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Sample records for oxygen electrode reactions

  1. 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...

  2. 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.

  3. 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.

  4. 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...

  5. 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.

  6. 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

  7. 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.

  8. 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)

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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...

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Robust high temperature oxygen sensor electrodes

    DEFF Research Database (Denmark)

    Lund, Anders

    Platinum is the most widely used material in high temperature oxygen sensor electrodes. However, platinum is expensive and the platinum electrode may, under certain conditions, suffer from poisoning, which is detrimental for an oxygen sensor. The objective of this thesis is to evaluate electrode...... materials as candidates for robust oxygen sensor electrodes. The present work focuses on characterising the electrochemical properties of a few electrode materials to understand which oxygen electrode processes are limiting for the response time of the sensor electrode. Three types of porous platinum......-Dansensor. The electrochemical properties of the electrodes were characterised by electrochemical impedance spectroscopy (EIS), and the structures were characterised by x-ray diffraction and electron microscopy. At an oxygen partial pressures of 0.2 bar, the response time of the sensor electrode was determined by oxygen...

  8. 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

  9. In situ formation of a 3D core-shell and triple-conducting oxygen reduction reaction electrode for proton-conducting SOFCs

    Science.gov (United States)

    Zhang, Zhenbao; Wang, Jian; Chen, Yubo; Tan, Shaozao; Shao, Zongping; Chen, Dengjie

    2018-05-01

    BaZrxCeyY1-x-yO3-δ are recognized proton-conducting electrolyte materials for proton-conducting solid oxide fuel cells (H+-SOFCs) below 650 °C. Here Co cations are incorporated into the BaZr0.4Ce0.4Y0.2O3-δ (BZCY) scaffold to generate a 3D core-shell and triple-conducting (H+/O2-/e-) electrode in situ via infiltrating and reactive sintering. The core is the bulk BZCY scaffold, while the shell is composed of the cubic Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ, cubic spinel Co3O4 and cubic fluorite (Ce, Zr, Y)O2. The obtained electrode exhibits an excellent compatibility with the BZCY electrolyte, and performs well in yielding a low and stable polarization resistance for oxygen reduction reaction for intermediate-temperature H+-SOFCs. In particular, it achieves polarization resistances as low as 0.094 and 0.198 Ω cm2 at 650 and 600 °C in wet air (3% H2O) when the sintering temperature for the electrode is 900 °C. In addition, a symmetrical cell also exhibits operation stability of 70 h at 650 °C. Furthermore, a fuel cell assembled with the 3D core-shell and triple-conducting electrode delivers a peak power density of ∼330 mW cm-2 at 650 °C. The substantially improved electrochemical performance and high stability are ascribed to the unique core-shell structure and the formation of Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ in the shell.

  10. 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.

  11. 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.

  12. Electron transfer number control of the oxygen reduction reaction on nitrogen-doped reduced graphene oxides for the air electrodes of zinc-air batteries and organic degradation

    International Nuclear Information System (INIS)

