometallic powders were decorated with Pt by a Galvanic Displacement Reaction. • The kinetic parameters on Co-20Pt/C conducted to the highest mass activity for the ORR reaction.

  6. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  7. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-06-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  8. Hydrogen/Oxygen Reactions at High Pressures and Intermediate Temperatures: Flow Reactor Experiments and Kinetic Modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Glarborg, Peter

    A series of experimental and numerical investigations into hydrogen oxidation at high pressures and intermediate temperatures has been conducted. The experiments were carried out in a high pressure laminar flow reactor at 50 bar pressure and a temperature range of 600–900 K. The equivalence ratio......, the mechanism is used to simulate published data on ignition delay time and laminar burning velocity of hydrogen. The flow reactor results show that at reducing, stoichiometric, and oxidizing conditions, conversion starts at temperatures of 750–775 K, 800–825 K, and 800–825 K, respectively. In oxygen atmosphere......, ignition occurs at the temperature of 775–800 K. In general, the present model provides a good agreement with the measurements in the flow reactor and with recent data on laminar burning velocity and ignition delay time....

  9. Theoretical and experimental investigation of carnosine and its oxygenated adducts. The reaction with the nickel ion

    Energy Technology Data Exchange (ETDEWEB)

    Pavlos, Dimitrios; Petropouleas, Panayiotis; Hatzipanayioti, Despina, E-mail: stambaki@chem.uoa.gr

    2015-11-05

    Highlights: • Study on models of neutral cations and anions of carnosine at the B3LYP/TZVP level. • The {sup 1}O{sub 2}-adducts of these models resulted in oxygenated carnosine. • Theoretical parameters correlated to experimental results for carn and carn-H{sub 2}O{sub 2}. • Theoretical models of Nickel-carn complexes have been investigated. • Isolation and characterization of the solid [Ni(carn){sub 2}(H{sub 2}O){sub 5}] have been performed. - Abstract: DFT theoretical calculations at B3LYP/TZVP or LANL2DZ level of theory, for neutral, zwitterions, protonated and anionic carnosine, were performed. Energies, the structural and spectroscopic parameters were calculated in the gas phase and aqueous medium. Additional H-bonds stabilize the ionized forms of carnosine, creating “nests” into which metal ions or bio-molecules may be sheltered. Based on Fukui functions, the reactivity of the abovementioned forms of carnosine, with {sup 1}O{sub 2}, may lead to oxygenated species. The theoretical spectroscopic parameters have been correlated to our experimental results. The effect of H{sub 2}O{sub 2} and the electrochemistry of aqueous carnosine solutions were examined. Theoretical models containing Ni(II), carnosine and water were constructed. In the isolated mauve solid, formulated [Ni(carn){sub 2}(H{sub 2}O){sub 5}], the COO−, N{sub π} and/or NH{sub 2} were bonded. When H{sub 2}O{sub 2} was added, the imidazole NMR signals disappeared. A redox couple clearly indicates one electron process, the electron coming from either the oxidation of imidazole ring or the nickel(II)/Ni(III) couple.

  10. In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

    Science.gov (United States)

    Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

    2018-05-14

    We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

  11. Evaluation of reaction selectivity at various Pt/C electrocatalysts using a porous microelectrode in the presence of methanol and oxygen

    International Nuclear Information System (INIS)

    Shironita, Sayoko; Zhang, Weiqi; Sakai, Tsukasa; Umeda, Minoru

    2014-01-01

    Pt is most useful metal for various electrochemical reactions as an electrocatalyst. In a direct methanol fuel cell, Pt performs a catalytic activity for both the methanol oxidation reaction and oxygen reduction reaction; therefore, a Pt-based catalyst is used as an anode and a cathode. For the coexistence of methanol and oxygen due to methanol crossover through an electrolyte membrane during the cell operation, the direct methanol fuel cell performance decreases. However, if a higher selective reaction electrocatalyst can be developed, the cell performance will not be suppressed. In this study, the reaction selectivities of seven types of Pt supported on carbon (Pt/C) electrocatalysts were evaluated using a porous microelectrode in the presence of methanol and oxygen. As a result, some Pt/C catalysts showed a methanol oxidation selectivity, while the other catalysts showed an oxygen reduction selectivity. It was found that the percentage of edge-atom in the Pt particle is related to the methanol oxidation selectivity or the oxygen reduction selectivity. Moreover, each current density decreases with the increasing chemical shift in the Pt binding energy

  12. Hollow Fluffy Co3O4 Cages as Efficient Electroactive Materials for Supercapacitors and Oxygen Evolution Reaction.

    Science.gov (United States)

    Zhou, Xuemei; Shen, Xuetao; Xia, Zhaoming; Zhang, Zhiyun; Li, Jing; Ma, Yuanyuan; Qu, Yongquan

    2015-09-16

    Nano-/micrometer multiscale hierarchical structures not only provide large surface areas for surface redox reactions but also ensure efficient charge conductivity, which is of benefit for utilization in areas of electrochemical energy conversion and storage. Herein, hollow fluffy cages (HFC) of Co3O4, constructed of ultrathin nanosheets, were synthesized by the formation of Co(OH)2 hollow cages and subsequent calcination at 250 °C. The large surface area (245.5 m2 g(-1)) of HFC Co3O4 annealed at 250 °C ensures the efficient interaction between electrolytes and electroactive components and provides more active sites for the surface redox reactions. The hierarchical structures minimize amount of the grain boundaries and facilitate the charge transfer process. Thin thickness of nanosheets (2-3 nm) ensures the highly active sites for the surface redox reactions. As a consequence, HFC Co3O4 as the supercapacitor electrode exhibits a superior rate capability, shows an excellent cycliability of 10,000 cycles at 10 A g(-1), and delivers large specific capacitances of 948.9 and 536.8 F g(-1) at 1 and 40 A g(-1), respectively. Catalytic studies of HFC Co3O4 for oxygen evolution reaction display a much higher turnover frequency of 1.67×10(-2) s(-1) in pH 14.0 KOH electrolyte at 400 mV overpotential and a lower Tafel slope of 70 mV dec(-1). HFC Co3O4 with the efficient electrochemical activity and good stability can remain a promising candidate for the electrochemical energy conversion and storage.

  13. Host-Guest Engineering of Layered Double Hydroxides towards Efficient Oxygen Evolution Reaction: Recent Advances and Perspectives

    Directory of Open Access Journals (Sweden)

    Jianming Li

    2018-05-01

    Full Text Available Electrochemical water splitting has great potential in the storage of intermittent energy from the sun, wind, or other renewable sources for sustainable clean energy applications. However, the anodic oxygen evolution reaction (OER usually determines the efficiency of practical water electrolysis due to its sluggish four-electron process. Layered double hydroxides (LDHs have attracted increasing attention as one of the ideal and promising electrocatalysts for water oxidation due to their excellent activity, high stability in basic conditions, as well as their earth-abundant compositions. In this review, we discuss the recent progress on LDH-based OER electrocatalysts in terms of active sites, host-guest engineering, and catalytic performances. Moreover, further developments and challenges in developing promising electrocatalysts based on LDHs are discussed from the viewpoint of molecular design and engineering.

  14. Oxygen plasma etching of graphene: A first-principles dynamical inspection of the reaction mechanisms and related activation barriers

    Science.gov (United States)

    Koizumi, Kenichi; Boero, Mauro; Shigeta, Yasuteru; Oshiyama, Atsushi; Dept. of Applied Physics Team; Institute of Physics and Chemistry of Strasbourg (IPCMS) Collaboration; Department Of Materials Engineering Science Collaboration

    2013-03-01

    Oxygen plasma etching is a crucial step in the fabrication of electronic circuits and has recently received a renovated interest in view of the realization of carbon-based nanodevices. In an attempt at unraveling the atomic-scale details and to provide guidelines for the control of the etching processes mechanisms, we inspected the possible reaction pathways via reactive first principles simulations. These processes involve breaking and formation of several chemical bonds and are characterized by different free-energy barriers. Free-energy sampling techniques (metadynamics and blue moon), used to enhance the standard Car-Parrinello molecular dynamics, provide us a detailed microscopic picture of the etching of graphene surfaces and a comprehensive scenario of the activation barriers involved in the various steps. MEXT, Japan - contract N. 22104005

  15. From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

    Science.gov (United States)

    Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

    2017-07-01

    Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

  16. Pt monolayer shell on hollow Pd core electrocatalysts: Scale up synthesis, structure, and activity for the oxygen reduction reaction

    Directory of Open Access Journals (Sweden)

    Vukmirovic Miomir B.

    2013-01-01

    Full Text Available We report on synthesis, characterization and the oxygen reduction reaction (ORR kinetics of Pt monolayer shell on Pd(hollow, or Pd-Au(hollow core electrocatalysts. Comparison between the ORR catalytic activity of the electrocatalysts with hollow cores and those of Pt solid and Pt hollow nanoparticles has been obtained using the rotating disk electrode technique. Hollow nanoparticles were made using Ni or Cu nanoparticles as sacrificial templates. The Pt ORR specific and mass activities of the electrocatalysts with hollow cores were found considerably higher than those of the electrocatalysts with the solid cores. We attribute this enhanced Pt activity to the smooth surface morphology and hollow-induced lattice contraction, in addition to the mass-saving geometry of hollow particles.

  17. A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction

    Science.gov (United States)

    Miao, Yue-E.; Yan, Jiajie; Ouyang, Yue; Lu, Hengyi; Lai, Feili; Wu, Yue; Liu, Tianxi

    2018-06-01

    The bio-inspired hierarchical "grape cluster" superstructure provides an effective integration of one-dimensional carbon nanofibers (CNF) with isolated carbonaceous nanoparticles into three-dimensional (3D) conductive frameworks for efficient electron and mass transfer. Herein, a 3D N-doped porous carbon electrocatalyst consisting of carbon nanofibers with grape-like N-doped hollow carbon particles (CNF@NC) has been prepared through a simple electrospinning strategy combined with in-situ growth and carbonization processes. Such a bio-inspired hierarchically organized conductive network largely facilitates both the mass diffusion and electron transfer during the oxygen reduction reactions (ORR). Therefore, the metal-free CNF@NC catalyst demonstrates superior catalytic activity with an absolute four-electron transfer mechanism, strong methanol tolerance and good long-term stability towards ORR in alkaline media.

  18. Heavily Graphitic-Nitrogen Self-doped High-porosity Carbon for the Electrocatalysis of Oxygen Reduction Reaction

    Science.gov (United States)

    Feng, Tong; Liao, Wenli; Li, Zhongbin; Sun, Lingtao; Shi, Dongping; Guo, Chaozhong; Huang, Yu; Wang, Yi; Cheng, Jing; Li, Yanrong; Diao, Qizhi

    2017-11-01

    Large-scale production of active and stable porous carbon catalysts for oxygen reduction reaction (ORR) from protein-rich biomass became a hot topic in fuel cell technology. Here, we report a facile strategy for synthesis of nitrogen-doped porous nanocarbons by means of a simple two-step pyrolysis process combined with the activation of zinc chloride and acid-treatment process, in which kidney bean via low-temperature carbonization was preferentially adopted as the only carbon-nitrogen sources. The results show that this carbon material exhibits excellent ORR electrocatalytic activity, and higher durability and methanol-tolerant property compared to the state-of-the-art Pt/C catalyst for the ORR, which can be mainly attributed to high graphitic-nitrogen content, high specific surface area, and porous characteristics. Our results can encourage the synthesis of high-performance carbon-based ORR electrocatalysts derived from widely-existed natural biomass.

  19. Effect of ordering of PtCu₃ nanoparticle structure on the activity and stability for the oxygen reduction reaction.

    Science.gov (United States)

    Hodnik, Nejc; Jeyabharathi, Chinnaiah; Meier, Josef C; Kostka, Alexander; Phani, Kanala L; Rečnik, Aleksander; Bele, Marjan; Hočevar, Stanko; Gaberšček, Miran; Mayrhofer, Karl J J

    2014-07-21

    In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.

  20. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    Science.gov (United States)

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Involvement of active oxygen in lipid peroxide radical reaction of epidermal homogenate following ultraviolet light exposure

    International Nuclear Information System (INIS)

    Nishi, J.; Ogura, R.; Sugiyama, M.; Hidaka, T.; Kohno, M.

    1991-01-01

    To elucidate the radical mechanism of lipid peroxidation induced by ultraviolet light (UV) irradiation, an electron spin resonance (ESR) study was made on epidermal homogenate prepared from albino rat skin. The exposure of the homogenate to UV light resulted in an increase in lipid peroxide content, which was proportional to the time of UV exposure. Using ESR spin trapping (dimethyl-1-pyrroline-N-oxide, DMPO), the DMPO spin adduct spectrum of lipid radicals (L.) was measured following UV exposure (DMPO-L.:aN = 15.5 G, aH = 22.7 G), as was the spectrum of DMPO-hydroxyl radical (DMPO-OH, aN = aH = 15.5 G). In the presence of superoxide dismutase, the DMPO spin adduct spectrum of lipid radicals was found to be reduced remarkably. Therefore, it was shown that the generation of the lipid radicals partially involves superoxide anion radicals, in addition to hydroxyl radicals. In the ESR free-radical experiment, an ESR signal appeared at g = 2.0064 when the ESR tube filled with homogenate was exposed to UV light at -150 degrees C. The temperature-dependent change in the ESR free radical signal of homogenate exposed to UV light was observed at temperatures varying from -150 degrees C to room temperature. By using degassed samples, it was confirmed that oxygen is involved in the formation of the lipid peroxide radicals (LOO.) from the lipid radicals (L.)

  2. Electrocatalytic Performance of Carbon Supported WO3-Containing Pd–W Nanoalloys for Oxygen Reduction Reaction in Alkaline Media

    Directory of Open Access Journals (Sweden)

    Nan Cui

    2018-05-01

    Full Text Available In this paper, we report that WOx containing nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 is easy to dissolve in NaOH solution. Carbon supported oxide-rich Pd–W alloy nanoparticles (PdW/C with different Pd:W atom ratios were prepared by the reduction–oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio exhibits the highest catalytic activity for the oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxide form. The Pd 3d5/2 binding energy of the oxide-rich Pd–W nanoalloys is higher than that of Pd/C, indicating the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of the oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C shifts to a higher potential. The current density (mA·mg Pd−1 at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrates that it is a prospective candidate for the cathode of fuel cells operating with alkaline electrolyte.

  3. Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

    Science.gov (United States)

    Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

    2008-12-18

    A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.

  4. Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

    Science.gov (United States)

    Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

    2017-06-01

    The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

  5. Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

    KAUST Repository

    Arashi, Takuya

    2014-09-01

    Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

  6. Investigation of a Pt-Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Castro Luna, A. M.; Bonesi, A.; Triaca, W. E.; Blasi, A. Di; Stassi, A.; Baglio, V.; Antonucci, V.; Arico, A. S.

    2010-01-01

    Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt-Fe/C), with a particle size of about 2-3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt-Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm 2 DEFC single cells at 60 and 80 o C. An improvement in single cell performance was observed in the presence of the Pt-Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm -2 at 2 bar rel. cathode pressure and 80 o C.

  7. Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

    KAUST Repository

    Arashi, Takuya; Seo, Jeongsuk; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-01

    Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

  8. Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

    Science.gov (United States)

    Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

    2017-10-01

    Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

  9. Proton-induced knockout reactions with netron-rich oxygen isotopes at R{sup 3}B

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla [IKP, TU Darmstadt (Germany); GSI (Germany); Collaboration: R3B-Collaboration

    2014-07-01

    Proton-induced knockout reactions are one of the main goal of the experimental program at the future R{sup 3}B (Reactions with Relativistic Radioactive Beams) Experiment at FAIR. It allows us to obtain spectroscopic information about valence and deeply bound single-nucleon states and to study their evolution over a large variation in isospin. Recent studies have shown that the occupancies of loosely bound valence nucleons in neutron- or proton-rich nuclei have a spectroscopic factor close to unity, whereas single-particle strength for deeply bound nucleons is suppressed in isospin asymmetric systems compared to the predictions of the many-body shell model. Further experimental and theoretical studies are needed for a qualitative and quantitative understanding. For this aim a series of measurements have been performed on the complete oxygen isotopic chain using the existing experimental setup LAND/R{sup 3}B at GSI. We present the main scientific goals, the concepts of the experiment and the preliminary results.

  10. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Science.gov (United States)

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  11. A new method to synthesize sulfur-doped graphene as effective metal-free electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhai, Chunyang; Sun, Mingjuan [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Zhu, Mingshan, E-mail: mingshanzhu@yahoo.com [School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Song, Shaoqing [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China); Jiang, Shujuan, E-mail: sjjiang@ecit.edu.cn [School of Chemistry, Biology and Materials Science, East China Institute of Technology, Nanchang 330013 (China)

    2017-06-15

    Highlights: • S doped graphene was facile synthesized by one-pot solvothermal method. • DMSO acted as S source as well as reaction solvent. • S-RGO worked as an efficient metal-free electrocatalyst for ORR. • S-RGO acted as a promising candidate instead of Pt-based catalyst. - Abstract: The exploration of a metal-free catalyst with highly efficient yet low-cost for the oxygen-reduction reaction (ORR) is under wide spread investigation. In this paper, by using dimethyl sulfoxide (DMSO) as S source as well as solvent, we report a new, low-cost, and facile solvothermal route to synthesize S-doped reduced graphene oxide (S-RGO). The existence of S element in the framework of RGO was solidly confirmed by energy-dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized S-RGO can be worked as an efficient metal-free electrocatalyst for ORR. Moreover, compared to commercial Pt/C electrocatalyst, the S-RGO displays superior resistance to crossover effect and stability by evaluating the addition of methanol and CO poisoning experiment. This result not only shows S-RGO as a promising candidate instead of Pt-based catalyst for ORR, but also provides a new approach for the preparation of metal-free electrocatalyst in future.

  12. Reaction of oxygen with γ, δ-ethylenic phenylhydrazones. Model reaction of end-group behavior in phenylhydrazine-accelerated oxidation of natural rubber

    International Nuclear Information System (INIS)

    El Hamdaoui, A.; Reyx, D.; Campistron, I.

    1995-01-01

    An accurate definition of terminal groups of chains in the liquid polymers obtained by the phenylhydrazine-accelerated oxidation of natural rubber is needed. The object of the work was to use model molecules to explore the behavior of γ,δ-ethylenic methylketone phenylhydrazone end-groups in oxidation conditions. We have investigated the synthesis and characterization of models of these hypothetical end-groups, methylketones and phenones 1, their phenylhydrazones 2, the α-(phenyldiazenyl)hydroperoxides 3 resulting from reaction of 2 with oxygen, and the α-(phenyldiazenyl)alcohols 4 as characteristic derivatives of 3 or as models of possible reduced structures in oxidized liquid natural rubber. Three original syntheses of γ,δ-ethylenic ketones were carried out. In the case of γ,δ-ethylenic phenylhydrazones, the oxidation led to the expected α-(phenyldiazenyl)hydroperoxides and to epoxide derivatives of α-(phenyldiazenyl)alcohols 5 and ketones 6. An intramolecular mechanism is proposed. The results are used to predict the possibilities of identification of the corresponding end-groups in liquid rubbers produced in this way. (authors). 16 refs., 12 figs., 3 tabs

  13. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  14. Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

    Science.gov (United States)

    Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

    2006-01-01

    The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

  15. Realization of two light particle correlation experiments: behaviour to very low relative momenta (measurement with a magnetic spectrometer) and influence of the violence of reaction on the emission sources (measured by the neutron detector ORION); Mise en oeuvre de deux experiences de correlations de particules legeres: comportement a tres faibles impulsions relatives (mesure avec un spectrometre magnetique) et influence de la violence de reaction sur les sources d`emission (mesuree avec le detecteur de neutrons ORION)

    Energy Technology Data Exchange (ETDEWEB)

    Sezac, L. [Grenoble-1 Univ., 38 (France)

    1993-01-20

    The correlation measurements between light particles emitted during heavy ion collisions allow to estimate the time-space extension of the emitting sources. This report about the preliminaries of two correlation experiments is split into two parts. The first one describes a test experiment, performed to study the feasibility of a correlation experiment at very low relative momenta with the help of a magnetic spectrometer. The results will allow to determine the still unknown relative effects from the final state interaction and the combination of both Coulomb interaction and quantum statistics. A correlation study without experimental selection of the impact parameter gives unclear answers about the sizes and the temporal characteristics of the emitting systems. The second part analyses the sources of the alpha particles detected in the reaction chamber of the multidetector ORION used as a violence of the reaction filter. The results show that it is possible to consider as a good filter a fast information called `prompt peak` (correlated to the neutron multiplicity detected with ORION). Under such conditions a study of two particle correlations from equilibrated systems with a reasonable statistics becomes thinkable. The results obtained allow to characterize the emitting sources (speed, intensity, temperature) as a function of the violence of the reaction for the system {sup 208} Pb + {sup 93} Nb at 29 MeV/u. (author) 85 refs.

  16. Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy

    International Nuclear Information System (INIS)

    Favaro, Marco; Yang, Jinhui; Nappini, Silvia; Magnano, Elena

    2017-01-01

    Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3 O 4 /Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3 O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3 O 4 catalyst supports this interpretation and reveals that the presence of Co(OH) 2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.

  17. Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Lim, JeongHoon; Shin, Hyeyoung; Kim, MinJoong; Lee, Hoin; Lee, Kug-Seung; Kwon, YongKeun; Song, DongHoon; Oh, SeKwon; Kim, Hyungjun; Cho, EunAe

    2018-04-11

    Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mg Pt -1 ) and a 17.3-fold improvement in the specific activity (2.53 mA cm -2 ) compared to the commercial Pt/C (0.106 A mg Pt -1 and 0.146 mA cm -2 ). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

  18. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  19. 57Fe-Mössbauer spectroscopy and electrochemical activities of graphitic layer encapsulated iron electrocatalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Zhong, Lijie; Frandsen, Cathrine; Mørup, Steen

    2018-01-01

    Graphitic layer encapsulated iron based nanoparticles (G@FeNPs) have recently been disclosed as an interesting type of highly active electrocatalysts for the oxygen reduction reaction (ORR). However, the complex composition of the metal-containing components and their contributions in catalysis r...

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

    DEFF Research Database (Denmark)

    Hu, Yang; Zhao, Xiao; Huang, Yunjie

    2013-01-01

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

  1. Carbon-supported manganese oxide nanoparticles as electrocatalysts for the Oxygen Reduction Reaction (ORR) in alkaline medium: Physical characterizations and ORR mechanism

    Czech Academy of Sciences Publication Activity Database

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2007-01-01

    Roč. 111, č. 3 (2007), s. 1434-1443 ISSN 1932-7447 R&D Projects: GA ČR GA104/02/0731; GA AV ČR KJB4813302 Institutional research plan: CEZ:AV0Z40320502 Keywords : Oxygen Reduction Reaction Subject RIV: CA - Inorganic Chemistry

  2. The Influence of Particle Shape and Size on the Activity of Platinum Nanoparticles for Oxygen Reduction Reaction: A Density Functional Theory Study

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Bligaard, Thomas

    2014-01-01

    We present first principle investigation of the influence of platinum nanoparticle shape and size on the oxygen reduction reaction activity. We compare the activities of nanoparticles with specific shapes (tetrahedron, octahedron, cube and truncated octahedron) with that of equilibrium particle s...

  3. Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)-electrodes: Effects of the heteroatomic junction on the reaction paths

    Science.gov (United States)

    Schulte, E.; Belletti, G.; Arce, M.; Quaino, P.

    2018-05-01

    The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the Osbnd O bond breaking in O2∗ and OOH∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O2∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The Osbnd O scission of the OOH∗ was found to be a barrierless process in Ausbnd Pt systems and nearly barrierless in all Ausbnd Pd systems, implying that the reduction ofO2 in these systems proceeds via the full reduction of O2 to H2O , avoiding H2O2 formation.

  4. 2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

    Science.gov (United States)

    Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

    2016-08-01

    Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

  5. Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soo, Li Ting, E-mail: nicolesoo90@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Loh, Kee Shyuan, E-mail: ksloh@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Mohamad, Abu Bakar, E-mail: drab@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Daud, Wan Ramli Wan, E-mail: wramli@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Wong, Wai Yin, E-mail: waiyin.wwy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); School of Engineering, Taylor' s University' s Lakeside Campus, No. 1, Jalan Taylor' s, 46500 Subang Jaya, Selangor (Malaysia)

    2016-08-25

    A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

  6. Core-Shell Structuring of Pure Metallic Aerogels towards Highly Efficient Platinum Utilization for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Cai, Bin; Hübner, René; Sasaki, Kotaro; Zhang, Yuanzhe; Su, Dong; Ziegler, Christoph; Vukmirovic, Miomir B; Rellinghaus, Bernd; Adzic, Radoslav R; Eychmüller, Alexander

    2018-03-05

    The development of core-shell structures remains a fundamental challenge for pure metallic aerogels. Here we report the synthesis of Pd x Au-Pt core-shell aerogels composed of an ultrathin Pt shell and a composition-tunable Pd x Au alloy core. The universality of this strategy ensures the extension of core compositions to Pd transition-metal alloys. The core-shell aerogels exhibited largely improved Pt utilization efficiencies for the oxygen reduction reaction and their activities show a volcano-type relationship as a function of the lattice parameter of the core substrate. The maximum mass and specific activities are 5.25 A mg Pt -1 and 2.53 mA cm -2 , which are 18.7 and 4.1 times higher than those of Pt/C, respectively, demonstrating the superiority of the core-shell metallic aerogels. The proposed core-based activity descriptor provides a new possible strategy for the design of future core-shell electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Solution-based synthesis and design of late transition metal chalcogenide materials for oxygen reduction reaction (ORR).

    Science.gov (United States)

    Gao, Min-Rui; Jiang, Jun; Yu, Shu-Hong

    2012-01-09

    Late transition metal chalcogenide (LTMC) nanomaterials have been introduced as a promising Pt-free oxygen reduction reaction (ORR) electrocatalysts because of their low cost, good ORR activity, high methanol tolerance, and facile synthesis. Herein, an overview on the design and synthesis of LTMC nanomaterials by solution-based strategies is presented along with their ORR performances. Current solution-based synthetic approaches towards LTMC nanomaterials include a hydrothermal/solvothermal approach, single-source precursor approach, hot-injection approach, template-directed soft synthesis, and Kirkendall-effect-induced soft synthesis. Although the ORR activity and stability of LTMC nanomaterials are still far from what is needed for practical fuel-cell applications, much enhanced electrocatalytic performance can be expected. Recent advances have emphasized that decorating the surface of the LTMC nanostructures with other functional nanoparticles can lead to much better ORR catalytic activity. It is believed that new synthesis approaches to LTMCs, modification techniques of LTMCs, and LTMCs with desirable morphology, size, composition, and structures are expected to be developed in the future to satisfy the requirements of commercial fuel cells. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrochemical kinetics and X-ray absorption spectroscopy investigations of select chalcogenide electrocatalysts for oxygen reduction reaction applications

    International Nuclear Information System (INIS)

    Ziegelbauer, Joseph M.; Murthi, Vivek S.; O'Laoire, Cormac; Gulla, Andrea F.; Mukerjee, Sanjeev

    2008-01-01

    Transition metal-based chalcogenide electrocatalysts exhibit a promising level of performance for oxygen reduction reaction applications while offering significant economic benefits over the state of the art Pt/C systems. The most active materials are based on Ru x Se y clusters, but the toxicity of selenium will most likely limit their embrace by the marketplace. Sulfur-based analogues do not suffer from toxicity issues, but suffer from substantially less activity and stability than their selenium brethren. The structure/property relationships that result in these properties are not understood due to ambiguities regarding the specific morphologies of Ru x S y -based chalcogenides. To clarify these properties, an electrochemical kinetics study was interpreted in light of extensive X-ray diffraction, scanning electron microscopy, and in situ X-ray absorption spectroscopy evaluations. The performance characteristics of ternary M x Ru y S z /C (M = Mo, Rh, or Re) chalcogenide electrocatalysts synthesized by the now-standard low-temperature nonaqueous (NA) route are compared to commercially available (De Nora) Rh- and Ru-based systems. Interpretation of performance differences is made in regards to bulk and surface properties of these systems. In particular, the overall trends of the measured activation energies in respect to increasing overpotential and the gross energy values can be explained in regards to these differences

  9. Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

    2016-01-01

    A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

  10. Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

    Science.gov (United States)

    Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

    2017-12-01

    Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

  11. Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

    Science.gov (United States)

    Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

    2017-07-01

    We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

  12. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  13. A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

    Science.gov (United States)

    Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

    2013-03-01

    This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

  14. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    Science.gov (United States)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  15. Improving biomass-derived carbon by activation with nitrogen and cobalt for supercapacitors and oxygen reduction reaction

    Science.gov (United States)

    Zhang, Man; Jin, Xin; Wang, Linan; Sun, Mengjia; Tang, Yang; Chen, Yongmei; Sun, Yanzhi; Yang, Xiaojin; Wan, Pingyu

    2017-07-01

    Biomass-derived carbon by activation with nitrogen and cobalt (denoted as NPACCo) was prepared by one-pot pyrolysis of pomelo peel with melamine, cobalt nitrate and potassium hydroxide, followed by acid leaching. NPACCo possesses high content of quaternary-N (2.5%) and pyridinic-N (1.7%), co-existences of amorphous and short-range ordered carbon, high specific surface area and pore structure with majority of micropores and small mesopores. As electrode material of supercapacitors, NPACCo exhibits high specific capacitance and good rate capability. At ultrahigh rate of 50 A g-1 (135 mA cm-2), the capacitance of NPACCo remains 246 F g-1, which is 6.3, 1.9 and 3.2 times as high as that of other three materials (PC, PAC and NPAC). The as-assembled symmetric supercapacitor of NPACCo delivers high energy density, high power density and excellent cycling stability. With respect to oxygen reduction reaction (ORR), NPACCo exhibits high onset potential (0.87 V), high half-wave potential (0.78 V), excellent methanol tolerance and low yield of H2O2. The ORR properties of NPACCo are comparable or superior to those of commercial Pt/C. This investigation of pomelo peel-based NPACCo would be valuable for development of both supercapacitor and ORR.

  16. Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

    Science.gov (United States)

    Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

    2018-03-01

    Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

  17. Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

    Science.gov (United States)

    Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

    2018-06-01

    Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Diab Hassan

    2016-09-01

    Full Text Available 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.

  19. Investigation of Supported Pd-Based Electrocatalysts for the Oxygen Reduction Reaction: Performance, Durability and Methanol Tolerance

    Directory of Open Access Journals (Sweden)

    Carmelo Lo Vecchio

    2015-11-01

    Full Text Available Next generation cathode catalysts for direct methanol fuel cells (DMFCs must have high catalytic activity for the oxygen reduction reaction (ORR, a lower cost than benchmark Pt catalysts, and high stability and high tolerance to permeated methanol. In this study, palladium catalysts supported on titanium suboxides (Pd/TinO2n–1 were prepared by the sulphite complex route. The aim was to improve methanol tolerance and lower the cost associated with the noble metal while enhancing the stability through the use of titanium-based support; 30% Pd/Ketjenblack (Pd/KB and 30% Pd/Vulcan (Pd/Vul were also synthesized for comparison, using the same methodology. The catalysts were ex-situ characterized by physico-chemical analysis and investigated for the ORR to evaluate their activity, stability, and methanol tolerance properties. The Pd/KB catalyst showed the highest activity towards the ORR in perchloric acid solution. All Pd-based catalysts showed suitable tolerance to methanol poisoning, leading to higher ORR activity than a benchmark Pt/C catalyst in the presence of low methanol concentration. Among them, the Pd/TinO2n–1 catalyst showed a very promising stability compared to carbon-supported Pd samples in an accelerated degradation test of 1000 potential cycles. These results indicate good perspectives for the application of Pd/TinO2n–1 catalysts in DMFC cathodes.

  20. Novel RuCoSe as non-platinum catalysts for oxygen reduction reaction in microbial fuel cells

    Science.gov (United States)

    Rozenfeld, Shmuel; Schechter, Michal; Teller, Hanan; Cahan, Rivka; Schechter, Alex

    2017-09-01

    Microbial electrochemical cells (MECs) are explored for the conversion of acetate directly to electrical energy. This device utilizes a Geobacter sulfurreducens anode and a novel RuCoSe air cathode. RuCoSe synthesized in selected compositions by a borohydride reduction method produces amorphous structures of powdered agglomerates. Oxygen reduction reaction (ORR) was measured in a phosphate buffer solution pH 7 using a rotating disc electrode (RDE), from which the kinetic current (ik) was measured as a function of potential and composition. The results show that ik of RuxCoySe catalysts increases in the range of XRu = 0.25 > x > 0.7 and y < 0.15 for all tested potentials. A poisoning study of RuCoSe and Pt catalysts in a high concentration acetate solution shows improved tolerance of RuCoSe to this fuel at acetate concentration ≥500 mM. MEC discharge plots under physiological conditions show that ∼ RuCo2Se (sample S3) has a peak power density of 750 mW cm-2 which is comparable with Pt 900 mW cm-2.

  1. Ultrafine and highly disordered Ni 2 Fe 1 nanofoams enabled highly efficient oxygen evolution reaction in alkaline electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang; Song, Junhua; Zhu, Chengzhou; Xu, Gui-Liang; Amine, Khalil; Sun, Chengjun; Li, Xiaolin; Engelhard, Mark H.; Du, Dan; Lin, Yuehe

    2018-02-01

    Nickel iron hydroxides are the most promising non-noble electrocatalysts for oxygen evolution reaction (OER) in alkaline media. By in situ reduction of metal precursors, compositionally controlled three-dimensional (3D) NixFeyB nanofoams (NFs) are synthesized with high surface area and uniformly distributed bimetallic networks. The resultant ultrafine amorphous Ni2Fe1B NFs exhibit extraordinary electrocatalytic performance toward OER and overall water splitting in alkaline media. At a potential as low as 1.42 V (vs. RHE), Ni2Fe1B NFs can deliver a current density of 10 mA/cm2 and show negligible activity loss after 12 hours’ stability test. Even at large current flux of 100 mA/cm2, an ultralow overpotential of 0.27 V is achieved, which is about 0.18 V more negative than benchmark RuO2. Both ex-situ Mӧssbauer spectroscopy and X-ray Absorption Spectroscopy (XAS) reveal a phase separation and transformation for the Ni2Fe1B catalyst during OER process. The evolution of oxidation state and disordered structure of Ni2Fe1B might be a key to the high catalytic performance for OER.

  2. Catalyst Stability Benchmarking for the Oxygen Evolution Reaction: The Importance of Backing Electrode Material and Dissolution in Accelerated Aging Studies.

    Science.gov (United States)

    Geiger, Simon; Kasian, Olga; Mingers, Andrea M; Nicley, Shannon S; Haenen, Ken; Mayrhofer, Karl J J; Cherevko, Serhiy

    2017-09-18

    In searching for alternative oxygen evolution reaction (OER) catalysts for acidic water splitting, fast screening of the material intrinsic activity and stability in half-cell tests is of vital importance. The screening process significantly accelerates the discovery of new promising materials without the need of time-consuming real-cell analysis. In commonly employed tests, a conclusion on the catalyst stability is drawn solely on the basis of electrochemical data, for example, by evaluating potential-versus-time profiles. Herein important limitations of such approaches, which are related to the degradation of the backing electrode material, are demonstrated. State-of-the-art Ir-black powder is investigated for OER activity and for dissolution as a function of the backing electrode material. Even at very short time intervals materials like glassy carbon passivate, increasing the contact resistance and concealing the degradation phenomena of the electrocatalyst itself. Alternative backing electrodes like gold and boron-doped diamond show better stability and are thus recommended for short accelerated aging investigations. Moreover, parallel quantification of dissolution products in the electrolyte is shown to be of great importance for comparing OER catalyst feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. MIL-100-Fe derived N-doped Fe/Fe3C@C electrocatalysts for efficient oxygen reduction reaction

    Science.gov (United States)

    Guo, Dakai; Han, Sancan; Wang, Jiacheng; Zhu, Yufang

    2018-03-01

    N-doped porous Fe/Fe3C@C electrocatalysts were prepared by the pyrolysis of the hexamethylenetetramine (HMT)-incorporated MIL-100-Fe at different temperatures (700-1000 °C) under N2 atmosphere. Rotary evaporation of MIL-100-Fe and HMT solution could make more N-enriched HMT molecules enter into the pores of MIL-100-Fe, thus improving nitrogen contents of the final pyrolyzed samples. All pyrolyzed samples show porous textures with middle specific surface areas. The X-ray photoelectron spectroscopy (XPS) results demonstrate the successful introduction of N atoms into carbon framework. Sample Fe-N2-800 prepared by annealing the precursors with the HMT/MIL-100-Fe weight ratio of 2 at 800 °C exhibits the best electrocatalytic activity towards the oxygen reduction reaction (ORR) in terms of onset potential and current density because of high graphitic N and pyridinic N content. The enwrapped Fe/Fe3C nanoparticles and Fe-Nx active sites in these samples could also boost the ORR activity synergistically. Moreover, sample Fe-N2-800 demonstrates a dominant four electron reduction process, as well as excellent long-term operation stability and methanol crossover resistance. Thus, the N-doped Fe/Fe3C@C composites derived from the HMT-incorporated MIL-100-Fe are promising electrocatalysts to replace Pt/C for ORR in practical applications.

  4. Oxygen Storage Capacity and Oxygen Mobility of Co-Mn-Mg-Al Mixed Oxides and Their Relation in the VOC Oxidation Reaction

    Directory of Open Access Journals (Sweden)

    María Haidy Castaño

    2015-05-01

    Full Text Available Co-Mn-Mg-Al oxides were synthesized using auto-combustion and co-precipitation techniques. Constant ratios were maintained with (Co + Mn + Mg/Al equal to 3.0, (Co + Mn/Mg equal to 1.0 and Co/Mn equal to 0.5. The chemical and structural composition, redox properties, oxygen storage capacity and oxygen mobility were analyzed using X-ray fluorescence (XRF, X-ray diffraction (XRD, Raman spectroscopy, scanning electron microscopy (SEM, temperature-programmed reduction of hydrogen (H2-TPR, oxygen storage capacity (OSC, oxygen storage complete capacity (OSCC and isotopic exchange, respectively. The catalytic behavior of the oxides was evaluated in the total oxidation of a mixture of 250 ppm toluene and 250 ppm 2-propanol. The synthesis methodology affected the crystallite size, redox properties, OSC and oxide oxygen mobility, which determined the catalytic behavior. The co-precipitation method got the most active oxide in the oxidation of the volatile organic compound (VOC mixture because of the improved mobility of oxygen and ability to favor redox processes in the material structure.

  5. Chemisorption of oxygen and subsequent reactions on low index surfaces of β-Mo2C

    DEFF Research Database (Denmark)

    Shi, Xue Rong; Wang, Shengguang; Wang, Jianguo

    2016-01-01

    to the carbon vacancy were identified. We examined the effect of oxygen coverage on the morphology of β-Mo2C by plotting the equilibrium crystal shape. Thermodynamic effect of temperature and reactant or product pressure on the CO/CO2 desorption were investigated. The CO/CO2 desorption is more favorable...... at the saturated oxygen coverage than the low oxygen coverage thermodynamically. The subsequent oxygen diffusion to the carbon vacancy after CO/CO2 desorption may happen depending on the surfaces and oxygen coverage....

  6. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  7. Effect of cathode porosity on the Lithium-air cell oxygen reduction reaction – A rotating ring-disk electrode investigation

    International Nuclear Information System (INIS)

    Seo, Jeongwook; Sankarasubramanian, Shrihari; Singh, Nikhilendra; Mizuno, Fuminori; Takechi, Kensuke; Prakash, Jai

    2017-01-01

    The kinetics of the oxygen reduction reaction (ORR) on the practical air cathode in a Lithium-air cell, which is conventionally composed of porous carbon with or without catalysts supported on it, was investigated. The mechanism and kinetics of the oxygen reduction reaction (ORR) was studied on a porous carbon electrode in an oxygen saturated solution of 0.1 M Lithium bis-trifluoromethanesulfonimide (LiTFSI) in Dimethoxyethane (DME) using cyclic voltammetery (CV) and the rotating ring-disk electrode (RRDE) technique. The oxygen reduction and evolution reactions were found to occur at similar potentials to those observed on a smooth, planar glassy carbon (GC) electrode. The effect of porosity and the resultant increase in surface area were readily observed in the increase in the transient time required for the intermediates to reach the ring and the much larger disk currents (compared to smooth, planar GC) recorded respectively. The RRDE data was analyzed using a kinetic model previously developed by us and the rate constants for the elementary reactions were calculated. The rates constant for the electrochemical reactions were found to be similar in magnitude to the rate constants calculated for smooth GC disks. The porosity of the electrode was found to decrease the rate of desorption of the intermediate and the product and delay their diffusion by shifting it from a Fickian regime in the electrolyte bulk to the Knudsen regime in the film pores. Thus, it is shown that the effect of the electrode porosity on the kinetics of the ORR is physical rather than electrochemical.

  8. Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction

    Science.gov (United States)

    Yan, Kai-Li; Shang, Xiao; Li, Zhen; Dong, Bin; Li, Xiao; Gao, Wen-Kun; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

    2017-09-01

    Designing mixed metal oxides with unique nanostructures as efficient electrocatalysts for water electrolysis has been an attractive approach for the storage of renewable energies. The ternary mixed metal spinel oxides FexNi1-xCo2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, 1) have been synthesized by a facile hydrothermal approach and calcination treatment using nickel foam as substrate. Fe/Ni ratios have been proved to affect the nanostructures of FexNi1-xCo2O, which imply different intrinsic activity for oxygen evolution reaction (OER). SEM images show that Fe0.5Ni0.5Co2O4 has the uniform nanowires morphology with about 30 nm of the diameter and 200-300 nm of the length. The OER measurements show that Fe0.5Ni0.5Co2O4 exhibits the better electrocatalytic performances with lower overpotential of 350 mV at J = 10 mA cm-2. In addition, the smaller Tafel slope of 27 mV dec-1 than other samples with different Fe/Ni ratios for Fe0.5Ni0.5Co2O4 is obtained. The improved OER activity of Fe0.5Ni0.5Co2O4 may be attributed to the synergistic effects from ternary mixed metals especially Fe-doping and the uniform nanowires supported on NF. Therefore, synthesizing Fe-doped multi-metal oxides with novel nanostructures may be a promising strategy for excellent OER electrocatalysts and it also provides a facile way for the fabrication of high-activity ternary mixed metal oxides electrocatalysts.

  9. The Effect of Support on Advanced Pt-based Cathodes towards the Oxygen Reduction Reaction. State of the Art

    International Nuclear Information System (INIS)

    Luo, Yun; Alonso-Vante, Nicolas

    2015-01-01

    Graphical abstract: TOC: This mini-review summarizes advanced Pt catalysts towards enhanced ORR activity and stability. Tunable ORR activity and stability can be achieved in tailoring Pt active center, depending on nature of supporting materials. - Highlights: • Substrate effect leads to ORR activity and stability enhancement of catalyst centers. • Carbon-based materials and oxide-carbon composite influences favorably the Pt electronic environment. • Pt surface modification induced via ligand effect, geometric effect, metal-substrate strong interaction, and interaction of rare earth oxide and Pt surface atoms. • Sources for enhancement of ORR activity and stability were identified. - Abstract: This work summarizes the advanced materials developed by various research groups for improving the stability of platinum (Pt), and Pt-based catalysts center toward the oxygen reduction reaction (ORR) in acid medium. The ORR stability enhancement of Pt catalytic center can be classified according to the different nature of the supporting materials, namely, carbon-, oxide-based-, and oxide-carbon composites. The enhancement and stability of a catalytic center can be related to either its electronic modification induced by a strong interaction with the support, another metal (alloy), or to geometric effects. In addition, other parameters come into play, the size, the morphology of the catalytic center, the temperature, the dispersion, and mass loading, along with the measuring methods. This mini-review mainly focusses on the stability improvement, depending on the substrate nature. This latter can be further modified via functionalization or by the chemical interaction nature between the substrate and catalyst.

  10. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian, E-mail: anjx@163.com; Shen, Yuhua, E-mail: s_yuhua@163.com

    2017-01-30

    Graphical abstract: This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass simultaneously for environment clean. And the typical sample exhibits excellent catalytic performance toward ORR, which is similar to that of commercial Pt/C. - Highlights: • This work demonstrates an example for turning rubbish into valuable products and addresses the disposal issue of waste biomass. • The HPC/RGO composite not only prevents the aggregation of RGO, but also takes advantage of the synergy between them. • This method was accessible, without using any activator, which is an effective strategy for the large scale application of FCs. - Abstract: Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) –doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m{sup 2}/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and

  11. Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

    Science.gov (United States)

    Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

    2016-09-01

    The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

  12. Lignin-derived electrospun carbon nanofiber mats with supercritically deposited Ag nanoparticles for oxygen reduction reaction in alkaline fuel cells

    International Nuclear Information System (INIS)

    Lai, Chuilin; Kolla, Praveen; Zhao, Yong; Fong, Hao; Smirnova, Alevtina L.

    2014-01-01

    Highlights: • Electrospun carbon nanofiber mats were prepared from a natural product of lignin. • The freestanding mats were flexible with BET specific surface area of ∼583 m 2 /g. • The mats were surface-deposited with Ag nanoparticles via the scCO 2 method. • Novel electrocatalytic systems of Ag/ECNFs exhibited high activities towards ORR. - Abstract: Ag nanoparticles (AgNPs) (11, 15, and 25 wt.%) were deposited on the surface of the freestanding and mechanically flexible mats consisting of lignin-derived electrospun carbon nanofibers (ECNFs) by the supercritical CO 2 method followed by the thermal treated at 180 °C. The electrochemical activity of Ag/ECNFs electrocatalyst systems towards oxygen reduction reaction (ORR) was studied in 0.1 M KOH aqueous solution using the rotating disk/rotating ring disk electrode (RDE/RRDE) technique. The SEM, TEM, and XRD results indicated that, the spherical AgNPs were uniformly distributed on the ECNF surface with sizes in the range of 2-10 nm. The electrocatalytic results revealed that, all of the Ag/ECNFs systems exhibited high activity in ORR and demonstrated close-to-theoretical four-electron pathway. In particular, the mass activity of 15 wt.% Ag/ECNFs system was the highest (119 mA mg −1 ), exceeding that of HiSPEC 4100™ commercial Pt/C catalyst (98 mA mg −1 ). This study suggested that the lignin-derived ECNF mats surface-deposited with AgNPs would be promising as cost-effective and highly efficient electrocatalyst for ORR in alkaline fuel cells

  13. Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Niu, Wenhan; Li, Ligui; Liu, Xiaojun; Wang, Nan; Liu, Ji; Zhou, Weijia; Tang, Zhenghua; Chen, Shaowei

    2015-04-29

    Thermally removable nanoparticle templates were used for the fabrication of self-supported N-doped mesoporous carbons with a trace amount of Fe (Fe-N/C). Experimentally Fe-N/C was prepared by pyrolysis of poly(2-fluoroaniline) (P2FANI) containing a number of FeO(OH) nanorods that were prepared by a one-pot hydrothermal synthesis and homogeneously distributed within the polymer matrix. The FeO(OH) nanocrystals acted as rigid templates to prevent the collapse of P2FANI during the carbonization process, where a mesoporous skeleton was formed with a medium surface area of about 400 m(2)/g. Subsequent thermal treatments at elevated temperatures led to the decomposition and evaporation of the FeO(OH) nanocrystals and the formation of mesoporous carbons with the surface area markedly enhanced to 934.8 m(2)/g. Electrochemical measurements revealed that the resulting mesoporous carbons exhibited apparent electrocatalytic activity for oxygen reduction reactions (ORR), and the one prepared at 800 °C (Fe-N/C-800) was the best among the series, with a more positive onset potential (+0.98 V vs RHE), higher diffusion-limited current, higher selectivity (number of electron transfer n > 3.95 at +0.75 V vs RHE), much higher stability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 M KOH solution. The remarkable ORR performance was attributed to the high surface area and sufficient exposure of electrocatalytically active sites that arose primarily from N-doped carbons with minor contributions from Fe-containing species.

  14. 2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon, E-mail: swjeon3380@naver.com

    2017-06-01

    Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H{sub 2}O{sub 2}. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H{sub 2}O{sub 2} yield.

  15. Iridium-decorated palladium-platinum core-shell catalysts for oxygen reduction reaction in proton exchange membrane fuel cell.

    Science.gov (United States)

    Wang, Chen-Hao; Hsu, Hsin-Cheng; Wang, Kai-Ching

    2014-08-01

    Carbon-supported Pt, Pd, Pd-Pt core-shell (Pt(shell)-Pd(core)/C) and Ir-decorated Pd-Pt core-shell (Ir-decorated Pt(shell)-Pd(core)/C) catalysts were synthesized, and their physical properties, electrochemical behaviors, oxygen reduction reaction (ORR) characteristics and proton exchange membrane fuel cell (PEMFC) performances were investigated herein. From the XRD patterns and TEM images, Ir-decorated Pt(shell)-Pd(core)/C has been confirmed that Pt was deposited on the Pd nanoparticle which had the core-shell structure. Ir-decorated Pt(shell)-Pd(core)/C has more positive OH reduction peak than Pt/C, which is beneficial to weaken the binding energy of Pt-OH during the ORR. Thus, Ir-decorated Pt(shell)-Pd(core)/C has higher ORR activity than Pt/C. The maximum power density of H2-O2 PEMFC using Ir-decorated Pt(shell)-Pd(core)/C is 792.2 mW cm(-2) at 70°C, which is 24% higher than that using Pt/C. The single-cell accelerated degradation test of PEMFC using Ir-decorated Pt(shell)-Pd(core)/C shows good durability by the potential cycling of 40,000 cycles. This study concludes that Ir-decorated Pt(shell)-Pd(core)/C has the low Pt content, but it can facilitate the low-cost and high-efficient PEMFC. Copyright © 2013 Elsevier Inc. All rights reserved.

  16. Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

    Science.gov (United States)

    Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

    2017-06-20

    An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

  17. 2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

    International Nuclear Information System (INIS)

    Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon

    2017-01-01

    Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H_2O_2. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H_2O_2 yield.

  18. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jie; Chen, Jinwei, E-mail: jwchen@scu.edu.cn; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin, E-mail: rl.wang@scu.edu.cn

    2016-12-15

    Graphical abstract: A hybrid catalyst was prepared via a quite green and simple method to achieve an one-pot synthesis of the N-doping carbon, tungsten carbides, and iron/cobalt carbides. It exhibited comparable electrocatalytic activity, higher durability and ability to methanol tolerance compared with commercial Pt/C to ORR. - Highlights: • A novel type of hybrid Fe/Co/WC@NC catalysts have been successfully synthesized. • The hybrid catalyst also exhibited better durability and methanol tolerance. • Multiple effective active sites of Fe{sub 3}C, Co{sub 3}C, WC, and NC help to improve catalytic performance. - Abstract: This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe{sub 3}C and Co{sub 3}C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe{sub 3}C, and Co{sub 3}C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

  19. The evolutionary pathway from anoxygenic to oxygenic photosynthesis examined by comparison of the properties of photosystem II and bacterial reaction centers.

    Science.gov (United States)

    Allen, J P; Williams, J C

    2011-01-01

    In photosynthetic organisms, such as purple bacteria, cyanobacteria, and plants, light is captured and converted into energy to create energy-rich compounds. The primary process of energy conversion involves the transfer of electrons from an excited donor molecule to a series of electron acceptors in pigment-protein complexes. Two of these complexes, the bacterial reaction center and photosystem II, are evolutionarily related and structurally similar. However, only photosystem II is capable of performing the unique reaction of water oxidation. An understanding of the evolutionary process that lead to the development of oxygenic photosynthesis can be found by comparison of these two complexes. In this review, we summarize how insight is being gained by examination of the differences in critical functional properties of these complexes and by experimental efforts to alter pigment-protein interactions of the bacterial reaction center in order to enable it to perform reactions, such as amino acid and metal oxidation, observable in photosystem II.

  20. Electro catalyst of platinum prepared by CVD for the oxygen reduction reaction; Electrocatalizador de platino preparado por CVD para la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Garcia C, M.A.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Vargas G, J.R. [IPN, ESIQIE, 07300 Mexico D.F. (Mexico)

    2004-07-01

    In this work it is reported the preparation and characterization of platinum films obtained by the technique of chemical vapor deposition at low pressure, better well-known as LPCVD for their initials in English (Low Pressure Chemical Vapor Deposition). The technique has several industrial applications and in this work it is explored their possible use to prepare applicable electrocatalysts in fuel cells. The films were characterized by XRD, SEM, EDS and they were proven for to determine their acting in the Oxygen reduction reaction (Orr) in sulfuric acid 0.5 M, the results show that the material presents good activity for the reaction in study. (Author)

  1. Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

    Science.gov (United States)

    Freund, F.; Batllo, F.; Leroy, R. C.; Lersky, S.; Masuda, M. M.; Chang, S.

    1991-01-01

    It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

  2. Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

    Science.gov (United States)

    Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

    2018-01-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

  3. Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H2SO4 0.5M

    International Nuclear Information System (INIS)

    Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

    2007-01-01

    Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H 2 SO 4 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

  4. Composite of TiN nanoparticles and few-walled carbon nanotubes and its application to the electrocatalytic oxygen reduction reaction

    KAUST Repository

    Isogai, Shunsuke

    2011-11-30

    Nanoparticles meet nanotubes! Direct synthesis of TiN nanoparticles in a three-dimensional network of few-walled carbon nanotubes (FWCNTs) was achieved by using mesoporous graphitic carbon nitride (C 3N 4) as both a hard template and a nitrogen source. The TiN/FWCNT composite showed high performance for the oxygen reduction reaction in acidic media. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine

    Science.gov (United States)

    Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

    2018-04-01

    Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.

  6. Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction

    International Nuclear Information System (INIS)

    Garcia C, M. A.

    2008-01-01

    In this research, the molecular oxygen reduction reaction (ORR) was investigated on electrocatalysts of Co, Ni, Pt and their alloys CoNi, PtCo, PtNi and PtCoNi by using H 2 SO 4 0.5 and KOH 0.5 M solutions as electrolytes. The electrocatalysts were synthesized by Mechanical Alloying (MA) and Chemical Vapor Deposition (CVD) processes. For MA, metallic powders were processed during 20 h of milling in a high energy SPEX 8000 mill. For CVD, a hot-wall reactor was utilized and Co, Ni and Pt acetilactetonates were used as precursors. Films were deposited at a total pressure of 1 torr and temperatures of 400-450 C. Electrocatalysts were characterized by X-Ray Diffraction (XRD). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Electrocatalysts prepared by mechanical alloying showed a homogeneously dispersed agglomeration of particles with nano metric size. Electrocatalysts obtained by CVD showed, in some cases, non uniform films, with particles of nano metric size, as well. The electrocatalytic performance was evaluated by using the Rotating Disk Electrode technique (RDE). Electrocatalysts prepared by MA showed higher activity than those obtained by CVD. All electrocatalysts were evaluated in alkaline media. Only electrocatalysts containing Pt were evaluated in acid media, because those materials with Co, Ni and their alloys showed instability in acidic media. Most electrocatalysts followed a mechanism for the ORR producing a certain proportion of H 2 O 2 . All electrocatalysts, exhibited a fair or good electrocatalytic activity in comparison with other similar reported materials. It was found that MA and CVD are appropriate processes to prepare electrocatalysts for the ORR with particles of nano metric size and performing with an acceptable catalytic activity. PtCoNi 70-23-7% by MA and PtCoNi-CVD electrocatalysts showed the highest activity in alkaline media, while in acidic electrolyte PtCoNi 70

  7. Electrocatalytic activity and stability of Ag-MnOx/C composites toward oxygen reduction reaction in alkaline solution

    International Nuclear Information System (INIS)

    Wu, Qiumei; Jiang, Luhua; Qi, Luting; Yuan, Lizhi; Wang, Erdong; Sun, Gongquan

    2014-01-01

    Ag-MnO x /C composites were prepared using AgNO 3 and KMnO 4 as the precursors and Vulcan XC-72 as the support. The physical properties of the Ag-MnO x /C composites were investigated via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The activity and the stability of the series of Ag-MnO x /C composites toward the oxygen reduction reaction (ORR) in alkaline media were investigated through the electrochemical techniques. The results show that the main species MnO 2 and Ag 2 O in the fresh sample convert into Mn 3 O 4 and Ag(0), respectively, after the heat treatment in N 2 at 300 °C (Ag-MnO x /C-300). The Ag-MnO x /C-300 sample shows the highest activity toward the ORR, with the half-wave potential of the ORR shifting negatively only 0.035 V compared to that on the commercial 40 wt. % Pt/C (JM). The electron transfer number during the ORR on the Ag-MnO x /C composite increases with the value close to four after the heat treatment at 300 °C, which is mainly attributed to the formation of Ag(0), rather than Mn 3 O 4 . The heat treatment brings about a better catalytic stability of the composite, and no obviously negative shift takes place for the half-wave potential of the ORR on the Ag-MnO x /C-300 composite after 1000 cycles accelerated aging test. The maximum power density of the zinc-air battery with the Ag-MnO x /C-300 air electrode reaches up to 130 mW cm −2 , higher than those based on the Pd/C and Pt/C cathode catalysts, which shows that the Ag-MnO x /C-300 composite is a promising candidate as the catalyst for the air electrode

  8. The roles of polycarboxylates in Cr(VI)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Bo, E-mail: bjiang86upc@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033 (China); Wang, Xianli; Liu, Yukun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wang, Zhaohui [College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Southern Cross GeoScience, Southern Cross University, Lismore, NSW 2480 (Australia); Zheng, Jingtang, E-mail: jtzheng03@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wu, Mingbo, E-mail: wumb@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China)

    2016-03-05

    Highlights: • The formations of SO{sub 4}·{sup −} and OH·, involve in Cr(VI) reduction induced by S(IV). • Affinity of polycarboxylate to Cr(VI) accelerates Cr(VI) reduction rate. • Polycarboxylates can act as electron donors for Cr(VI) reduction retrenching S(IV). • Only oxalate can enhance the formations of SO{sub 4}·{sup −} and OH· in Cr(VI)/S(IV) system. - Abstract: In this study, the effects of polycarboxylates on both Cr(VI) reduction and S(IV) consumption in Cr(VI)/S(IV) system was investigated in acidic solution. Under aerobic condition, the productions of reactive oxygen species (ROS), i.e., SO{sub 4}·{sup −} and OH·, have been confirmed in S(IV) reducing Cr(VI) process by using electron spin resonance and fluorescence spectrum techniques, leading to the excess consumption of S(IV). However, when polycarboxylates (oxalic, citric, malic and tartaric acid) were present in Cr(VI)/S(IV) system, the affinity of polycarboxylates to CrSO{sub 6}{sup 2−} can greatly promote the reduction of Cr(VI) via expanding the coordination of Cr(VI) species from tetrahedron to hexahedron. Besides, as alternatives to S(IV), these polycarboxylates can also act as electron donors for Cr(VI) reduction via intramolecular electron transfer reaction, which is dependent on the energies of the highest occupied molecular orbital of these polycarboxylates. Notably, the variant electron donating capacity of these polycarboxylates resulted in different yield of ROS and therefore the oxidation efficiencies of other pollutants, e.g., rhodamine B and As(III). Generally, this study does not only shed light on the mechanism of S(IV) reducing Cr(VI) process mediated by polycarboxylates, but also provides an escalated, cost-effective and green strategy for the remediation of Cr(VI) using sulfite as a reductant.

  9. The effect of coadsorbed oxygen on the reaction of methanol on Rh(111) and on a rhodium/vanadium surface alloy

    International Nuclear Information System (INIS)

    Schennach, R.; Krenn, G.; Rendulic, K.D.

    2002-01-01

    Full text: Molecular adsorption of methanol can be observed on all transition metal surfaces at low temperatures. Methanol is adsorbed on Rh (111) at 98 K. With increasing methanol exposure first a mono-layer and then multi-layers of methanol are formed at this surface temperature. During heating, desorption of the methanol from physisorbed multi-layers is detected at about 120 K, followed by desorption of methanol from a chemisorbed mono-layer at 170 K. About 50 % of the adsorbed methanol undergoes a dehydrogenation reaction to form hydrogen and carbon monoxide adsorbed on the surface. These reaction products desorb at 300 K and 480 K, respectively. Less than 0.05 monolayers of coadsorbed oxygen increases the amount of methanol that reacts on the surface to about 80 %. Experiments using a Rh/V surface alloy were performed, in order to distinguish between steric and electronic effects in the adsorption and reaction processes. Deposition of 0.3 monolayers of V on the Rh (111) surface leads to the formation of a subsurface alloy, with V atoms in the second atomic layer only. The initial reaction probability was measured as a function of surface temperature and molecular beam energy. A marked difference was found between the two surfaces. On the clean surface methanol adsorption and reaction stops above 198 K, whereas on the alloy surface adsorption and subsequent reaction occurs up to 473 K. The effects of coadsorbed oxygen are similar on both surfaces. The results are discussed in terms of the possible reactions of the adsorbed methanol on the surface. (author)

  10. Direct observation of the dealloying process of a platinum–yttrium nanoparticle fuel cell cathode and its oxygenated species during the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Malacrida, Paolo; Sanchez Casalongue, Hernan G.; Masini, Federico

    2015-01-01

    . It proceeds through the progressive oxidation of alloyed Y atoms, soon leading to the accumulation of Y3+ cations at the cathode. Acid leaching with sulfuric acid is capable of accelerating the dealloying process and removing these Y3+ cations which might cause long term degradation of the membrane. The use...... of APXPS under near operating conditions allowed observing the population of oxygenated surface species as a function of the electrochemical potential. Similar to the case of pure Pt nanoparticles, non-hydrated hydroxide plays a key role in the ORR catalytic process....

  11. Contribution to the study of isotopic exchange of oxygen between nickel oxide and the gases arising from the oxidation reaction of carbon monoxide; Contribution a l'etude de l'echange isotopique de l'oxygene entre l'oxyde de nickel et les gaz de la reaction d'oxydation de l'oxyde de carbone

    Energy Technology Data Exchange (ETDEWEB)

    Bailly, J C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-12-01

    The 3 isotopic reactions of oxygen: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, and C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O between CO, CO{sub 2}, O{sub 2} and NiO are studied using a mass spectrometer. The isotopic gaseous mixtures are prepared from oxygen-18 enriched water. A first order kinetic law has been found for these reactions in the gaseous phase, and the activation energies have been determined. Only CO and CO{sub 2} exchange oxygen, at room temperature, but only with part of the oxide surface. Gaseous O{sub 2} reacts with the whole surface at 250 C, the slow step of the exchange process, in the gaseous phase, being certainly the mobility of oxygen ions on the surface of NiO. (author) [French] Les 3 reactions d'echange isotopique de l'oxygene: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, et C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O entre l'oxyde de carbone, l'oxygene gazeux, le gaz carbonique et l'oxyde de nickel sont etudiees par spectrometrie de masse. Les melanges isotopiques gazeux sont prepares a partir d'une eau enrichie en isotope 18 de l'oxygene. Une loi cinetique du premier ordre a ete trouvee pour les trois reactions d'echange en phase gazeuse, et des energies d'activation de ces reactions ont ete determinees. Seuls CO et CO{sub 2} echangent l'oxygene, des la temperature ambiante, mais avec une fraction seulement de la surface de l'oxyde. O{sub 2} gazeux reagit avec toute la surface du solide a 250 C, l'etape lente du processus d'echange en phase gazeuse etant vraisemblablement liee a la mobilite des ions oxygene superficiels de NiO. (auteur)

  12. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

    International Nuclear Information System (INIS)

    Kelley, D.

    1990-01-01

    The kinetics of the reactions of C 2 H 5 radical with Co(NH 3 ) 5 X 2+ , Ru(NH 3 ) 5 X 2+ , and Co(dmgH) 2 (X) (Y) (X = Br, Cl, N 3 , SCN; Y = H 2 O, CH 3 CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with β-Ni(cyclam) 2+ were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ were studied. Activation parameters were obtained for the unimolecular homolysis of C 2 H 5 Ni(cyclam)H 2 O 2+ . Kinetic and thermodynamic data obtained from these reactions were compared with those for the σ-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ complexes were studied by monitoring the formation of the oxygen insertion product RO 2 Ni(cyclam)H 2 O 2+ . The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs

  13. Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

    Science.gov (United States)

    Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

    2018-06-01

    Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

  14. Electro-deposition of Pd on carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

    CSIR Research Space (South Africa)

    Modibedi, RM

    2014-05-01

    Full Text Available Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions usingthe electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substratesfor the electrodeposition of the metal...

  15. Phenol by direct hydroxylation of benzene with nitrous oxide - role of surface oxygen species in the reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Reitzmann, A.; Klemm, E.; Emig, G. [Erlangen-Nuernberg Univ., Erlangen (Germany). Lehrstuhl fuer Technische Chemie 1; Buchholz, S.A.; Zanthoff, H.W. [Bochum Univ. (Germany). Inst. of Technical Chemistry

    1998-12-31

    Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a pseudo steady state phenol yield. (orig.)

  16. Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes

    International Nuclear Information System (INIS)

    Le Bozec, N.

    2000-01-01

    Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

  17. Analytic study of the chain dark decomposition reaction of iodides - atomic iodine donors - in the active medium of a pulsed chemical oxygen-iodine laser: 1. Criteria for the development of the branching chain dark decomposition reaction of iodides

    International Nuclear Information System (INIS)

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, Aleksandr I; Sorokin, Vadim N

    2009-01-01

    The scheme of chemical processes proceeding in the active medium of a pulsed chemical oxygen-iodine laser (COIL) is analysed. Based on the analysis performed, the complete system of differential equations corresponding to this scheme is replaced by a simplified system of equations describing in dimensionless variables the chain dark decomposition of iodides - atomic iodine donors, in the COIL active medium. The procedure solving this system is described, the basic parameters determining the development of the chain reaction are found and its specific time intervals are determined. The initial stage of the reaction is analysed and criteria for the development of the branching chain decomposition reaction of iodide in the COIL active medium are determined. (active media)

  18. Study of the oxygen reduction reaction using Pt-Rare earths (La, Ce, Er) electrocatalysts for application of PEM fuel cells

    International Nuclear Information System (INIS)

    Gomes, Thiago Bueno

    2013-01-01

    The complexity of the oxygen reduction reaction (ORR) and its potential losses make it responsible for the most part of efficiency losses at the Fuel Cells. For this reaction the electrocatalyst witch is most appropriated and shows better performance is platinum, a noble metal that elevates the cost, raising barriers for Fuel Cells technology to enter the market. First this work focuses on reducing the amount of platinum used in the cathode, by being replaced by rare earths. The most common methods of synthesis involves a large amount of steps and this work proposed to prepare the electrocatalyst through a simpler way that would not take so many steps and time to be done. Using an ultrasound mixer the electrocatalyst was prepared mixing platinum supported on carbon black and the rare earths lanthanum, cerium and erbium oxides to be applied in a half-cell study of the ORR. The Koutecky-Levich plots shows that among the electrocatalysts prepared the Pt80Ce20/C had the catalytic activity close to the commercial BASF platinum on carbon black, suggesting that the reaction was taken by the 4-electron path. As found in some works in literature, among the rare earth used to study the ORR, cerium is the one witch shows the better performance because it is able to store and provide oxygen. This feature is of great interest for the ORR because this reaction is first order to the oxygen concentration. Results show that is possible to reduce the amount of platinum maintaining the same electrocatalyst activity. (author)

  19. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Lewera, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw (Poland); Inukai, J. [Clean Energy Research Center, University of Yamanashi, 7-32 Miyamae-cho, Kofu 400-0006 (Japan); Zhou, W.P. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Cao, D. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Duong, H.T. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States); Alonso-Vante, N. [Laboratory of Electrocatalysis, UMR-CNRS 6503, University of Poitiers, F-86022 Poitiers (France)]. E-mail: Nicolas.Alonso.Vante@univ-poitiers.fr; Wieckowski, A. [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801 (United States)]. E-mail: andrzej@scs.uiuc.edu

    2007-05-10

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO{sub 2} or SO {sub x} forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples.

  20. Chalcogenide oxygen reduction reaction catalysis: X-ray photoelectron spectroscopy with Ru, Ru/Se and Ru/S samples emersed from aqueous media

    International Nuclear Information System (INIS)

    Lewera, A.; Inukai, J.; Zhou, W.P.; Cao, D.; Duong, H.T.; Alonso-Vante, N.; Wieckowski, A.

    2007-01-01

    Oxygen reduction Ru/Se and Ru/S fuel cell surface chalcogenide catalysts were prepared via chemical reaction of reduced Ru nanoparticles with selenium and sulfur in xylenes [D. Cao, A. Wieckowski, J. Inukai, N. Alonso-Vante, J. Electrochem. Soc. 153 (2006) A869]. The chalcogenide samples - as well as the starting chalcogens-free Ru nanoparticle material - were immobilized on a gold disk for X-ray Photoelectron Spectroscopy (XPS) characterization. While we found oxygen in most of the samples, predominantly from Ru oxides, we conclude that the oxygen on Ru/S may be located in subsurface sites: the subsurface oxygen. We also found that the transformation of the oxidized Ru black to metallic Ru required intensive electrochemical treatment, including hydrogen evolution. In contrast, five cyclic voltammetric scans in the potential range from 0.00 and 0.75 V versus RHE were sufficient to remove the oxygen forms from Ru/Se and, to a large extent, from Ru/S. We therefore conclude that Ru metal is protected against oxidation to Ru oxides by the chalcogens additives. The voltammetric treatment in the 0.00 and 0.75 V range also removed the SeO 2 or SO x forms leaving anionic/elemental Se or S on the surface. Upon larger amplitude voltammetric cycling, from 0.00 to 1.20 V versus RHE, both Se and S were dissolved and the dissolution process was coincidental with the oxygen growth in/on the Ru samples

  1. Facile synthesis of pyrite-type binary nickel iron diselenides as efficient electrocatalyst for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chi, Jing-Qi; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liang, Fei [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Li, Xiao; Liu, Yan-Ru; Yan, Kai-Li [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Gao, Wen-Kun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang, E-mail: cgliu@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-04-15

    Highlights: • Binary pyrite-type Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC was prepared by a facile two-step process. • The effect of Ni/Fe (Ni{sub x}Fe{sub 1-x}Se{sub 2} x = 0, 0.2, 0.5, 0.8, 1) on OER was investigated. • Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC (x = 0.5) possesses the better electrocatalytic activity for OER. • The enhanced activity may be attributed to binary Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} and CFC support. - Abstract: Pyrite-type binary nickel iron diselenides (Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}) supported on carbon fiber cloth (CFC) as electrocatalysts for oxygen evolution reaction (OER) have been prepared by a facile two-step process. Firstly, binary Ni{sub 0.5}Fe{sub 0.5} hydroxide nanosheets have been electrodeposited on CFC. Secondly, a solvothermal selenization process has been used to convert Ni{sub 0.5}Fe{sub 0.5}/CFC into Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC. XRD shows that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} on CFC has the typically octahedral crystalline. XPS proves the existence and valence of Ni, Fe and Se. SEM images show that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} has novel pyrite-type octahedral morphology with uniform size and good dispersion on the surface of CFC. SEM elemental mapping images confirm the good distribution of Ni, Fe, Se element on CFC. TEM and SAED provide the clear diffraction rings of octahedral Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}, which is consistent with the results of XRD. Furtherly, the effect of different ratio of Ni/Fe (Ni{sub x}Fe{sub 1-x}Se{sub 2} x = 0, 0.2, 0.5, 0.8, 1) on OER performances has been systematically investigated. The electrochemical measurements results show that Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC (x = 0.5) possesses the better electrocatalytic activity with the lower overpotential, Tafel slope and long-term stability than other samples. The enhanced activity of Ni{sub 0.5}Fe{sub 0.5}Se{sub 2}/CFC may be attributed to the intrinsic activity of binary Ni{sub 0.5}Fe{sub 0.5}Se{sub 2} and faster electron

  2. N,2,3,4-Tetrasubstituted Pyrrolidines through Tandem Lithium Amide Conjugate Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Kafka, František; Pohl, Radek; Císařová, I.; Mackman, R.; Bahador, G.; Jahn, Ullrich

    2016-01-01

    Roč. 2016, č. 22 (2016), s. 3862-3871 ISSN 1434-193X R&D Projects: GA ČR GA13-40188S Grant - others:COST(XE) CM1201 Institutional support: RVO:61388963 Keywords : tandem reactions * nitrogen heterocycles * Michael addition * radical reactions * cyclization * enolates Subject RIV: CC - Organic Chemistry Impact factor: 2.834, year: 2016

  3. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    Science.gov (United States)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  4. Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

    Science.gov (United States)

    Sad, María E; Neurock, Matthew; Iglesia, Enrique

    2011-12-21

    This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

  5. Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

    Science.gov (United States)

    Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

    2018-04-04

    Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

  6. Stability of a Cu0.7Co2.3O4 electrode during the oxygen evolution reaction for alkaline anion-exchange membrane water electrolysis

    Science.gov (United States)

    Kang, Kyoung Eun; Kim, Chi Ho; Lee, Myung Sup; Jung, Chang Wook; Kim, Yang Do; Lee, Jae Ho

    2018-01-01

    The electrode materials for oxygen evolution, especially non-platinum group metal oxides, have attracted increasing attention. Among the spinel-type transition metal oxides, Cu0.7Co2.3O4 powders were evaluated as a potential replacement for expensive dimensionally stabilized anode materials. Cu0.7Co2.3O4 powder for use as an electrode material for oxygen evolution in an alkaline anion-exchange membrane water electrolyzer was prepared using a thermal decomposition method. The Cu0.7Co2.3O4 powders heat-treated at 250 °C exhibited the same X-ray diffraction patterns without any secondary phases as the Co3O4 spinel structure did. The Cu0.7Co2.3O4 powders heat-treated at 250 °C for 30 minutes showed the smallest mean particle size of approximately 376 nm with the powders having a homogeneous shape and size distribution. The fine powders with a relatively homogeneous size distribution showed a higher current density during the oxygen evolution reaction. The lifetime of the Cu0.7Co2.3O4 electrode was relatively long at a low current density, but was quickly shortened due to physical detachment of the Cu0.7Co2.3O4 powders as the current density was increased. This study showed that the efficiency and the stability of Cu0.7Co2.3O4 powders during the oxygen evolution reaction were related directly to the active electrode area.

  7. Carbon-14 studies on the role of oxygen-containing compounds in the reaction mechanism of the Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Aksoy, H.A.

    1975-01-01

    In this work the behaviour of organic oxygen compounds has been studied in the reaction mechanism of Fischer-Tropsch synthesis using the tracer method. As an oxygen carrying tracer materials i-propanole (2- 14 C), acetone (2- 14 C) and ethanole (1- 14 C) have been added to the synthesis gas. The synthesis experiments are performed under standard conditions: The synthesis products are separated in suitable fractions and then studied by gas- and radio-gaschromatography. As a result the C-number distributions of the synthesis products are obtained as a function of concentration (weight %, mol %) and radioactivity (activity %). On this basis the relative molar activities have been calculated for certain compounds and fractions. Adding i-propanole- 14 C a great part of the tracer compound is transformed to acetone- 14 C, however adding acetone- 14 C to the synthesis gas a large amount of i-propanole- 14 C is produced. The main hydrocarbon reaction product from i-propanol and acetone is propane. Besides propane also propene is produced with equal molar radioactivity. This indicates that the formation of adsorbed oxygen compounds, as they may also be produced by chemisorption from alcohols or carbonyle compounds, is the first step in the formation of hydrocarbons by hydrogenolytic separation of oxygen. Comparing the results obtained with ethanole- 14 C and i-propanole- 14 C as a tacer material, for ethane an essentially lower molar activity is obtained when adding ethanole- 14 C compared with propane when adding i-propanole- 14 C. This corresponds with a particularly low desorption probability at the C 2 -hydrocarbon level. (orig./HK) [de

  8. Comparison between the Oxygen Reduction Reaction Activity of Pd5Ce and Pt5Ce

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Zheng, Jian; Rizzi, Gian Andrea

    2015-01-01

    A set of electrochemical and X-ray spectroscopy measurements have been used conjointly with density functional theory (DFT) simulations to study the activity and stability of Pd5Ce for the oxygen reduction reaction. A polycrystalline Pd5Ce rod has been selected as a model catalyst to test if resu......-Pd5Ce is more facile, requires less atom rearrangement, than transformation from Pt5Ce to Pt3Ce, which might explain the kinetic stability of Pt5Ce at low temperatures....

  9. Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

    Science.gov (United States)

    Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

    2011-01-01

    The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

  10. l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

    2017-10-15

    In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like shape for oxygen evolution reaction with enhanced catalytic activity

    Directory of Open Access Journals (Sweden)

    Tao Ding

    2016-01-01

    Full Text Available Self-assembly growth of alloyed NiPt nanocrystals with holothuria-like wire shape has been achieved via a facile and moderate hydrothermal process at 120 °C for 1 h from the reaction of nickel nitrate and chloroplatinic acid in alkaline solution in the presence of ethanediamine and hydrazine hydrate. The holothuria-like alloyed NiPt wires are Ni-rich in composition (Ni23.6Pt and uniform in diameter with many tiny tips outstretched from the wires surface. The holothuria-like wires are assembled from granular subunits with the assistance of capping molecular of ethanediamine and the wires display an improved oxygen evolution reaction catalytic activity.

  12. Hydrothermal synthesis of Fe_2O_3/polypyrrole/graphene oxide composites as highly efficient electrocatalysts for oxygen reduction reaction in alkaline electrolyte

    International Nuclear Information System (INIS)

    Ren, Suzhen; Ma, Shaobo; Yang, Ying; Mao, Qing; Hao, Ce

    2015-01-01

    Graphical abstract: Fe_2O_3/polypyrrole/graphene oxide electrocatalysts for oxygen reduction reaction (ORR) are successfully prepared through one simple polypyrrole-assisted hydrothermal method and possess very high ORR activity and are able to selectively reduce O_2 to water through the four-electron transfer reaction mechanism in alkaline electrolyte. - Abstract: Advantages in low cost, and excellent catalytic activity of Fe-based nanomaterials dispersed on nitrogen-doped graphene supports render them to be good electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Here, Fe_2O_3/polypyrrole/graphene oxide (Fe_2O_3/Ppy/GO) composites with the Fe_2O_3 embedded in the Ppy modified GO are synthesized using hydrothermal method. With an optimal iron atom content ratio of 1.6% in graphene oxide and heat treatment at 800 °C, the Fe_2O_3/Ppy/GO exhibited enhanced catalytic performance for ORR with the onset potential of −0.1 V (vs SCE), cathodic potential of −0.24 V (vs SCE), an approximate 4e"− transfer process in O_2-saturated 0.1 M KOH, and superior stability that only reduced 5% catalytic activity after 5000 cycles. The decisive factors in improving the electrocatalytic and durable performance are the intimate and large contact interfaces between nanocrystallines of Fe_2O_3 and Ppy/GO, in addition to the high electron withdrawing/storing ability and the high conductivity of GO doped with nitrogen from Ppy during the hydrothermal reaction. The Fe_2O_3/Ppy/GO showed significantly improved ORR properties and confirmed that Fe-N-C-based electrocatalysts played a key role in fuel cells.

  13. Synergy of Cobalt and Silver Microparticles Electrodeposited on Glassy Carbon for the Electrocatalysis of the Oxygen Reduction Reaction: An Electrochemical Investigation

    Directory of Open Access Journals (Sweden)

    Claudio Zafferoni

    2015-08-01

    Full Text Available The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR, yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break the O–O bond of molecular oxygen, thus accelerating the first step of the reduction mechanism. At the same time, research is to further reduce the catalyst’s cost, reducing the amount of Ag, which, even though being much less expensive than Pt, is still a noble metal. From this point of view, using a small amount of Ag together with an inexpensive material, such as graphite, represents a good compromise. The aim of this work was to verify if the synergic effects are still operating when very small amounts of cobalt (2–10 μg·cm−2 are added to the microparticles of silver electrodeposited on glassy carbon, described in a preceding paper from us. To better stress the different behaviour observed when cobalt and silver are contemporarily present in the deposit, the catalytic properties of cobalt alone were investigated. The analysis was completed by the Levich plots to evaluate the number of electrons involved and by Tafel plots to show the effects on the reaction mechanism.

  14. Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes at the R3B-LAND setup

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla; Aumann, Thomas [TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerce (United States); Paschalis, Stefanos [TU Darmstadt, Darmstadt (Germany); Nociforo, Chiara [GSI, Darmstadt (Germany); Collaboration: R3B-Collaboration

    2016-07-01

    Recent experiments have showed a reduction of spectroscopic strengths of about 60-70% for stable nuclei. When going to driplines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with a secondary beam {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  15. Heterojunction-Assisted Co3 S4 @Co3 O4 Core-Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions.

    Science.gov (United States)

    Yan, Yibo; Li, Kaixin; Chen, Xiaoping; Yang, Yanhui; Lee, Jong-Min

    2017-12-01

    Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CRR). A heterojunction prototype on Co 3 S 4 @Co 3 O 4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co 3 O 4 core and n-type Co 3 S 4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO 2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

    Science.gov (United States)

    He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

    2017-12-13

    We report on the new facile synthesis of mesoporous NiO/MnO 2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm -2 for the OER and -3 mA cm -2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

  17. Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

    2017-01-01

    Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  18. Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

    2017-08-01

    Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

  19. Molecule-Level g-C3N4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions

    KAUST Repository

    Zheng, Yao

    2017-02-21

    Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C3N4) coordinated transition metals (M-C3N4) as a new generation of M-N/C catalysts for these oxygen electrode reactions. As a proof-of-concept example, we conducted theoretical evaluation and experimental validation on a cobalt-C3N4 catalyst with a desired molecular configuration, which possesses comparable electrocatalytic activity to that of precious metal benchmarks for the ORR and OER in alkaline media. The correlation of experimental and computational results confirms that this high activity originates from the precise M-N2 coordination in the g-C3N4 matrix. Moreover, the reversible ORR/OER activity trend for a wide variety of M-C3N4 complexes has been constructed to provide guidance for the molecular design of this promising class of catalysts.

  20. Enhanced Oxygen Reduction Reaction by In Situ Anchoring Fe2N Nanoparticles on Nitrogen-Doped Pomelo Peel-Derived Carbon

    Directory of Open Access Journals (Sweden)

    Yiqing Wang

    2017-11-01

    Full Text Available The development of effective oxygen electrode catalysts for renewable energy technologies such as metal-air batteries and fuel cells remains challenging. Here, we prepared a novel high-performance oxygen reduction reaction (ORR catalyst comprised of Fe2N nanoparticles (NPs in situ decorated over an N-doped porous carbon derived from pomelo peel (i.e., Fe2N/N-PPC. The decorated Fe2N NPs provided large quantities of Fe-N-C bonding catalytic sites. The as-obtained Fe2N/N-PPC showed superior onset and half-wave potentials (0.966 and 0.891 V, respectively in alkaline media (0.1 M KOH compared to commercial Pt/C through a direct four-electron reaction pathway. Fe2N/N-PPC also showed better stability and methanol tolerance than commercial Pt/C. The outstanding ORR performance of Fe2N/N-PPC was attributed to its high specific surface area and the synergistic effects of Fe2N NPs. The utilization of agricultural wastes as a precursor makes Fe2N/N-PPC an ideal non-precious metal catalyst for ORR applications.

  1. Vertically oriented CoO@FeOOH nanowire arrays anchored on carbon cloth as a highly efficient electrode for oxygen evolution reaction

    International Nuclear Information System (INIS)

    Wang, Yin; Ni, Yuanman; Liu, Bing; Shang, Shuxia; Yang, Song; Cao, Minhua; Hu, Changwen

    2017-01-01

    Graphical abstract: Three-dimensional CoO@FeOOH nanowire arrays grown on carbon cloth were constructed, which exhibit good electrocatalytic activity towards OER in alkaline solution. Display Omitted -- Abstract: Developing high efficiency electrocatalysts for electrocatalytic oxygen evolution reaction (OER) is a key to water splitting. In this work, we demonstrate the preparation of CoO@FeOOH core-shell nanowire (NWs) grown on three-dimensional (3D) carbon cloth (CC@CoO@FeOOH-NWAs) by hydrothermal method followed by electrodeposition process as well as its highly efficient activity for water oxidation. In this hybrid structure, CoO@FeOOH-NWs with an average diameter of 100 nm is vertically grown on the surface of carbon fibers of the carbon cloth. The combination of CoO@FeOOH catalyst with good electron transfer substrate exhibits exceptionally good electrocatalytic activity and long-term durability towards oxygen evolution reaction in alkaline solution. It needs an overpotential as low as 255 mV to achieve the current density of 10 mA cm −2 , with a Tafel slope of 82 mV dec −1 and also exhibits a good stability in 20 h. In addition, the nanowire array structure is well retained after the durability test with high current density of 50 mA cm −2 . Our strategy provides a guide to rational design of micro-structures of the materials to achieve their high performance.

  2. Template-free synthesis of hierarchical yolk-shell Co and N codoped porous carbon microspheres with enhanced performance for oxygen reduction reaction

    Science.gov (United States)

    Chao, Shujun; Cui, Qian; Wang, Kui; Bai, Zhengyu; Yang, Lin; Qiao, Jinli

    2015-08-01

    The structures and compositions of materials have important influences on their performance. Herein, hierarchically structured yolk-shell Co and N codoped porous carbon microspheres (YS-Co/N-PCMs) have been successfully synthesized by using low-cost melamine, formaldehyde and cobalt acetate as raw materials via a facile template-free hydrothermal method and a subsequent pyrolysis. The formation process of the yolk-shell precursor is systematically investigated, involving a morphological evolution process from solid microspheres, ultrathin and wrinkled shells wrap, to yolk-shell structure formation. More importantly, the unique structure combines the favorable features towards oxygen reduction reaction (ORR), such as high surface area, sufficient Co-Nx and graphitic N active sites and suitable pore structures. As a result, the YS-Co/N-PCMs catalyst shows high catalytic activity for ORR in alkaline media for fuel cells, which not only outperforms commercial Pt-based catalysts in terms of resistance to methanol crossover and long-time stability, but is also better than many non-precious metal doped carbon-based catalysts reported previously. In addition, the YS-Co/N-PCMs catalyst also has high catalytic activity toward oxygen evolution reaction (OER). Therefore, the YS-Co/N-PCMs catalyst may serve as a promising alternative to Pt/C catalyst for ORR and OER in alkaline media.

  3. CaCu3Ti4O12: A Bifunctional Perovskite Electrocatalyst for Oxygen Evolution and Reduction Reaction in Alkaline Medium

    International Nuclear Information System (INIS)

    Kushwaha, H.S.; Halder, Aditi; Thomas, P.; Vaish, Rahul

    2017-01-01

    Highlights: •A cost effective double perovskite CaCu 3 Ti 4 O 12 have been synthesized using oxalate precursor method. •CCTO electrocatalyst exhibit enhanced bifunctional electrocatalytic activities. •CCTO electrocatalyst have lower overpotential and higher mass activity as compared to noble metal oxide and well-known perovskite catalysts. •Electrochemical impedance spectroscopy investigations of oxygen reactions on perovskite surfaces. -- Abstract: Perovskite oxides are prominent materials as the bifunctional electrocatalysts for both oxygen reduction/evolution reactions (ORR/OER) for the electrochemical energy conversion and storage using regenerative fuel cells and rechargeable metal-air batteries. In this work, a quadruple perovskite CaCu 3 Ti 4 O 12 has been synthesized oxalate precursor route. X-ray diffraction pattern shows phase purity of the synthesized electrocatalyst. The synthesized CCTO electrocatalyst have crystallite size of 26 nm. Electrochemical investigations reveal that CCTO exhibit efficient catalytic activity. More interestingly, an extremely high OER activity is observed for CCTO electrocatalysts which is found superior than similar class of perovskites. Additionally, CCTO shows efficient ORR activity with an onset potential of 0.83 V which is better than that of Pt/C catalyst (≈0.94 V). These results demonstrate the significant potential of CCTO perovskite as a bifunctional electrode material for alkaline fuel cells and metal-air batteries.

  4. Crystal structure and surface characteristics of Sr-doped GdBaCo2O6−δ double perovskites: oxygen evolution reaction and conductivity

    KAUST Repository

    Pramana, Stevin S.

    2017-12-04

    A cheap and direct solution towards engineering better catalysts through identification of novel materials is required for a sustainable energy system. Perovskite oxides have emerged as potential candidates to replace the less economically attractive Pt and IrO2 water splitting catalysts. In this work, excellent electrical conductivity (980 S cm−1) was found for the double perovskite of composition GdBa0.6Sr0.4Co2O6−δ which is consistent with a better oxygen evolution reaction activity with the onset polarisation of 1.51 V with respect to a reversible hydrogen electrode (RHE). GdBa1−xSrxCo2O6−δ with increasing Sr content was found to crystallise in the higher symmetry tetragonal P4/mmm space group in comparison with the undoped GdBaCo2O6−δ which is orthorhombic (Pmmm), and yields higher oxygen uptake, accompanied by higher Co oxidation states. This outstanding electrochemical performance is explained by the wider carrier bandwidth, which is a function of Co–O–Co buckling angles and Co–O bond lengths. Furthermore the higher oxygen evolution activity was observed despite the formation of non-lattice oxides (mainly hydroxide species) and enrichment of alkaline earth ions on the surface.

  5. Crystal structure and surface characteristics of Sr-doped GdBaCo2O6−δ double perovskites: oxygen evolution reaction and conductivity

    KAUST Repository

    Pramana, Stevin S.; Cavallaro, Andrea; Li, Cheng; Handoko, Albertus D.; Chan, Kuang Wen; Walker, Robert J.; Regoutz, Anna; Herrin, Jason S.; Yeo, Boon Siang; Payne, David J.; Kilner, John A.; Ryan, Mary P.; Skinner, Stephen J.

    2017-01-01

    A cheap and direct solution towards engineering better catalysts through identification of novel materials is required for a sustainable energy system. Perovskite oxides have emerged as potential candidates to replace the less economically attractive Pt and IrO2 water splitting catalysts. In this work, excellent electrical conductivity (980 S cm−1) was found for the double perovskite of composition GdBa0.6Sr0.4Co2O6−δ which is consistent with a better oxygen evolution reaction activity with the onset polarisation of 1.51 V with respect to a reversible hydrogen electrode (RHE). GdBa1−xSrxCo2O6−δ with increasing Sr content was found to crystallise in the higher symmetry tetragonal P4/mmm space group in comparison with the undoped GdBaCo2O6−δ which is orthorhombic (Pmmm), and yields higher oxygen uptake, accompanied by higher Co oxidation states. This outstanding electrochemical performance is explained by the wider carrier bandwidth, which is a function of Co–O–Co buckling angles and Co–O bond lengths. Furthermore the higher oxygen evolution activity was observed despite the formation of non-lattice oxides (mainly hydroxide species) and enrichment of alkaline earth ions on the surface.

  6. DEVELOPMENT OF REACTION-DRIVEN IONIC TRANSPORT MEMBRANES (ITMs) TECHNOLOGY: PHASE IV/BUDGET PERIOD 6 “Development of ITM Oxygen Technology for Integration in IGCC and Other Advanced Power Generation Systems”

    Energy Technology Data Exchange (ETDEWEB)

    David, Studer

    2012-03-01

    Air Products and Chemicals, along with development participants and in association with the U.S. Department of Energy, has made substantial progress in developing a novel air separation technology. Unlike conventional cryogenic processes, this method uses high-temperature ceramic membranes to produce high-purity oxygen. The membranes selectively transport oxygen ions with high flux and infinite theoretical selectivity. Reaction-driven ceramic membranes are fabricated from non-porous, multi-component metallic oxides, operate at temperatures typically over 700°C, and have exceptionally high oxygen flux and selectivity. Oxygen from low-pressure air permeates as oxygen ions through the ceramic membrane and is consumed through chemical reactions, thus creating a chemical driving force that pulls oxygen ions across the membrane at high rates. The oxygen reacts with a hydrocarbon fuel in a partial oxidation process to produce a hydrogen and carbon monoxide mixture – synthesis gas. This project expands the partial-oxidation scope of ITM technology beyond natural gas feed and investigates the potential for ITM reaction-driven technology to be used in conjunction with gasification and pyrolysis technologies to provide more economical routes for producing hydrogen and synthesis gas. This report presents an overview of the ITM reaction-driven development effort, including ceramic materials development, fabrication and testing of small-scale ceramic modules, ceramic modeling, and the investigation of gasifier integration schemes

  7. Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO2 films] revealed that MnO2 film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO2 films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO2 films showed that the Fe(III)-doped RuO2-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO2 films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H2O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb10Sn20Ti70, Cu63Ni37 and Cu25Ni75 alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu63Ni37 alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO3- at the Cu-Ni alloy electrode is superior to

  8. [Study of blood oxygen saturation, heart rate changes and plateau reaction of the Antarctic Kunlun station investigation team in different plateau environments].

    Science.gov (United States)

    Zhao, Shun-yun; Wu, Xin-min; Guo, Ya-min; Zhang, Shu-shun; An, Yan-ming; Li, Bing; Wang, Hao

    2013-06-11

    To explore the blood oxygen saturation and heart rate changes of the Antarctic explorers. During August 2010 to April 2011, the changes in blood oxygen saturation, heart rate and plateau reaction of 16 Antarctic expedition team in different plateau environments (Tibetan plateau versus Antarctic plateau) were monitored with the noninvasive pulse oximeter MD300-C. The extent of acute mountain sickness was determined according to the Lake Louise Consensus acute mountain reaction symptom scores and judgment method. The changes of blood oxygen saturation, heart rate at different altitudes of 110, 3650, 4300 m (96.8% ± 1.2%,89.1% ± 1.2%, 86.1% ± 2.0%, (75.0 ± 5.4) times/min, (104.0 ± 4.3) times/min, (113.0 ± 5.2) times/min,F = 214.155, 240.088,both P rate at different altitudes of 2000, 2500, 3000, 3500 and 4087 m(91.9% ± 1.3%,90.5% ± 1.3%,87.6% ± 1.4%,85.0% ± 1.8%,81.5% ± 2.2%, (85.9 ± 3.2) times/min, (90.6 ± 2.8) times/min, (97.8 ± 4.1) times/min, (102.0 ± 3.4) times/min, (106.3 ± 3.9) times/min, F = 105.418, 90.174, both P rate were both correlated with the risk of altitude sickness (r = -0.446 and 0.565, both P rate of the Antarctic explorers. And with the increases of altitude, the risk of altitude sickness gradually increases.

  9. A Moessbauer spectroscopic study of corrosion related reactions in the iron-hydrogen fluoride-water-oxygen system

    International Nuclear Information System (INIS)

    Crouse, P.L.

    1989-03-01

    The results of a study of a number of corrosion related reactions in the Fe-HF-H 2 O-O2 system are presented. The primary techniques used were transmission and conversion electron Moessbauer spectroscopy. Conversion electron Moessbauer spectra were recorded at very low γ-photon glancing angles and at normal incidence. Depth profiles of surface layers were obtained by recording spectra at different glancing angles. The initial product which forms when an iron surface is exposed to the vapour of azeotropic hydrofluoric acid was identified as FeF 25 ·47H 2 O. With increasing film thickness, a product, identified as non-stoichiometric Fe 2 F 5 ·7H 2 O, was shown to occur. A thermodynamic analysis of the system is presented which shows FeF 3 ·3H 2 O to be the most stable compound under the experimental conditions used, and suggests a stepwise reaction sequence in which FeF 2 ·4H 2 O forms first, followed by Fe 2 F 5 ·7H 2 O and finally FeF 3 ·3H 2 O. Results obtained in a gravimetric study reveal the rate of reaction of metallic iron with the azeotropic vapour to be controlled by the rate of diffusion of the gaseous species through the product layer. In the case of the reactions with the vapour of higher dilutions of aqueous HF, the chemical reaction between the iron substrate and the gaseous species is rate controlling. 86 refs., 61 figs., 14 tabs

  10. Reactions of plutonium dioxide with water and oxygen-hydrogen mixtures: Mechanisms for corrosion of uranium and plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, John M.; Allen, Thomas H.; Morales, Luis A.

    1999-06-18

    Investigation of the interactions of plutonium dioxide with water vapor and with an oxygen-hydrogen mixture show that the oxide is both chemically reactive and catalytically active. Correspondence of the chemical behavior with that for oxidation of uranium in moist air suggests that similar catalytic processes participate in the mechanism of moisture-enhanced corrosion of uranium and plutonium. Evaluation of chemical and kinetic data for corrosion of the metals leads to a comprehensive mechanism for corrosion in dry air, water vapor, and moist air. Results are applied in confirming that the corrosion rate of Pu in water vapor decreases sharply between 100 and 200 degrees C.

  11. Three-dimensional B,N-doped Graphene Foam as a Metal-free Catalyst for Oxygen Reduction Reaction

    Science.gov (United States)

    2013-01-01

    evaluated by the cyclic voltammetry and linear sweep voltammetry techniques on rotating disk electrodes ( RDE ). Durability testing of the BN-GF...conditions. Fig. 8 (a) RDE voltammograms of the undoped GF/GC electrode, the B-GF/GC electrode, the N-GF/GC electrode, the BN-GF/GC electrode, and the...Pt–C/GC electrode in an oxygen saturated 0.1 M KOH solution at a rotation rate of 1600 rpm. Scan rate: 10 mV s1. (b) RDE voltammograms of the BN-GF

  12. Importance of the support and the grade of Pt in the oxygen reduction reaction; Importancia del soporte y del grado del Pt en la reaccion de reduccion de oxigeno

    Energy Technology Data Exchange (ETDEWEB)

    Enriquez M, O.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2004-07-01

    The technology of the fuel cells type Proton Exchange Membrane (PEM), needs to define clearly the influence of the different involved parameters, this is made in general using methods of electrochemical impedance, in which the involved reactions can be presupposed. Another form of making is identifying experimentally the influence of the different parameters. In this work the obtained results are reported with for the oxygen reduction reaction using as electro catalyst platinum analytical grade and fuel cell grade and like support graphite and vulcan. It was found that as much the support as the particle size modify the over potential for the oxygen reduction reaction (Orr). (Author)

  13. A facile-operation tubular electro-Fenton system combined with oxygen evolution reaction for flutriafol degradation: Modeling and Parameters optimizing

    International Nuclear Information System (INIS)

    Xu, Anlin; Wei, Kajia; Zhang, Yonghao; Han, Weiqing; Li, Jiansheng; Sun, Xiuyun; Shen, Jinyou; Wang, Lianjun

    2017-01-01

    Highlights: •A novel tubular cathode coated by carbon black and Fe 2 O 3 -NPs was fabricated and tested. •Effective flutriafol degradation of in dual tubular EF reactor was optimized by RSM. •Ti/RuO 2 and Ti/SnO 2 -Sb anode as oxygen provider can reach high oxygen utilization (78.8%). •The best flutriafol removal (76.5%) without circulation was gained if Ti/RuO 2 was selected as anode. •The simplest operation by the EOC process without aeration, pH and iron adjustment was obtained in the system. -- Abstract: An effective tubular membrane cathode coated by heterogeneous Fe 2 O 3 nanoparticles with carbon black (CB), combined with oxygen evolution reaction (OER), was fabricated to simplify the operation of electro-Fenton system. It was demonstrated that the cathode had a favorable suitability for this system owing to the excellent performance presented on Field emission scanning electron microscopy (FE-SEM), Transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and Cyclic voltammetry (CV). An optimal condition was obtained by response surface methodology (RSM) including pH of 6.7, current density of 13.0 A m −2 , membrane flux of 82.9 L m −2 h −1 , and CB/Fe of 6.2:1. Meanwhile, we achieved an estimated degradation efficiency of flutriafol (79.6%) in optimal condition without circulation of the influent. Effects of OER on the degradation of flutriafol via Ti/RuO 2 and Ti/SnO 2 -Sb tubular anodes were further interpreted by the gas production rate and the H 2 /O 2 value. High oxygen utilization of 78.8% was acquired when Ti/RuO 2 anode served as a sufficient oxygen provider. The electrocatalytic oxygen cycle, a key loop process, was firstly interpreted in this system, which achieved a great comprehensive electrocatalytic effect with the simplest operation and had a 74.5% removal of flutriafol in the verified experiment.

  14. Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

    Science.gov (United States)

    Thorn, Robert Peyton, Jr.

    A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic

  15. Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

    2015-06-15

    Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

  16. Reactions of State-Selected Atomic Oxygen Ions O+(S-4, D-2, P-2) with Methane

    Czech Academy of Sciences Publication Activity Database

    de Miranda, B. C.; Romanzin, C.; Chefdeville, M.; Vuitton, V.; Žabka, Ján; Polášek, Miroslav; Alcaraz, C.

    2015-01-01

    Roč. 119, č. 23 (2015), s. 6082-6098 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GA14-19693S; GA MŠk(CZ) LD14024 Institutional support: RVO:61388955 Keywords : CHARGE-TRANSFER REACTIONS * PHOTOELECTRON-PHOTOION COINCIDENCE * TRANSLATIONAL ENERGY-DEPENDENCE Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.883, year: 2015

  17. M3C (M: Fe, Co, Ni) Nanocrystals Encased in Graphene Nanoribbons: An Active and Stable Bifunctional Electrocatalyst for Oxygen Reduction and Hydrogen Evolution Reactions.

    Science.gov (United States)

    Fan, Xiujun; Peng, Zhiwei; Ye, Ruquan; Zhou, Haiqing; Guo, Xia

    2015-07-28

    Transition metal carbide nanocrystalline M3C (M: Fe, Co, Ni) encapsulated in graphitic shells supported with vertically aligned graphene nanoribbons (VA-GNRs) are synthesized through a hot filament chemical vapor deposition (HF-CVD) method. The process is based on the direct reaction between iron group metals (Fe, Co, Ni) and carbon source, which are facilely get high purity carbide nanocrystals (NCs) and avoid any other impurity at relatively low temperature. The M3C-GNRs exhibit superior enhanced electrocatalystic activity for oxygen reduction reaction (ORR), including low Tafel slope (39, 41, and 45 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively), positive onset potential (∼0.8 V), high electron transfer number (∼4), and long-term stability (no obvious drop after 20 000 s test). The M3C-GNRs catalyst also exhibits remarkable hydrogen evolution reaction (HER) activity with a large cathodic current density of 166.6, 79.6, and 116.4 mA cm(-2) at an overpotential of 200 mV, low onset overpotential of 32, 41, and 35 mV, small Tafel slope of 46, 57, and 54 mV dec(-1) for Fe3C-GNRs, Co3C-GNRs, and Ni3C-GNRs, respectively, as well as an excellent stability in acidic media.

  18. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Science.gov (United States)

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  19. TiO2 obtained by laser ablation and it response in alkaline medium for the oxygen detachment reaction

    International Nuclear Information System (INIS)

    Jimenez B, J.; Escobar A, L.; Fernandez V, S.M.

    2007-01-01

    The performance of the photo electrocatalysts materials depends on one hand of the it structures of the crystalline lattice and of their surface properties, those which in turn are determined by the material preparation method. In this work the laser ablation technique to obtain thin films of titanium dioxide on recovered glass with tin oxide is presented. The carried out analyses showed homogeneous films, one of amorphous titanium oxide with a band width of 3.43 eV and the other one with anatase structure with a band energy of 3.41 eV. The photoresponse for the oxygen detachment it was better for the anatase. In a 0.1M KOH medium it was found corrosion in the films. (Author)

  20. Theoretical study of coupling mechanisms between oxygen diffusion, chemical reaction, mechanical stresses in a solid-gas reactive system

    International Nuclear Information System (INIS)

    Creton, N.; Optasanu, V.; Montesin, T.; Garruchet, S.

    2008-01-01

    This paper offers a study of oxygen dissolution into a solid, and its consequences on the mechanical behaviour of the material. In fact, mechanical strains strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO 2 compound near the internal interface is consistent with some oxidation mechanisms of oxidation experimentally observed. More generally, this work will be extended to the simulation to an oxide layer growth on a metallic substrate. (authors)

  1. Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Le Bozec, N

    2000-01-15

    Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

  2. Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

    Energy Technology Data Exchange (ETDEWEB)

    Le Bozec, N

    2000-01-15

    Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

  3. Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

    Science.gov (United States)

    Zhang, Chun; Feng, Peng; Jiao, Ning

    2013-10-09

    The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

  4. The competition between cathodic oxygen and ozone reduction and its role in dictating the reaction mechanisms of an electro-peroxone process.

    Science.gov (United States)

    Xia, Guangsen; Wang, Yujue; Wang, Bin; Huang, Jun; Deng, Shubo; Yu, Gang

    2017-07-01

    Previous studies indicate that effective generation of hydrogen peroxide (H 2 O 2 ) from cathodic oxygen (O 2 ) reduction is critical for the improved water treatment performance (e.g., enhanced pollutant degradation and reduced bromate formation) during the electro-peroxone (E-peroxone) process (a combined process of electrolysis and ozonation). However, undesired reactions (e.g., O 3 , H 2 O 2 , and H 2 O reductions) may occur in competition with O 2 reduction at the cathode. To get a better understanding of how these side reactions would affect the process, this study investigated the cathodic reaction mechanisms during electrolysis with O 2 /O 3 gas mixture sparging using various electrochemical techniques (e.g., linear sweep voltammetry and stepped-current chronopotentiometry). Results show that when a carbon brush cathode was used during electrolysis with O 2 /O 3 sparging, H 2 O and H 2 O 2 reductions were usually negligible cathodic reactions. However, O 3 can be preferentially reduced at much more positive potentials (ca. 0.9 V vs. SCE) than O 2 (ca. -0.1 V vs. SCE) at the carbon cathode. Therefore, cathodic O 2 reduction was inhibited when the process was operated under current limited conditions for cathodic O 3 reduction. The inhibition of O 2 reduction prevented the desired E-peroxone process (cathodic O 2 reduction to H 2 O 2 and ensuing reaction of H 2 O 2 with O 3 to OH) from occurring. In contrast, when cathodic O 3 reduction was limited by O 3 mass transfer to the cathode, cathodic O 2 reduction to H 2 O 2 could occur, thus enabling the E-peroxone process to enhance pollutant degradation and mineralization. Many process and water parameters (applied current, ozone dose, and reactivity of water constituents with O 3 ) can cause fundamental changes in the cathodic reaction mechanisms, thus profoundly influencing water treatment performance during the E-peroxone process. To exploit the benefits of H 2 O 2 in water treatment, reaction conditions

  5. Nuclear reaction analysis of Ge ion-implanted ZnO bulk single crystals: The evaluation of the displacement in oxygen lattices

    Energy Technology Data Exchange (ETDEWEB)

    Kamioka, K.; Oga, T.; Izawa, Y. [College of Engineering and Research Center of Ion Beam Technology, Hosei University, Koganei, Tokyo 184-8584 (Japan); Kuriyama, K., E-mail: kuri@ionbeam.hosei.ac.jp [College of Engineering and Research Center of Ion Beam Technology, Hosei University, Koganei, Tokyo 184-8584 (Japan); Kushida, K. [Department of Arts and Science, Osaka Kyouiku University, Kashiwara, Osaka 582-8582 (Japan); Kinomura, A. [National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568 (Japan)

    2014-08-01

    The displacement of oxygen lattices in Ge ion-implanted ZnO bulk single crystals is studied by nuclear reaction analysis (NAR), photoluminescence (PL), and Van der Pauw methods. The Ge ion-implantation (net concentration: 2.6 × 10{sup 20} cm{sup −3}) into ZnO is performed using a multiple-step energy. The high resistivity of ∼10{sup 3} Ω cm in un-implanted samples remarkably decreased to ∼10{sup −2} Ω cm after implanting Ge-ion and annealing subsequently. NRA measurements of as-implanted and annealed samples suggest the existence of the lattice displacement of O atoms acting as acceptor defects. As O related defects still remain after annealing, these defects are not attributed to the origin of the low resistivity in 800 and 1000 °C annealed ZnO.

  6. Ni-O4 species anchored on N-doped graphene-based materials as molecular entities and electrocatalytic performances for oxygen reduction reaction

    Science.gov (United States)

    Jang, Dawoon; Lee, Seungjun; Shin, Yunseok; Ohn, Saerom; Park, Sunghee; Lim, Donggyu; Park, Gilsoo; Park, Sungjin

    2017-12-01

    The generation of molecular active species on the surface of nano-materials has become promising routes to produce efficient electrocatalysts. Development of cost-effective catalysts with high performances for oxygen reduction reaction (ORR) is an important challenge for fuel cell and metal-air battery applications. In this work, we report a novel hybrid produced by room-temperature solution processes using Ni-based organometallic molecules and N-doped graphene-based materials. Chemical and structural characterizations reveal that Ni-containing species are well-dispersed on the surface of graphene network as molecular entity. The hybrid shows excellent electrocatalytic performances for ORR in basic medium with an onset potential of 0.87 V (vs. RHE), superior durability and good methanol tolerance.

  7. A polyacrylonitrile copolymer-silica template for three-dimensional hierarchical porous carbon as a Pt catalyst support for the oxygen reduction reaction.

    Science.gov (United States)

    Liu, Minmin; Li, Jian; Cai, Chao; Zhou, Ziwei; Ling, Yun; Liu, Rui

    2017-08-01

    Herein, we report a novel route to construct a hierarchical three-dimensional porous carbon (3DC) through a copolymer-silica assembly. In the synthesis, silica acts as a hard template and leads to the formation of an interconnected 3D macropore, whereas styrene-co-acrylonitrile polymer has been used as both a carbon source and a soft template for micro- and meso-pores. The obtained 3DC materials possess a large surface area (∼550.5 m 2 g -1 ), which facilitates high dispersion of Pt nanoparticles on the carbon support. The 3DC-supported Pt electrocatalyst shows excellent performance in the oxygen reduction reaction (ORR). The easy processing ability along with the characteristics of hierarchical porosity offers a new strategy for the preparation of carbon nanomaterials for energy application.

  8. Density functional study on the mechanism for the highly active palladium monolayer supported on titanium carbide for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Mao, Jianjun; Zhang, Yanxing; Chu, Xingli; Li, Shasha; Yang, Zongxian

    2016-01-01

    The adsorption, diffusion, and dissociation of O 2 on the palladium monolayer supported on TiC(001) surface, MLPd/TiC(001), are investigated using ab initio density functional theory calculations. Strong adhesion of palladium monolayer to the TiC(001) support, accompanied by a modification of electronic structure of the supported palladium, is evidenced. Compared with Pt(111) surface, the MLPd/TiC(001) can enhance the adsorption of O 2 , leading to comparable dissociation barrier and a smaller diffusion barrier of O 2 . Whilst the adsorption strength of atomic O (the dissociation product of O 2 ) on MLPd/TiC(001) is similar to that on the Pt(111) surface, possessing high mobility, our theoretical results indicate that MLPd/TiC(001) may serve as a good catalyst for the oxygen reduction reaction.

  9. Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

    Science.gov (United States)

    Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

    2018-02-01

    In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

  10. Nuclear reaction analysis of Ge ion-implanted ZnO bulk single crystals: The evaluation of the displacement in oxygen lattices

    Science.gov (United States)

    Kamioka, K.; Oga, T.; Izawa, Y.; Kuriyama, K.; Kushida, K.; Kinomura, A.

    2014-08-01

    The displacement of oxygen lattices in Ge ion-implanted ZnO bulk single crystals is studied by nuclear reaction analysis (NAR), photoluminescence (PL), and Van der Pauw methods. The Ge ion-implantation (net concentration: 2.6 × 1020 cm-3) into ZnO is performed using a multiple-step energy. The high resistivity of ∼103 Ω cm in un-implanted samples remarkably decreased to ∼10-2 Ω cm after implanting Ge-ion and annealing subsequently. NRA measurements of as-implanted and annealed samples suggest the existence of the lattice displacement of O atoms acting as acceptor defects. As O related defects still remain after annealing, these defects are not attributed to the origin of the low resistivity in 800 and 1000 °C annealed ZnO.

  11. Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

    International Nuclear Information System (INIS)

    Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

    2016-01-01

    Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

  12. Spillover effect induced Pt-TiO2/C as ethanol tolerant oxygen reduction reaction catalyst for direct ethanol fuel cells

    International Nuclear Information System (INIS)

    Meenakshi, S.; Nishanth, K.G.; Sridhar, P.; Pitchumani, S.

    2014-01-01

    Hypo-hyper-d-electronic interactive nature is used to develop a new carbon supported HT-Pt-TiO 2 composite catalyst comprising Pt and Ti in varying atomic ratio, namely 1:1, 2:1 and 3:1. The electro-catalysts are characterized by XRD, TEM, SEM-EDAX, Cyclic Voltammetry (CV) and Linear sweep voltammetry (LSV) techniques. HT-Pt-TiO 2 /C catalysts exhibit significant improvement in oxygen reduction reaction (ORR) over Pt/C. The effect of composition towards ORR with and without ethanol has been studied. The direct ethanol fuel cell (DEFC) with HT-Pt-TiO 2 /C cathode catalyst exhibits an enhanced peak power density of 41 mW cm −2 , whereas 21 mW cm −2 is obtained for the DEFCs with carbon-supported Pt catalyst operating under identical conditions

  13. Bimetallic NiFe2O4 synthesized via confined carburization in NiFe-MOFs for efficient oxygen evolution reaction

    Science.gov (United States)

    Fang, Zhiqiang; Hao, Zhaomin; Dong, Qingsong; Cui, Yong

    2018-04-01

    Transition metal oxides that derived from metal-organic framework (MOF) precursor have intensively received attention because of their numerous electrochemical applications. Bimetallic Ni-Fe oxides have been rarely reported on the basis of MOF-related strategy. Herein, a bimetallic NiFe2O4 was successfully synthesized via confined carburization in NiFe-MOF precursors and characterized by XRD, XPS, SEM, and TEM. After conducting an investigation of oxygen evolution reaction (OER), the as-synthesized NiFe2O4 material exhibited good catalytic efficiency and high stability and durability in alkaline media. The as-synthesized NiFe2O4 material would promote the development of MOFs in non-noble-metal OER catalyst.

  14. Formation of short-lived positron emitters in reactions of protons of energies up to 200 MeV with the target elements carbon, nitrogen and oxygen

    CERN Document Server

    Kettern, K; Qaim, S M; Shubin, Yu N; Steyn, G F; Van der Walt, T N; 10.1016/j.apradiso.2004.02.007

    2004-01-01

    Excitation functions were measured by the stacked-foil technique for proton induced reactions on carbon, nitrogen and oxygen leading to the formation of the short-lived positron emitters /sup 11/C (T/sub 1 /2/=20.38 min) and /sup 13/N (T/sub 1/2/=9.96 min). The energy region covered extended up to 200 MeV. The product activity was measured non-destructively via gamma -ray spectrometry. A careful decay curve analysis of the positron annihilation radiation was invariably performed. The experimental results were compared with theoretical data obtained using the modified hybrid nuclear model code ALICE-IPPE for intermediate energies. The agreement was found to be generally satisfactory. The data are of importance in proton therapy.

  15. Testing of a Liquid Oxygen/Liquid Methane Reaction Control Thruster in a New Altitude Rocket Engine Test Facility

    Science.gov (United States)

    Meyer, Michael L.; Arrington, Lynn A.; Kleinhenz, Julie E.; Marshall, William M.

    2012-01-01

    A relocated rocket engine test facility, the Altitude Combustion Stand (ACS), was activated in 2009 at the NASA Glenn Research Center. This facility has the capability to test with a variety of propellants and up to a thrust level of 2000 lbf (8.9 kN) with precise measurement of propellant conditions, propellant flow rates, thrust and altitude conditions. These measurements enable accurate determination of a thruster and/or nozzle s altitude performance for both technology development and flight qualification purposes. In addition the facility was designed to enable efficient test operations to control costs for technology and advanced development projects. A liquid oxygen-liquid methane technology development test program was conducted in the ACS from the fall of 2009 to the fall of 2010. Three test phases were conducted investigating different operational modes and in addition, the project required the complexity of controlling propellant inlet temperatures over an extremely wide range. Despite the challenges of a unique propellant (liquid methane) and wide operating conditions, the facility performed well and delivered up to 24 hot fire tests in a single test day. The resulting data validated the feasibility of utilizing this propellant combination for future deep space applications.

  16. Matching the reaction-diffusion simulation to dynamic [18F]FMISO PET measurements in tumors: extension to a flow-limited oxygen-dependent model.

    Science.gov (United States)

    Shi, Kuangyu; Bayer, Christine; Gaertner, Florian C; Astner, Sabrina T; Wilkens, Jan J; Nüsslin, Fridtjof; Vaupel, Peter; Ziegler, Sibylle I

    2017-02-01

    Positron-emission tomography (PET) with hypoxia specific tracers provides a noninvasive method to assess the tumor oxygenation status. Reaction-diffusion models have advantages in revealing the quantitative relation between in vivo imaging and the tumor microenvironment. However, there is no quantitative comparison of the simulation results with the real PET measurements yet. The lack of experimental support hampers further applications of computational simulation models. This study aims to compare the simulation results with a preclinical [ 18 F]FMISO PET study and to optimize the reaction-diffusion model accordingly. Nude mice with xenografted human squamous cell carcinomas (CAL33) were investigated with a 2 h dynamic [ 18 F]FMISO PET followed by immunofluorescence staining using the hypoxia marker pimonidazole and the endothelium marker CD 31. A large data pool of tumor time-activity curves (TAC) was simulated for each mouse by feeding the arterial input function (AIF) extracted from experiments into the model with different configurations of the tumor microenvironment. A measured TAC was considered to match a simulated TAC when the difference metric was below a certain, noise-dependent threshold. As an extension to the well-established Kelly model, a flow-limited oxygen-dependent (FLOD) model was developed to improve the matching between measurements and simulations. The matching rate between the simulated TACs of the Kelly model and the mouse PET data ranged from 0 to 28.1% (on average 9.8%). By modifying the Kelly model to an FLOD model, the matching rate between the simulation and the PET measurements could be improved to 41.2-84.8% (on average 64.4%). Using a simulation data pool and a matching strategy, we were able to compare the simulated temporal course of dynamic PET with in vivo measurements. By modifying the Kelly model to a FLOD model, the computational simulation was able to approach the dynamic [ 18 F]FMISO measurements in the investigated

  17. Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum nanocomposite as an efficient electrocatalyst for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Li, Zesheng; Liu, Zhisen; Li, Bolin; Liu, Zhenghui; Li, Dehao; Wang, Hongqiang; Li, Qingyu

    2016-01-01

    Graphical abstract: Newfashioned hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite with interesting three-dimensional architecture bas been successfully fabricated as an efficient electrocatalyst for the oxygen reduction reaction. - Highlights: • Hollow hemisphere-shaped macroporous graphene is proposed as ORR catalyst support. • Honeycomb-like macroporous graphene/WC/Pt electrocatalyst is firsy prepared for ORR. • The present electrocatalyst exhibited greatly enhanced ORR catalytic activity and stability. - Abstract: Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite has been synthesized as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The HMG/WC/Pt sample has been systematically characterized by the X-ray diffraction (XRD), Scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The analysis results indicate that the sample has an interesting three-dimensional hollow hemisphere-shaped macroporous architecture. The results also demonstrate the successful integration of WC and Pt nanoparticles on the HMG, in which the WC nanoparticles are in size of about 10 nm and the Pt nanoparticles are in size of about 3 nm. The as-prepared HMG/WC/Pt electrode displays excellent electrocatalytic performances for the ORR in 0.1 mol L −1 HClO 4 electrolyte. The mass activity (i m at 0.9 V) of HMG/WC/Pt is 206 mA mg −1 Pt, which is about 85% higher than that of Pt/C (112 mA mg −1 Pt). It also displayed a very high activity retention of 84.5% after 2000 cyclic voltammetry cycles for the HMG/WC/Pt, while that of the Pt/C is only 70.5%. The HMG/WC/Pt nanocomposite would be a promising electrocatalytic material for the ORR in Fuel cell applications.

  18. Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

    Science.gov (United States)

    Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

    2006-05-04

    The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

  19. Facile preparation of three-dimensional Co1-xS/sulfur and nitrogen-codoped graphene/carbon foam for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Liang, Hui; Li, Chenwei; Chen, Tao; Cui, Liang; Han, Jingrui; Peng, Zhi; Liu, Jingquan

    2018-02-01

    Because of the urgent need for renewable resources, oxygen reduction reaction (ORR) has been widely studied. Finding efficient and low cost non-precious metal catalyst is increasingly critical. In this study, melamine foam is used as template to obtain porous sulfur and nitrogen-codoped graphene/carbon foam with uniformly distributed cobalt sulfide nanoparticles (Co1-xS/SNG/CF) which is prepared by a simple infiltration-drying-sulfuration method. It is noteworthy that melamine foam not only works as a three-dimensional support skeleton, but also provides a nitrogen source without any environmental pollution. Such Co1-xS/SNG/CF catalyst shows excellent oxygen reduction catalytic performance with an onset potential of only 0.99 V, which is the same as that of Pt/C catalyst (Eonset = 0.99 V). Furthermore, the stability and methanol tolerance of Co1-xS/SNG/CF are more outstanding than those of Pt/C catalyst. Our work manifests a facile method to prepare S and N-codoped 3D graphene network decorated with Co1-xS nanoparticles, which may be utilized as potential alternative to the expensive Pt/C catalysts toward ORR.

  20. CoM(M=Fe,Cu,Ni)-embedded nitrogen-enriched porous carbon framework for efficient oxygen and hydrogen evolution reactions

    Science.gov (United States)

    Feng, Xiaogeng; Bo, Xiangjie; Guo, Liping

    2018-06-01

    Rational synthesis and development of earth-abundant materials with efficient electrocatalytic activity and stability for water splitting is a critical but challenging step for sustainable energy application. Herein, a family of bimetal (CoFe, CoCu, CoNi) embedded nitrogen-doped carbon frameworks is developed through a facile and simple thermal conversion strategy of metal-doped zeolitic imidazolate frameworks. Thanks to collaborative superiorities of abundant M-N-C species, modulation action of secondary metal, cobalt-based electroactive phases, template effect of MOFs and unique porous structure, bimetal embedded nitrogen-doped carbon frameworks materials manifest good oxygen and hydrogen evolution catalytic activity. Especially, after modulating the species and molar ratio of metal sources, optimal Co0.75Fe0.25 nitrogen-doped carbon framework catalyst just requires a low overpotential of 303 mV to achieve 10 mA cm-2 with a low Tafel slope (39.49 mV dec-1) for oxygen evolution reaction, which even surpasses that of commercial RuO2. In addition, the optimal catalyst can function as an efficient bifunctional electrocatalyst for overall water splitting with satisfying activity and stability. This development offers an attractive direction for the rational design and fabrication of porous carbon materials for electrochemical energy applications.

  1. From two-dimension to one-dimension: the curvature effect of silicon-doped graphene and carbon nanotubes for oxygen reduction reaction.

    Science.gov (United States)

    Zhang, Peng; Hou, Xiuli; Mi, Jianli; He, Yanqiong; Lin, Lin; Jiang, Qing; Dong, Mingdong

    2014-09-07

    For the goal of practical industrial development of fuel cells, inexpensive, sustainable, and highly efficient electrocatalysts for oxygen reduction reactions (ORR) are highly desirable alternatives to platinum (Pt) and other rare metals. In this work, based on density functional theory, silicon (Si)-doped carbon nanotubes (CNTs) and graphene as metal-free, low cost, and high-performance electrocatalysts for ORR are studied systematically. It is found that the curvature effect plays an important role in the adsorption and reduction of oxygen. The adsorption of O2 becomes weaker as the curvature varies from positive values (outside CNTs) to negative values (inside CNTs). The free energy change of the rate-determining step of ORR on the concave inner surface of Si-doped CNTs is smaller than that on the counterpart of Si-doped graphene, while that on the convex outer surface of Si-doped CNTs is larger than that on Si-doped graphene. Uncovering this new ORR mechanism on silicon-doped carbon electrodes is significant as the same principle could be applied to the development of various other metal-free efficient ORR catalysts for fuel cell applications.

  2. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    Science.gov (United States)

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Fabrication of iron-doped cobalt oxide nanocomposite films by electrodeposition and application as electrocatalyst for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jingxuan; Wang, Xuemei; Qin, Dongdong; Xue, Zhonghua; Lu, Xiaoquan, E-mail: luxq@nwnu.edu.cn

    2014-11-30

    Highlights: • We fabricated the Fe-doped Co{sub 3}O{sub 4} nanofilms for the first time by potentiostatic electrodeposition method. • The Fe was doped homogeneously in the nanofilms by this method. • Among the different concentration ratios of Co{sup 2+}/Fe{sup 2+}, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. • The Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit good electrocatalytic activity toward oxygen reduction and appear to be promising cathodic electrocatalyst in alkaline fuel cells. - Abstract: In this work, Fe-doped Co{sub 3}O{sub 4} nanofilms were fabricated by electrodeposition on FTO glass substrates for the first time. The structures of the as-prepared nanofilms were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Characterization results demonstrate that Fe was doped homogeneously in the nanofilms. As the different concentration ratios of Fe{sup 2+}/Co{sup 2+} were explored, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. It is considered that the difference in the catalytic activities for the ORR of the samples may be due to the fact that the joining of iron changed the catalyst surface's electric state and enhanced the acidity of cobalt centers, on the other hand, the doping process probably modified the absorption property of the nanofilms. The experimental results suggest that the Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit favorable electrocatalytic activity toward ORR and appear to be promising cathodic electrocatalyst in alkaline fuel cells.

  4. Two Light Sterile Neutrinos that Mix Maximally with Each Other and Moderately with Three Active Neutrinos

    International Nuclear Information System (INIS)

    Krolikowski, W.

    2004-01-01

    Since the 3+1 neutrino models with one light sterile neutrino turn out to be not very effective, at least two light sterile neutrinos may be needed to reconcile the solar and atmospheric neutrino experiments with the LSND result, if this is confirmed by the ongoing MiniBooNE experiment (and when the CPT invariance is assumed to hold for neutrino oscillations). We present an attractive 3+2 neutrino model, where two light sterile neutrinos mix maximally with each other, in analogy to the observed maximal mixing of muon and tauon active neutrinos. But, while the mixing of ν e and (ν μ - ν τ )/√2 is observed as large (though not maximal), the mixing of ν e with the corresponding combination of two light sterile neutrinos is expected to be only moderate because of the reported smallness of LSND oscillation amplitude. The presented model turns out, however, not to be more effective in explaining the hypothetic LSND result than the simplest 3+1 neutrino model. On the other hand, in the considered 3+2 model, the deviations from conventional oscillations of three active neutrinos appear to be minimal within a larger class of 3+2 models. (author)

  5. Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

    2015-12-01

    Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

  6. Facile Synthesis of Quasi-One-Dimensional Au/PtAu Heterojunction Nanotubes and Their Application as Catalysts in an Oxygen-Reduction Reaction.

    Science.gov (United States)

    Cai, Kai; Liu, Jiawei; Zhang, Huan; Huang, Zhao; Lu, Zhicheng; Foda, Mohamed F; Li, Tingting; Han, Heyou

    2015-05-11

    An intermediate-template-directed method has been developed for the synthesis of quasi-one-dimensional Au/PtAu heterojunction nanotubes by the heterogeneous nucleation and growth of Au on Te/Pt core-shell nanostructures in aqueous solution. The synthesized porous Au/PtAu bimetallic nanotubes (PABNTs) consist of porous tubular framework and attached Au nanoparticles (AuNPs). The reaction intermediates played an important role in the preparation, which fabricated the framework and provided a localized reducing agent for the reduction of the Au and Pt precursors. The Pt7 Au PABNTs showed higher electrocatalytic activity and durability in the oxygen-reduction reaction (ORR) in 0.1 M HClO4 than porous Pt nanotubes (PtNTs) and commercially available Pt/C. The mass activity of PABNTs was 218 % that of commercial Pt/C after an accelerated durability test. This study demonstrates the potential of PABNTs as highly efficient electrocatalysts. In addition, this method provides a facile strategy for the synthesis of desirable hetero-nanostructures with controlled size and shape by utilizing an intermediate template. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media.

    Science.gov (United States)

    McBean, Coray L; Liu, Haiqing; Scofield, Megan E; Li, Luyao; Wang, Lei; Bernstein, Ashley; Wong, Stanislaus S

    2017-07-26

    The oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating "high aspect ratio" LaNiO 3 and LaMnO 3 nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. We observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2 .

  8. AN INVESTIGATION ON THE EFFECT OF FUNCTIONALISED GRAPHENE COMPOSITED WITH NCNT AND FE-NCNT ON THE OXYGEN REDUCTION REACTION VIA PHYSICAL MIXING METHOD

    Directory of Open Access Journals (Sweden)

    CHONG W.Z.

    2016-02-01

    Full Text Available Oxygen reduction reaction plays a major role in fuel cell applications to generate electricity by an electrochemical reaction. In this study, functionalised graphene composited with Fe-NCNT or NCNT were investigated on its ORR activity using a physical mixing method. Initially, functionalised graphene was produced via oxidation of graphene. NCNT and Fe-NCNT was obtained from the previously prepared samples using chemical vapour deposition technique and electrochemical reduction method for Fe-NCNT. The physical mixing between functionalised graphene and NCNT or Fe-NCNT was performed using sonication with the presence of pyrrole to produce the desired nanocatalyst. The surface morphologies and microstructures of the synthesised nanocatalysts were studied using field emission scanning electron microscopy. Surface chemical functionality of the nanocatalysts was investigated using X-ray photoelectron microscopy. Meanwhile, the ORR performance of nanocatalysts in a half cell were investigated using cyclic voltammetry techniques in both alkaline and acidic electrolytes. From this study, agglomeration of functionalised graphene (f-graphene was observed on the Fe-NCNTs indicating a hindrance in transfer of electrons within the catalyst surface. NCNT/f-graphene showed to contain higher percentage of pyridinic-N which claimed to have favored the catalytic activity compared to Fe-NCNT/f-graphene. Likewise, a higher onset potential was recorded for NCNT/f-graphene which indicated a higher ORR activity than the Fe-NCNT/f-graphene.

  9. Refining cocoon to prepare (N, S, and Fe) ternary-doped porous carbon aerogel as efficient catalyst for the oxygen reduction reaction in alkaline medium

    Science.gov (United States)

    Li, Changqing; Sun, Fengzhan; Lin, Yuqing

    2018-04-01

    Various advanced sulfur doped Fe-N-C non-noble metal catalysts of oxygen reduction reaction (ORR) have been recently designed and reported with excellent catalytic activity. Herein, we refined cocoon with several steps to form silk fibroin solution, treated with iron salt to prepare an easy available, heteroatom (N, S, and Fe) ternary-doped, porous carbon aerogel (HDCA). Heteroatom existed in organic compounds in silk fibroin endow active site for ORR of the resultant carbon frameworks. Moreover, the amino acids presented in silk fibroin acted as ligands, functioning with Fe ions to form FeNx coordination compounds, which also served as active sites towards ORR. The synthesized HDCA electrocatalysts, especially HDCA-800 (obtained at 800 °C) displayed excellent catalytic activity with onsets, half-wave potential of 0.94 V, 0.79 V and higher limited current density of 3.80 mA cm-2 through a near four-electron reduction pathway with an average electron transferred number of 3.86, making them promising alternatives for state-of-the-art ORR electrocatalysts in fuel cell field. The porous structure with synergistic effect of N and S heteroatom doping has been proposed to play a key role in facilitating the desired ORR reaction.

  10. Pt/Cr and Pt/Ni catalysts for oxygen reduction reaction: to alloy or not to alloy?

    Science.gov (United States)

    Escaño, Mary Clare; Gyenge, Elod; Nakanishi, Hiroshi; Kasai, Hideaki

    2011-04-01

    Bimetallic systems such as Pt-based alloys or non-alloys have exhibited interesting catalytic properties but pose a major challenge of not knowing a priori how the electronic and chemical properties will be modified relative to the parent metals. In this work, we present the origin of the changes in the reactivity of Pt/Cr and Pt/Ni catalysts, which have been of wide interest in fuel cell research. Using spin-polarized density functional theory calculations, we have shown that the modification of Pt surface reactivity in Pt/Ni is purely of geometric origin (strain). We have also found that the Pt-Ni bonding is very weak, which explains the observed instability of Pt-Ni catalysts under electrochemical measurements. On the other hand, Pt/Cr systems are governed by strong ligand effect (metal-metal interaction), which explains the experimentally observed reactivity dependence on the relative composition of the alloying components. The general characteristics of the potential energy curves for O2 dissociative adsorption on the bimetallic systems and the pure Pt clarify why the d-band center still works for Pt/Cr despite the strong Pt-Cr bonding and high spin polarization of Pt d-states. On the basis of the above clarifications, viable Pt-Cr and Pt-Ni structures, which involve nano-sized alloys and non-alloy bulk catalyst, which may strike higher than the currently observed oxidation reduction reaction activity are proposed.

  11. Oxygen reduction activity of carbon fibers cathode, and application for current generation from the NAD+ and NADH recycling reaction

    Directory of Open Access Journals (Sweden)

    H. Maeda

    2012-03-01

    Full Text Available Carbon fibers treated at 700 oC for 10 min were found to have O2 reduction activity when being used as a cathode. The special type of partition combined with both cationic and anionic exchange membranes was applied between anode cell and cathode cell in order to use a highly acidic solution such as 0.5 M H2SO4 as an electrolyte of the cathode cell for increasing the efficiency of O2 reduction activity. The current generation from NAD+ and NADH recycling system combined with D-gluconolactone production from 500 mg of D-glucose was performed by applying only carbon fibers for both anode and cathode. The total current volume obtained was 81.4 mAh during the reaction for 10 h, and the current efficiency was 93%. One gram of carbon fibers was pressed with Nafion paste on a piece of carbon paper(area : 50 mm×50mm with heating to prepare the cathode, and this construct was combined with conventional fuel cell. The power density was 3.6 mW/cm2, and the total power volume was calculated to be 90 mW per 1 g of carbon fibers.

  12. Mass-Producible 2D-MoS2-Impregnated Screen-Printed Electrodes That Demonstrate Efficient Electrocatalysis toward the Oxygen Reduction Reaction.

    Science.gov (United States)

    Rowley-Neale, Samuel J; Smith, Graham C; Banks, Craig E

    2017-07-12

    Two-dimensional molybdenum disulfide (2D-MoS 2 ) screen-printed electrodes (2D-MoS 2 -SPEs) have been designed, fabricated, and evaluated toward the electrochemical oxygen reduction reaction (ORR) within acidic aqueous media. A screen-printable ink has been developed that allows for the tailoring of the 2D-MoS 2 content/mass used in the fabrication of the 2D-MoS 2 -SPEs, which critically affects the observed ORR performance. In comparison to the graphite SPEs (G-SPEs), the 2D-MoS 2 -SPEs are shown to exhibit an electrocatalytic behavior toward the ORR which is found, critically, to be reliant upon the percentage mass incorporation of 2D-MoS 2 in the 2D-MoS 2 -SPEs; a greater percentage mass of 2D-MoS 2 incorporated into the 2D-MoS 2 -SPEs results in a significantly less electronegative ORR onset potential and a greater signal output (current density). Using optimally fabricated 2D-MoS 2 -SPEs, an ORR onset and a peak current of approximately +0.16 V [vs saturated calomel electrode (SCE)] and -1.62 mA cm -2 , respectively, are observed, which exceeds the -0.53 V (vs SCE) and -635 μA cm -2 performance of unmodified G-SPEs, indicating an electrocatalytic response toward the ORR utilizing the 2D-MoS 2 -SPEs. An investigation of the underlying electrochemical reaction mechanism of the ORR within acidic aqueous solutions reveals that the reaction proceeds via a direct four-electron process for all of the 2D-MoS 2 -SPE variants studied herein, where oxygen is electrochemically favorably reduced to water. The fabricated 2D-MoS 2 -SPEs are found to exhibit no degradation in the observed achievable current over the course of 1000 repeat scans. The production of such inks and the resultant mass-producible 2D-MoS 2 -SPEs mitigates the need to modify post hoc an electrode via the drop-casting technique that has been previously shown to result in a loss of achievable current over the course of 1000 repeat scans. The 2D-MoS 2 -SPEs designed, fabricated, and tested herein could

  13. Chemical properties and reactive oxygen and nitrogen species quenching activities of dry sugar-amino acid maillard reaction mixtures exposed to baking temperatures.

    Science.gov (United States)

    Chen, Xiu-Min; Liang, Ningjian; Kitts, David D

    2015-10-01

    Maillard reaction products (MRPs) derived from 10 different, dry sugar-amino acid reaction model systems were examined for changes in color index (E), sugar loss, and formation of α-dicarbonyl compounds; the changes were correlated with relative activities to quench both reactive oxygen (ROS) and reactive nitrogen (RNS) species. Reducing sugars, xylose, ribose, fructose, glucose, and non-reducing sucrose were reacted with glycine (Xyl-Gly, Rib-Gly, Fru-Gly, Glc-Gly, and Suc-Gly), or lysine (Xyl-Lys, Rib-Lys, Fru-Lys, Glc-Lys, and Suc-Lys), respectively, at temperatures of 150°C and 180°C for time periods ranging from 5 to 60min. ROS quenching capacity was negatively correlated with color index (E) (r=-0.604, P<0.001), and positively correlated with sugar loss (r=0.567, P<0.001). MRPs also exhibited activity to quench RNS as assessed by nitric oxide (NO) inhibition in differentiated Caco-2 cells that were induced with interferon-γ (IFN-γ) and phorbol ester (PMA) cocktail. We also showed a correlation between RNS and color index, sugar loss, and ROS quenching activities for MR mixtures that were heated for a short time (e.g. 10min) at 150°C. MRP quenching of ROS was largely influenced by sugar type, whereas, RNS quenching was dependent more so on the interaction between reactants and reaction conditions used to generate MRPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Electrochemical quartz crystal microbalance analysis of the oxygen reduction reaction on Pt-based electrodes. Part 2: adsorption of oxygen species and ClO4(-) anions on Pt and Pt-Co alloy in HClO4 solutions.

    Science.gov (United States)

    Omura, J; Yano, H; Tryk, D A; Watanabe, M; Uchida, H

    2014-01-14

    To gain deeper insight into the role of adsorbed oxygenated species in the O2 reduction reaction (ORR) kinetics on platinum and platinum-cobalt alloys for fuel cells, we carried out a series of measurements with the electrochemical quartz crystal microbalance (EQCM) and the rotating disk electrode (RDE) in acid solution. The effects of anion adsorption on the activities for the ORR were first assessed in HClO4 and HF electrolyte solutions at various concentrations. In our previous work (Part 1), we reported that the perchlorate anion adsorbs specifically on bulk-Pt, with a Frumkin-Temkin isotherm, that is, a linear relationship between Δm and log[HClO4]. Here, we find that the specific adsorption on the Pt-skin/Pt3Co alloy was significantly stronger than that on bulk-Pt, in line with its modified electronic properties. The kinetically controlled current density j(k) for the O2 reduction at the Pt-skin/Pt3Co-RDE was about 9 times larger than that of the bulk-Pt-RDE in 0.01 M HClO4 saturated with air, but the j(k) values on Pt-skin/Pt3Co decreased with increasing [HClO4] more steeply than in the case of Pt, due to the blocking of the active sites by the specifically adsorbed ClO4(-). We have detected reversible mass changes for one or more adsorbed oxygen-containing species (Ox = O2, O, OH, H2O) on the Pt-skin/Pt3Co-EQCM and Pt-EQCM in O2-saturated and He-purged 0.01 M HClO4 solutions, in which the specific adsorption of ClO4(-) anions was negligible. The coverages of oxygen species θ(Ox) on the Pt-skin/Pt3Co in the potential range from 0.86 to 0.96 V in the O2-saturated solution were found to be larger than those on pure Pt, providing strong evidence that the higher O2 reduction activity on the Pt3Co is correlated with higher θ(Ox), contrary to the conventional view.

  15. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    Science.gov (United States)

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    recognized. This remarkable feature suggested that the original [4Fe-4S] cluster can be restored using persulfide as the source of sulfide ion. We have demonstrated that only iron and a source of electrons are required to promote efficient conversion back from the [2Fe-2S] to the [4Fe-4S] form. We propose this as a novel in vivo repair mechanism that does not require the intervention of an iron-sulfur cluster biogenesis pathway. A number of iron-sulfur regulators have evolved to function as sensors of NO. Although it has long been known that the iron-sulfur clusters of many phylogenetically unrelated proteins are vulnerable to attack by NO, our recent studies of Wbl proteins and FNR have provided new insights into the mechanism of cluster nitrosylation, which overturn the commonly accepted view that the product is solely a mononuclear iron dinitrosyl complex (known as a DNIC). The major reaction is a rapid, multiphase process involving stepwise addition of up to eight NO molecules per [4Fe-4S] cluster. The major iron nitrosyl product is EPR silent and has optical characteristics similar to Roussin's red ester, [Fe2(NO)4(RS)2] (RRE), although a species similar to Roussin's black salt, [Fe4(NO)7(S)3](-) (RBS) cannot be ruled out. A major future challenge will be to clarify the nature of these species.

  16. Matrix-isolation studies on the radiation-induced chemistry in H₂O/CO₂ systems: reactions of oxygen atoms and formation of HOCO radical.

    Science.gov (United States)

    Ryazantsev, Sergey V; Feldman, Vladimir I

    2015-03-19

    The radiation-induced transformations occurring upon X-ray irradiation of solid CO2/H2O/Ng systems (Ng = Ar, Kr, Xe) at 8-10 K and subsequent annealing up to 45 K were studied by Fourier transform infrared spectroscopy. The infrared (IR) spectra of deposited matrices revealed the presence of isolated monomers, dimers, and intermolecular H2O···CO2 complexes. Irradiation resulted in effective decomposition of matrix-isolated carbon dioxide and water yielding CO molecules and OH radicals, respectively. Annealing of the irradiated samples led to formation of O3, HO2, and a number of xenon hydrides of HXeY type (in the case of xenon matrices). The formation of these species was used for monitoring of the postirradiation thermally induced chemical reactions involving O and H atoms generated by radiolysis. It was shown that the radiolysis of CO2 in noble-gas matrices produced high yields of stabilized oxygen atoms. In all cases, the temperatures at which O atoms become mobile and react are lower than those of H atoms. Dynamics and reactivity of oxygen atoms was found to be independent of the precursor nature. In addition, the formation of HOCO radicals was observed in all the noble-gas matrices at remarkably low temperatures. The IR spectra of HOCO and DOCO were first characterized in krypton and xenon matrices. It was concluded that the formation of HOCO was mainly due to the radiation-induced evolution of the weakly bound H2O···CO2 complexes. This result indicates the significance of weak intermolecular interactions in the radiation-induced chemical processes in inert low-temperature media.

  17. Navigator-gated 3D blood oxygen level-dependent CMR at 3.0-T for detection of stress-induced myocardial ischemic reactions.

    Science.gov (United States)

    Jahnke, Cosima; Gebker, Rolf; Manka, Robert; Schnackenburg, Bernhard; Fleck, Eckart; Paetsch, Ingo

    2010-04-01

    This study determined the value of navigator-gated 3-dimensional blood oxygen level-dependent (BOLD) cardiac magnetic resonance (CMR) at 3.0-T for the detection of stress-induced myocardial ischemic reactions. Although BOLD CMR has been introduced for characterization of myocardial oxygenation status, previously reported CMR approaches suffered from a low signal-to-noise ratio and motion-related artifacts with impaired image quality and a limited diagnostic value in initial patient studies. Fifty patients with suspected or known coronary artery disease underwent CMR at 3.0-T followed by invasive X-ray angiography within 48 h. Three-dimensional BOLD images were acquired during free breathing with full coverage of the left ventricle in a short-axis orientation. The BOLD imaging was performed at rest and under adenosine stress, followed by stress and rest first-pass perfusion and delayed enhancement imaging. Quantitative coronary X-ray angiography (QCA) was used for coronary stenosis definition (diameter reduction > or =50%). The BOLD and first-pass perfusion images were semiquantitatively evaluated (for BOLD imaging, signal intensity differences between stress and rest [DeltaSI]; for perfusion imaging, myocardial perfusion reserve index [MPRI]). The image quality of BOLD CMR at rest and during adenosine stress was considered good to excellent in 90% and 84% of the patients, respectively. The DeltaSI measurements differed significantly between normal myocardium, myocardium supplied by a stenotic coronary artery, and infarcted myocardium (p exogenous contrast-enhancement studies. Copyright 2010 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

  18. Synthesis and electrocatalytic properties of La0.8Sr0.2FeO3−δ perovskite oxide for oxygen reactions

    Directory of Open Access Journals (Sweden)

    R.A. Silva

    2017-09-01

    Full Text Available Perovskites are important alternatives for precious metals as catalysts for bifunctional oxygen electrodes, involving oxygen evolution (OER and reduction (ORR reactions as is the case of regenerative fuel cells. In this work, strontium doped lanthanum ferrite La1−xSrxFeO3−δ (x = 0; 0.1; 0.2; 0.3; 0.4; 0.6 and 1.0 powders were prepared by a self-combustion route. The oxides, in the form of carbon paste electrodes, were characterised by cyclic voltammetry in alkaline solutions. Data analyses lead to the selection of La0.8Sr0.2FeO3−δ to prepare gas diffusion electrodes (GDEs. Cyclic voltammetry and steady state polarization curves were used, respectively, to assess the electrochemical behaviour of GDEs and to obtain kinetic data for both OER and ORR. It is concluded that the oxide preparation conditions/electrode configuration determine the electrode performance. The bifunctionality of the electrodes was assessed, under galvanostatic control, using a cycling protocol within the potential domains for OER and ORR. The potential window, i.e., the total combined overpotential between OER and ORR was found to be of ≈770 mV, value which compares well with that obtained under potentiostatic control. Even though the potential window keeps constant during 140 cycles, the increase in cycling time and/or current density (≥2.5 mA·cm−2 led to a gradual metallization of the GDE surface, as confirmed by Scanning Electron Microscopy and X-ray diffraction analysis.

  19. Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.

    Science.gov (United States)

    Mitra, Mainak; Nimir, Hassan; Demeshko, Serhiy; Bhat, Satish S; Malinkin, Sergey O; Haukka, Matti; Lloret-Fillol, Julio; Lisensky, George C; Meyer, Franc; Shteinman, Albert A; Browne, Wesley R; Hrovat, David A; Richmond, Michael G; Costas, Miquel; Nordlander, Ebbe

    2015-08-03

    Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L(1)) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L(2)), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [Fe(II)(CH3CN)(L)](2+) (L = L(1) (1); L(2) (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [Fe(IV)(O)(L)](2+) (L = L(1) (3); L(2) (4)), which were characterized by UV-vis spectroscopy, high resolution mass spectrometry, and Mössbauer spectroscopy. Complexes 3 and 4 are relatively stable with half-lives at room temperature of 40 h (L = L(1)) and 2.5 h (L = L(2)). The redox potentials of 1 and 2, as well as the visible spectra of 3 and 4, indicate that the ligand field weakens as ligand pyridyl substituents are progressively substituted by (N-methyl)benzimidazolyl moieties. The reactivities of 3 and 4 in hydrogen-atom transfer (HAT) and oxygen-atom transfer (OAT) reactions show that both complexes exhibit enhanced reactivities when compared to the analogous N4Py complex ([Fe(IV)(O)(N4Py)](2+)), and that the normalized HAT rates increase by approximately 1 order of magnitude for each replacement of a pyridyl moiety; i.e., [Fe(IV)(O)(L(2))](2+) exhibits the highest rates. The second-order HAT rate constants can be directly related to the substrate C-H bond dissociation energies. Computational modeling of the HAT reactions indicates that the reaction proceeds via a high spin transition state.

  20. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-01

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic

  1. Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

    Science.gov (United States)

    Gu, Daguo; Zhou, Yao; Ma, Ruguang; Wang, Fangfang; Liu, Qian; Wang, Jiacheng

    2018-06-01

    A series of N-doped carbon materials (NCs) were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile one-step pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C3N4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6, show the highest N content of 6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of 66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal-air batteries.

  2. Ternary Hollow Mesoporous TiN/N-Graphene/Pt Hybrid Results in Enhanced Electrocatalytic Performance for Methanol Oxidation and Oxygen Reduction Reaction

    International Nuclear Information System (INIS)

    Liu, Baocang; Huo, Lili; Zhang, Geng; Zhang, Jun

    2016-01-01

    Highlights: • A novel hollow mesoporous ternary @M-TiN/N-G/Pt electrocatalysts were synthesized. • The @M-TiN/N-G/Pt electrocatalysts displayed outstanding activity and stability toward MOR and ORR. • The activity and stability of @M-TiN/N-G/Pt electrocatalysts were higher than Pt/TiN, @M-TiN/Pt, and Pt/C catalysts. • The excellent electrocatalytic performance rooted in its unique configuration. • Several reasons were proposed to explain the enhanced electrocatalytic performance of @M-TiN/N-G/Pt. - Abstract: A novel hollow mesoporous TiN/N-graphene (N-G) hybrid architecture (@M-TiN/N-G) composed of N-doped graphene wrapped mesoporous TiN nanoparticle shells was constructed for the first time. It can be used as an efficient support for creating a highly efficient ternary @M-TiN/N-G/Pt electrocatalyst with superior catalytic activity and stability for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) through decorating well-dispersed Pt nanoparticles on @M-TiN/N-G surface. By optimizing the content of N-G in catalysts, the @M-TiN/N-G/Pt catalysts display superior catalytic activity and stability toward MOR and ORR to traditional Pt/C and graphene-free Pt/TiN and @M-TiN/Pt catalysts. The various characterization results reveal that the outstanding electrocatalytic performance of @M-TiN/N-G/Pt catalyst roots in its large surface area, high porosity, strong interaction among Pt, TiN, and N-G, excellent electron transfer property facilitated by N-doped graphene, and small size of Pt and TiN nanocrystals. The synthetic approach may be available for constructing other graphene based hollow metal nitrides, carbides, and phosphides for various electrocatalytic applications.

  3. Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal-Organic Frameworks and Ti3C2Tx Nanosheets for Electrocatalytic Oxygen Evolution.

    Science.gov (United States)

    Zhao, Li; Dong, Biliang; Li, Shaozhou; Zhou, Lijun; Lai, Linfei; Wang, Zhiwei; Zhao, Shulin; Han, Min; Gao, Kai; Lu, Min; Xie, Xiaoji; Chen, Bo; Liu, Zhengdong; Wang, Xiangjing; Zhang, Hao; Li, Hai; Liu, Juqing; Zhang, Hua; Huang, Xiao; Huang, Wei

    2017-06-27

    Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti 3 C 2 T x (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm -2 at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec -1 in 0.1 M KOH. These results outperform those obtained by the standard IrO 2 -based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic Ti 3 C 2 T x nanosheets enabled the rapid charge and ion transfer across the well-defined Ti 3 C 2 T x -CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

  4. Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Liu, Ying; Wu, Yan-Ying; Lv, Guo-Jun; Pu, Tao; He, Xing-Quan; Cui, Li-Li

    2013-01-01

    Graphical abstract: The fabricated FePc-Gr catalyst for ORR exhibited high activity, favoring a direct 4-electron process, good stability and selectivity, all of which should be attributed to its high conductivity, the synergistic effect between FePc and graphene, as well as the formation of stable FePc-Gr composite through covalent bonding and π–π interaction. - Abstract: A novel iron(II) phthalocyanine covalently modified graphene (FePc-Gr) was synthesized by reduction of the product obtained through an amidation reaction between carboxyl-functionalized graphene oxide (CFGO) and iron(II) tetra-aminophthalocyanine (FeTAPc). The FePc-Gr hybird was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic properties of FePc-Gr toward the oxygen reduction reaction (ORR) were evaluated using cyclic voltammetry (CV) and linear sweep voltammetry methods. The peak potential of the ORR on the FePc-Gr catalyst was found to be about −0.12 V vs. SCE in 0.1 M NaOH solution, which was 180 and 360 mV more positive than that on FeTAPc and bare GCE, respectively. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements revealed that the ORR mechanism was nearly via a direct four-electron pathway to water on FePc-Gr. The current still remained 83.5% of its initial after chronoamperometric test for 10,000 s. Nevertheless, Pt/C catalyst only retained 40.5% of its initial current. The peak potential and peak current changed slightly when 3 M methanol was introduced. So the FePc-Gr composite catalyst for ORR exhibited high activity, good stability and methanol-tolerance, which could be used as a promising Pt-free catalyst for ORR in alkaline direct methanol fuel cell (DMFC)

  5. Facile solvothermal synthesis of monodisperse Pt2.6Co1 nanoflowers with enhanced electrocatalytic activity towards oxygen reduction and hydrogen evolution reactions

    International Nuclear Information System (INIS)

    Jiang, Liu-Ying; Lin, Xiao-Xiao; Wang, Ai-Jun; Yuan, Junhua; Feng, Jiu-Ju; Li, Xin-Sheng

    2017-01-01

    Highlights: • Uniform Pt 2.6 Co 1 nanoflowers were prepared by a simple solvothermal method. • Glucose and CTAC were used as the green reductant and structure director, respectively. • The architectures had the enlarged ECSA. • The architectures exhibited excellent catalytic performances for HER in acid and alkaline media. • The architectures showed highly catalytic performances for ORR in acid media. - Abstract: Herein, uniform Pt 2.6 Co 1 nanoflowers (NFs) were synthesized in oleylamine by a one-pot solvothermal method, using cetyltrimethylammonium chloride (CTAC) and glucose as the capping agent and green reducing agent. The samples were mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning TEM (HAADF-STEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The architectures had larger electrochemically active surface area (ECSA) of 23.84 m 2 g −1 Pt than Pt 1.2 Co 1 nanocrystals (NCs, 14.96 m 2 g −1 Pt ), Pt 3.7 Co 1 NCs (16.96 m 2 g −1 Pt ) and commercial Pt black (20.35 m 2 g −1 Pt ). And the as-obtained Pt 2.6 Co 1 catalyst displayed superior catalytic performance and better durability for hydrogen evolution reaction (HER) as compared to Pt 1.2 Co 1 NCs, Pt 3.7 Co 1 NCs, commercial 50% Pt/C and Pt black catalysts in acid and alkaline media. Meanwhile, the electrocatalytic performance of Pt 2.6 Co 1 NFs for oxygen reduction reaction (ORR) is better in acid media as compared with that in alkaline media. It indicates the great potential applications of the as-prepared catalyst in fuel cells.

  6. Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

    Science.gov (United States)

    Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

    2018-08-15

    The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

  7. Chemical and Electrochemical Properties of La0.58Sr0.4Fe0.8Co0.2O3-δ (LSCF) Thin Films upon Oxygen Reduction and Evolution Reactions

    DEFF Research Database (Denmark)

    Pitscheider, Simon; Machala, Michael; Guan, Zixuan

    2017-01-01

    The Oxygen Evolution and Oxygen Reduction Reactions (OER/ORR), occurring at the oxygen electrode of Solid Oxide Cells (SOCs) in the two possible ways of operation, require substantial overpotentials, therefore lowering the operating efficiency of the cells. The reaction mechanisms occurring...... at these electrodes are still not completely understood due to their complexity and localized character at the interfaces between different materials or between the gas atmosphere and the electrocatalyst, and need in situ techniques with very high chemical sensitivity, with the additional difficulty of probing...... the materials as close as possible to their realistic operating conditions. In addition, the properties of LSCF are, despite numerous studies, still unclear in many aspects, despite LSCF being one of the state-of-the-art electrocatalysts used for SOCs. It is understood that the surface chemical composition...

  8. Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

    2006-07-01

    This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

  9. Nitrogen-Doped Hollow Carbon Spheres with Embedded Co Nanoparticles as Active Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Ruohao Xing

    2018-02-01

    Full Text Available Transition metal (Fe, Co, Ni complexes on carbon nanomaterials are promising candidates as electrocatalysts towards the oxygen reduction reaction (ORR. In this paper, nitrogen-doped hollow carbon spheres with embedded Co nanoparticles were successfully prepared via a controllable synthesis strategy. The morphology characterization shows that the hollow carbon spheres possess an average diameter of ~150 nm with a narrow size distribution and a shell thickness of ~14.5 nm. The content of N doping ranges from 2.1 to 6.6 at.% depending on the calcination temperature from 900 to 1050 °C. Compared with commercial Pt/C, the Co-containing nitrogen-doped hollow carbon spheres prepared at 900 °C (CoNHCS-900 as an ORR electrocatalyst shows a half-wave potential shift of only ∆E1/2 = 55 mV, but a superior stability of about 90.2% maintenance after 20,000 s in the O2-saturated 0.1 M KOH at a rotating speed of 1600 rpm. This could be ascribed to the synergistic effects of N-containing moieties, Co-Nx species, and Co nanoparticles, which significantly increase the density of active sites and promote the charge transfer during the ORR process.

  10. Microwave-Assisted Synthesis of Reduced Graphene Oxide/SnO2 Nanocomposite for Oxygen Reduction Reaction in Microbial Fuel Cells.

    Science.gov (United States)

    Garino, Nadia; Sacco, Adriano; Castellino, Micaela; Muñoz-Tabares, José Alejandro; Chiodoni, Angelica; Agostino, Valeria; Margaria, Valentina; Gerosa, Matteo; Massaglia, Giulia; Quaglio, Marzia

    2016-02-01

    We report on an easy, fast, eco-friendly, and reliable method for the synthesis of reduced graphene oxide/SnO2 nanocomposite as cathode material for application in microbial fuel cells (MFCs). The material was prepared starting from graphene oxide that has been reduced to graphene during the hydrothermal synthesis of the nanocomposite, carried out in a microwave system. Structural and morphological characterizations evidenced the formation of nanocomposite sheets, with SnO2 crystals of few nanometers integrated in the graphene matrix. Physico-chemical analysis revealed the formation of SnO2 nanoparticles, as well as the functionalization of the graphene by the presence of nitrogen atoms. Electrochemical characterizations put in evidence the ability of such composite to exploit a cocatalysis mechanism for the oxygen reduction reaction, provided by the presence of both SnO2 and nitrogen. In addition, the novel composite catalyst was successfully employed as cathode in seawater-based MFCs, giving electrical performances comparable to those of reference devices employing Pt as catalyst.

  11. Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

    2016-05-01

    Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

    Science.gov (United States)

    Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

    2016-02-01

    High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

  13. N/S/B-doped graphitized carbon encased Fe species as a highly active and durable catalyst towards oxygen reduction reaction.

    Science.gov (United States)

    Li, Guang-Lan; Cheng, Guang-Chun; Chen, Wen-Wen; Liu, Cai-Di; Yuan, Li-Fang; Yang, Bei-Bei; Hao, Ce

    2018-03-15

    Exploring cost-effective, high-performance and durable non-precious metal catalysts is of great significance for the acceleration of sluggish oxygen reduction reaction (ORR). Here, we report an intriguing heteroatom-doped graphitized carbon encased Fe species composite by introducing N, S and B sequentially. The experimental approach was designed ingeniously for that the FeCl 3 ·6H 2 O could catalyze thiourea to synthesize N, S co-doped carbon materials which would further react with H 3 BO 3 and NH 3 (emerged at the heat-treatment process) to prepare N, S and B co-doped carbon materials (Fe-N/S/B-C). The Fe-N/S/B-C exhibits an impressive ORR activity for its half-wave potential of -0.1 V, which is 36 mV or 19 mV higher than that of the corresponding single or dual doped counterparts (Fe-N-C or Fe-N/S-C) and 31 mV positive than that of Pt/C catalyst, respectively. Further chronoamperometric measurement and accelerated aging test confirm the excellent electrochemical durability of Fe-N/S/B-C with the stable core-shell structure. The remarkable ORR performance and facile preparation method enable Fe-N/S/B-C as a potential candidate in electrochemical energy devices. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Co3O4/TiO2 films obtained by laser ablation and sol-gel for the reaction of oxygen liberation in alkaline medium

    International Nuclear Information System (INIS)

    Perez A, J.; Fernandez V, S. M.; Escobar A, L.; Jimenez B, J.

    2008-01-01

    The laser ablation technique known as Pulsed Laser Deposition (PLD) is used for obtaining thin films of TiO 2 /SnO 2 , which was later modified with Co 3 O 4 by PLD or by sol-gel technique. The films were characterized by X-ray diffraction, ultraviolet Vis and Raman spectroscopies, scanning electron microscopy and energy analysis of the dispersed X-rays produced by Auger decay. The anatase phase with particles of nano metric size was obtained by depositing the titanium dioxide in argon atmosphere. The Co 3 O 4 films obtained by PLD on the TiO 2 showed the same morphology. The electrocatalytic activity of the films that were used as photo anodes for the reaction of oxygen liberation was carried out in the darkness, with environment light and the light emitted by a xenon lamp. The current density was higher for films of Co 3 O 4 /TiO 2 /SnO 2 obtained by PLD that for cobalt dioxide of mixed valence obtained by sol-gel. (Author)

  15. Synergistic Effect of Nitrogen Doping and MWCNT Intercalation for the Graphene Hybrid Support for Pt Nanoparticles with Exemplary Oxygen Reduction Reaction Performance

    Directory of Open Access Journals (Sweden)

    Kang Fu

    2018-04-01

    Full Text Available The potential of graphene–multi-walled-carbon nanotube (G-M hybrids prepared by the one-pot modified Hummers method followed by thermal annealing has been demonstrated by employing one as an electrocatalyst support for oxygen reduction reaction (ORR. N doping effectively modified the electronic structure of the G-M hybrid support, which was beneficial for the uniform distribution of Pt nanoparticles, and ORR activities were further improved. The newly prepared Pt/N-G-M catalyst demonstrated higher electrochemical activity than Pt/G-M and Pt/G catalysts. Even compared with commercial 20 wt % Pt/C (JM20, Pt/N-G-M delivered a better half-wave potential and mass activity. In terms of the durability test, Pt/N-G-M maintained 72.7% of its initial electrochemical active surface area (ECSA after 2000 repeated potential cycles between 0 and 1.2 V in acidic media in relation to the 44.4% retention for JM20. Moreover, the half-wave potential for Pt/N-G-M showed only a minimal change, significantly superior to the 139 mV of loss for JM20. It is expected that Pt/N-G-M can be the potential candidate as a highly efficient and durable catalyst if utilized in proton exchange membrane fuel cells (PEMFCs.

  16. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei; Gehrig, Dominik; Zhang, Fan; Lu, Chenbao; Zhang, Chao; Cai, Ming; Wang, Yuanyuan; Laquai, Fré dé ric; Zhuang, Xiaodong; Feng, Xinliang

    2016-01-01

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  17. The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

    International Nuclear Information System (INIS)

    Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

    2016-01-01

    We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

  18. Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

    2015-01-01

    Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

  19. General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

    Science.gov (United States)

    Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

    2016-11-01

    A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities.

  20. Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

    Science.gov (United States)

    Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

    2014-01-22

    Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

  1. Rudimentary simple, single step fabrication of nano-flakes like AgCd alloy electro-catalyst for oxygen reduction reaction in alkaline fuel cell

    International Nuclear Information System (INIS)

    Bhandary, Nimai; Basu, Suddhasatwa; Ingole, Pravin P.

    2016-01-01

    In this work, for the first time, we report rudimentary simple, single step fabrication of an electro-catalyst based on AgCd alloy nanoparticles with flakes like geometry which shows highly efficient activity towards oxygen reduction reaction (ORR). A simple potentiostatic deposition method has been employed for co-depositing AgCd alloy nanostructures with flakes like shapes along with dendrites on the surface of carbon fibre paper. The chemico-physical properties of the catalyst are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS). Electro-catalytic activity of AgCd alloy based electro-catalyst towards ORR is studied in alkaline medium by cyclic voltammetry and rotating ring disk electrode (RRDE) technique. Electrochemical in-situ FTIR measurements are also performed to identify the species generated during ORR process. Based on the results from electro-catalysis experiment, it is concluded that nano-alloyed AgCd electrodeposited on carbon paper shows excellent activity for ORR, following four electron pathways with H_2O_2 yield less than 15%. The combination of low cost of Ag and Cd, fast and facile method of its fabrication and higher activity towards ORR makes the AgCd electro-catalyst an attractive catalyst of choice for alkaline fuel cell.

  2. High content of pyridinic- and pyrrolic-nitrogen-modified carbon nanotubes derived from blood biomass for the electrocatalysis of oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Zheng, Jie; Guo, Chaozhong; Chen, Chunyan; Fan, Mingzhi; Gong, Jianping; Zhang, Yanfang; Zhao, Tianxin; Sun, Yuelin; Xu, Xiaofan; Li, Mengmeng; Wang, Ran; Luo, Zhongli; Chen, Changguo

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: •An ORR electrocatalyst was fabricated from blood biomass and carbon nanotube. •The N-CNT catalyst exhibits good ORR activity, methanol resistance and stability. •The pyrolysis process produces high contents of pyridinic and pyrrolic N species. •The pyridinic-N group may play more important role in the active sites for ORR. -- Abstract: Here we present a facile synthetic route to design nitrogen-doped nanostructured carbon-based electrocatalyst for oxygen reduction reaction (ORR) by the copyrolysis of blood biomass from pig and carbon nanotubes (CNTs) at high temperatures. The nitrogen-doped CNTs obtained at 800 °C not only results in excellent ORR activity with four-electron transfer selectivity in alkaline medium, but also exhibits superior methanol-tolerant property and long-term stability. It is confirmed that high-temperature pyrolysis processes can facilitate to produce higher contents of pyridinic- and pyrrolic-N binding groups in electrocatalysts, contributing to the enhancement of ORR performance in terms of onset potential, half-wave potential, and limited current density. We also propose that the planar-N configuration may be the active site that is responsible for the improved ORR electrocatalytic performance. The straight-forward and cheap synthesis of the active and stable electrocatalyst makes it a promising candidate for electrochemical power sources such as fuel cells or metal-air batteries

  3. Effect of cationic molecules on the oxygen reduction reaction on fuel cell grade Pt/C (20 wt%) catalyst in potassium hydroxide (aq, 1 mol dm(-3)).

    Science.gov (United States)

    Ong, Ai Lien; Inglis, Kenneth K; Whelligan, Daniel K; Murphy, Sam; Varcoe, John R

    2015-05-14

    This study investigates the effect of 1 mmol dm(-3) concentrations of a selection of small cationic molecules on the performance of a fuel cell grade oxygen reduction reaction (ORR) catalyst (Johnson Matthey HiSPEC 3000, 20 mass% Pt/C) in aqueous KOH (1 mol dm(-3)). The cationic molecules studied include quaternary ammonium (including those based on bicyclic systems) and imidazolium types as well as a phosphonium example: these serve as fully solubilised models for the commonly encountered head-groups in alkaline anion-exchange membranes (AAEM) and anion-exchange ionomers (AEI) that are being developed for application in alkaline polymer electrolyte fuel cells (APEFCs), batteries and electrolysers. Both cyclic and hydrodynamic linear sweep rotating disk electrode voltammetry techniques were used. The resulting voltammograms and subsequently derived data (e.g. apparent electrochemical active surface areas, Tafel plots, and number of [reduction] electrons transferred per O2) were compared. The results show that the imidazolium examples produced the highest level of interference towards the ORR on the Pt/C catalyst under the experimental conditions used.

  4. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  5. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei

    2016-10-11

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  6. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

    Science.gov (United States)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-11-21

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

  7. A facile template approach for the synthesis of mesoporous Fe3C/Fe-N-doped carbon catalysts for efficient and durable oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    Shuai Li; Bo Li; Liang Ma; Jia Yang; Hangxun Xu

    2017-01-01

    Facile synthetic approaches toward the development of efficient and durable nonprecious metal catalysts for the oxygen reduction reaction (ORR) are very important for commercializing advanced electrochemical devices such as fuel cells and metal-air batteries.Here we report a novel template approach to synthesize mesoporous Fe-N-doped carbon catalysts encapsulated with Fe3C nanoparticles.In this approach,the layer-structured FeOCl was first used as a template for the synthesis of a three-dimensional polypyrrole (PPy) structure.During the removal of the FeOCl template,the Fe3+ can be absorbed by PPy and then converted into Fe3C nanoparticles and Fe-N-C sites during the pyrolyzing process.As a result,the as-prepared catalysts could exhibit superior electrocatalytic ORR performance to the commercial Pt/C catalyst in alkaline solutions.Furthermore,the Zn-air battery assembled using the mesoporous carbon catalyst as the air electrode could surpass the commercial Pt/C catalyst in terms of the power density and energy density.

  8. Synthesis of an excellent electrocatalyst for oxygen reduction reaction with supercritical fluid: Graphene cellular monolith with ultrafine and highly dispersive multimetallic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yazhou; Cheng, Xiaonong; Yen, Clive H.; Wai, Chien M.; Wang, Chongmin; Yang, Juan; Lin, Yuehe

    2017-04-01

    Graphene cellular monolith (GCM) can be used as an excellent support for nanoparticles in widespread applications. However, it's still a great challenge to deposit the desirable nanoparticles in GCM that have small size, controllable structure, composition, and high dispersion using the current methods. Here we demonstrate a green, efficient and large-scale method to address this challenge using supercritical fluid (SCF). By this superior method, graphene hydrogel can be transferred into GCM while being deposited with ultrafine and highly dispersive nanoparticles. Specifically, the bimetallic PtFe/GCM and the trimetallic PtFeCo/GCM catalysts are successfully synthesized, and their electrocatalytic performances toward oxygen reduction reaction (ORR) are also studied. The resultant PtFe/GCM shows the significant enhancement in ORR activity, including a factor of 8.47 enhancement in mass activity (0.72 A mgPt-1), and a factor of 7.67 enhancement in specific activity (0.92 mA cm-2), comparing with those of the commercial Pt/C catalyst (0.085 A mgPt-1, 0.12 mA cm-2). Importantly, by introducing the Co, the trimetallic PtFeCo/GCM exhibits the further improved ORR activities (1.28 A mgPt-1, 1.80 mA cm-2). The high ORR activity is probably attributed to the alloying structure, ultrafine size, highly dispersive, well-defined, and a better interface with 3D porous graphene support.

  9. Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

    KAUST Repository

    AlYami, Noktan

    2016-05-17

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  10. Porous VO(x)N(y) nanoribbons supported on CNTs as efficient and stable non-noble electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Huang, K; Bi, K; Lu, Y K; Zhang, R; Liu, J; Wang, W J; Tang, H L; Wang, Y G; Lei, M

    2015-11-30

    Novel nanocomposites of carbon nanotubes supported porous VO(x)N(y) nonoribbons (VO(x)N(y)-CNTs) have been synthesized by the annealing of the sol-gel mixture of CNTs and V2O5 under NH3 atmosphere as well as the ageing process in air. Besides the morphological and structural characterizations revealed by TEM, SEAD, EDS, XRD and XPS measurements, typical electrochemical tests including cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry have been employed to determine the oxygen reduction reaction (ORR) performance of VO(x)N(y)-CNTs. Inspiringly, the results indicate that VO(x)N(y)-CNTs catalyst exhibits a 0.4 mA/cm(2) larger diffusion-limited current density, a 0.10  V smaller onset potential value, a 10.73% less of ORR current decay and an excellent methanol-tolerance compared with commercial Pt/C catalyst. Therefore, we have reasonable grounds to believe that this new VO(x)N(y)-CNTs nanocomposites can be regarded as a promising non-precious methanol-tolerant ORR catalyst candidate for alkaline fuel cells.

  11. Photoassisted oxygen reduction reaction on mpg-C3N4: The effects of elements doping on the performance of ORR

    Science.gov (United States)

    He, Qiuchen; Zhou, Feng; Zhan, Su; Huang, Naibao; Tian, Yu

    2018-02-01

    The oxygen reduction reaction (ORR) is a crux step in the fuel cells, which is limited to the catalysts. Low-cost nonmetal inorganic catalysts were considered to be the best prospect that may replace platinum. Graphitic carbon nitride (g-C3N4), which has wide prospect in photocatalysis, was found with the activity of ORR. In calculation work, we used the elements of the VIA family (O, S, and Se) to dope g-C3N4 and investigated the electronic properties and the ability of O2 adsorption in details based on the first principle. The result suggested that the performance of ORR of g-C3N4 may be enhanced by O doping, which can uplift the Fermi level of g-C3N4 and weaken the OH- absorption ability to enhance the O2 adsorption ability. After that, we synthetised O/g-C3N4 and S/g-C3N4 to test their ORR performance. According to the result, O doping can significantly enhance the performance of ORR of g-C3N4 which correspond with the calculation result. Then, the photo-assistant method was used to further enhance the ORR of g-C3N4 which was caused by the transition of the photo-induced electrons of g-C3N4 from VB to CB.

  12. N, S co-doped carbon spheres with highly dispersed CoO as non-precious metal catalyst for oxygen reduction reaction

    Science.gov (United States)

    Chen, Linlin; Guo, Xingpeng; Zhang, Guoan

    2017-08-01

    It is still a great challenge in preparing non-precious metal catalysts with high activity and long-term stability to substitute for precious metal catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we report a novel and facile catalyst-N, S co-doped carbon spheres with highly dispersed CoO (CoO@NS-CSs), where biomass glucose spheres act as carbon precursor and H2S, NH3 derived from the decomposition of thiourea not only provide N, S sources but also can etch carbon spheres to produce nanoporous structure. CoO@NS-CSs catalyst exhibits excellent ORR activity with a high onset potential of 0.946 V vs. RHE (reversible hydrogen electrode) and a half-wave potential of 0.821 V vs. RHE through a four-electron pathway in alkaline solution, which is comparable to commercial Pt/C catalyst (onset potential: 0.926 V vs. RHE, half-wave potential: 0.827 V vs. RHE). Furthermore, both the long-term stability and methanol-tolerance of CoO@NS-CSs catalyst are superior to those of commercial Pt/C catalyst. The excellent ORR performance of CoO@NS-CSs catalyst can be attributed to its micro-mesopore structure, high specific surface area (667 m2 g-1), and highly dispersed CoO. This work manifests that the obtained CoO@NS-CSs catalyst is promising to be applied to fuel cells.

  13. Porous carbon supported Fe-N-C composite as an efficient electrocatalyst for oxygen reduction reaction in alkaline and acidic media

    Science.gov (United States)

    Liu, Baichen; Huang, Binbin; Lin, Cheng; Ye, Jianshan; Ouyang, Liuzhang

    2017-07-01

    In recent years, non-precious metal electrocatalysts for oxygen reduction reaction (ORR) have attracted tremendous attention due to their high catalytic activity, long-term stability and excellent methanol tolerance. Herein, the porous carbon supported Fe-N-C catalysts for ORR were synthesized by direct pyrolysis of ferric chloride, 6-Chloropyridazin-3-amine and carbon black. Variation of pyrolysis temperature during the synthesis process leads to the difference in ORR catalytic activity. High pyrolysis temperature is beneficial to the formation of the "N-Fe" active sites and high electrical conductivity, but the excessive temperature will cause the decomposition of nitrogen-containing active sites, which are revealed by Raman, TGA and XPS. A series of synthesis and characterization experiments with/without nitrogen or iron in carbon black indicate that the coordination of iron and nitrogen plays a crucial role in achieving excellent ORR performances. Electrochemical test results show that the catalyst pyrolyzed at 800 °C (Fe-N-C-800) exhibits excellent ORR catalytic activity, better methanol tolerance and higher stability compared with commercial Pt/C catalyst in both alkaline and acidic conditions.

  14. High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts.

    Science.gov (United States)

    Sebastián, David; Serov, Alexey; Artyushkova, Kateryna; Gordon, Jonathan; Atanassov, Plamen; Aricò, Antonino S; Baglio, Vincenzo

    2016-08-09

    Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A Platinum Monolayer Core-Shell Catalyst with a Ternary Alloy Nanoparticle Core and Enhanced Stability for the Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Haoxiong Nan

    2015-01-01

    Full Text Available We synthesize a platinum monolayer core-shell catalyst with a ternary alloy nanoparticle core of Pd, Ir, and Ni. A Pt monolayer is deposited on carbon-supported PdIrNi nanoparticles using an underpotential deposition method, in which a copper monolayer is applied to the ternary nanoparticles; this is followed by the galvanic displacement of Cu with Pt to generate a Pt monolayer on the surface of the core. The core-shell Pd1Ir1Ni2@Pt/C catalyst exhibits excellent oxygen reduction reaction activity, yielding a mass activity significantly higher than that of Pt monolayer catalysts containing PdIr or PdNi nanoparticles as cores and four times higher than that of a commercial Pt/C electrocatalyst. In 0.1 M HClO4, the half-wave potential reaches 0.91 V, about 30 mV higher than that of Pt/C. We verify the structure and composition of the carbon-supported PdIrNi nanoparticles using X-ray powder diffraction, X-ray photoelectron spectroscopy, thermogravimetry, transmission electron microscopy, and energy dispersive X-ray spectrometry, and we perform a stability test that confirms the excellent stability of our core-shell catalyst. We suggest that the porous structure resulting from the dissolution of Ni in the alloy nanoparticles may be the main reason for the catalyst’s enhanced performance.

  16. Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

    KAUST Repository

    AlYami, Noktan; LaGrow, Alec P.; Joya, khurram; Hwang, Jinyeon; Katsiev, Khabiboulakh; Anjum, Dalaver H.; Losovyj, Yaroslav; Sinatra, Lutfan; Kim, Jin Young; Bakr, Osman

    2016-01-01

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  17. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed; Merzougui, Belabbes A.; Akinpelu, Akeem; Laoui, Tahar; Hedhili, Mohamed N.; Swain, Greg M.; Shao, Minhua

    2014-01-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  18. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Imran Jafri, Razack; Sujatha, N.; Ramaprabhu, S. [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai (India); Rajalakshmi, N. [Center for Fuel Cell Technology (ARCI), Madavakkam, Chennai (India)

    2009-08-15

    Bi-functional catalysts based on Au supported on oxide based nanomaterials for use in fuel cells were evaluated by electrochemical methods for oxygen reduction reaction (ORR) in Polymer Electrolyte Membrane Fuel Cell (PEMFC). Metal oxide coated multi walled carbon nanotubes (MWNTs) (MnO{sub 2}/MWNT and ZnO/MWNT) were prepared by reduction of potassium permanganate and oxidation of Zn powder on MWNT surface respectively. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT were prepared by chemical reduction of chloroauric acid on MnO{sub 2}/MWNT and ZnO/MWNT. The samples were characterized and linear sweep voltammetric studies were performed in N{sub 2} saturated, O{sub 2} saturated and methanol containing 1 M KOH solution and the results have been discussed. A single fuel cell was also constructed using Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as ORR electrocatalysts. A maximum power density of 45 mW/cm{sup 2} and 56 mW/cm{sup 2} was obtained with Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT respectively. Additionally, the methanol tolerance of these electrocatalysts has been investigated and results have been discussed. (author)

  19. Fe-N-C electrocatalysts for oxygen reduction reaction synthesized by using aniline salt and Fe3+/H2O2 catalytic system

    KAUST Repository

    Bukola, Saheed

    2014-11-01

    Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe3+/H2O2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts\\' porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO4. The catalysts show improved ORR activities close to that of Pt-based catalysts, low H2O2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

  20. Facile preparation of efficient electrocatalysts for oxygen reduction reaction: One-dimensional meso/macroporous cobalt and nitrogen Co-doped carbon nanofibers

    Science.gov (United States)

    Yoon, Ki Ro; Choi, Jinho; Cho, Su-Ho; Jung, Ji-Won; Kim, Chanhoon; Cheong, Jun Young; Kim, Il-Doo

    2018-03-01

    Efficient electrocatalyst for oxygen reduction reaction (ORR) is an essential component for stable operation of various sustainable energy conversion and storage systems such as fuel cells and metal-air batteries. Herein, we report a facile preparation of meso/macroporous Co and N co-doped carbon nanofibers (Co-Nx@CNFs) as a high performance and cost-effective electrocatalyst toward ORR. Co-Nx@CNFs are simply obtained from electrospinning of Co precursor and bicomponent polymers (PVP/PAN) followed by temperature controlled carbonization and further activation step. The prepared Co-Nx@CNF catalyst carbonized at 700 °C (Co-Nx@CNF700) shows outstanding ORR performance, i.e., a low onset potential (0.941 V) and half wave potential (0.814 V) with almost four-electron transfer pathways (n= 3.9). In addition, Co-Nx@CNF700 exhibits a superior methanol tolerance and higher stability (>70 h) in Zn-air battery in comparison with Pt/C catalyst (∼30 h). The outstanding performance of Co-Nx@CNF700 catalysts is attributed to i) enlarged surface area with bimodal porosity achieved by leaching of inactive species, ii) increase of exposed ORR active Co-Nx moieties and graphitic edge sites, and iii) enhanced electrical conductivity and corrosion resistance due to the existence of numerous graphitic flakes in carbon matrix.