    Wu, Sheng-Hui; Li, Po-Chieh; Hu, Chi-Chang

    2016-01-01

    The mean electron transfer number (n) of the oxygen reduction reaction (ORR) on reduced graphene oxide (rGO) is controlled by nitrogen doping for the air electrodes of Zn-air batteries and electrochemical organic degradation. Melamine and pyrrole are employed as the nitrogen sources for fabricating N-doped rGO (N-rGO) by microwave-assisted hydrothermal synthesis (MAHS). The n value of the ORR is determined by the rotating ring-disk electrode (RRDE) voltammetry and is successfully controlled from 2.34 to 3.93 by preparation variables. The N-doped structures are examined by the x-ray photoelectron spectroscopic (XPS) analysis. The morphology and the defect degree of N-rGOs are characterized by high resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy. N-rGOs with high and low n values are employed as the air electrode catalysts of zinc-air batteries and in-situ hydrogen peroxide (H_2O_2) generation, respectively. The highest discharge cell voltage of 1.235 V for a Zn-air battery is obtained at 2 mA cm"−"2 meanwhile the current efficiency of H_2O_2 generation in 1-h electrolysis at 0 V (vs. RHE) reaches 43%. The electrocatalytic degradation of orange G (OG), analyzed by UV-VIS absorption spectra, reveals a high decoloration degree from the relative absorbance of 0.38 for the azo π-conjugation structure of OG. - Highlights: • The mean electron transfer number (n) is controlled by nitrogen doping. • Melamine and pyrrole are used as the nitrogen sources for fabricating N-rGO. • The n value is successfully controlled from 2.34 to 3.93 by preparation variables. • The highest discharge cell voltage of 1.235 V for a Zn-air battery. • The current efficiency of H_2O_2 generation 1-h electrolysis reaches 43%.

  13. Electron transfer number control of the oxygen reduction reaction on nitrogen-doped reduced graphene oxides for the air electrodes of zinc-air batteries and organic degradation

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Sheng-Hui; Li, Po-Chieh; Hu, Chi-Chang, E-mail: cchu@che.nthu.edu.tw

    2016-11-01

    The mean electron transfer number (n) of the oxygen reduction reaction (ORR) on reduced graphene oxide (rGO) is controlled by nitrogen doping for the air electrodes of Zn-air batteries and electrochemical organic degradation. Melamine and pyrrole are employed as the nitrogen sources for fabricating N-doped rGO (N-rGO) by microwave-assisted hydrothermal synthesis (MAHS). The n value of the ORR is determined by the rotating ring-disk electrode (RRDE) voltammetry and is successfully controlled from 2.34 to 3.93 by preparation variables. The N-doped structures are examined by the x-ray photoelectron spectroscopic (XPS) analysis. The morphology and the defect degree of N-rGOs are characterized by high resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy. N-rGOs with high and low n values are employed as the air electrode catalysts of zinc-air batteries and in-situ hydrogen peroxide (H{sub 2}O{sub 2}) generation, respectively. The highest discharge cell voltage of 1.235 V for a Zn-air battery is obtained at 2 mA cm{sup −2} meanwhile the current efficiency of H{sub 2}O{sub 2} generation in 1-h electrolysis at 0 V (vs. RHE) reaches 43%. The electrocatalytic degradation of orange G (OG), analyzed by UV-VIS absorption spectra, reveals a high decoloration degree from the relative absorbance of 0.38 for the azo π-conjugation structure of OG. - Highlights: • The mean electron transfer number (n) is controlled by nitrogen doping. • Melamine and pyrrole are used as the nitrogen sources for fabricating N-rGO. • The n value is successfully controlled from 2.34 to 3.93 by preparation variables. • The highest discharge cell voltage of 1.235 V for a Zn-air battery. • The current efficiency of H{sub 2}O{sub 2} generation 1-h electrolysis reaches 43%.

  14. Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

    Science.gov (United States)

    Okubo, Masashi; Yamada, Atsuo

    2017-10-25

    Lithium-ion batteries are key energy-storage devices for a sustainable society. The most widely used positive electrode materials are LiMO 2 (M: transition metal), in which a redox reaction of M occurs in association with Li + (de)intercalation. Recent developments of Li-excess transition-metal oxides, which deliver a large capacity of more than 200 mAh/g using an extra redox reaction of oxygen, introduce new possibilities for designing higher energy density lithium-ion batteries. For better engineering using this fascinating new chemistry, it is necessary to achieve a full understanding of the reaction mechanism by gaining knowledge on the chemical state of oxygen. In this review, a summary of the recent advances in oxygen-redox battery electrodes is provided, followed by a systematic demonstration of the overall electronic structures based on molecular orbitals with a focus on the local coordination environment around oxygen. We show that a π-type molecular orbital plays an important role in stabilizing the oxidized oxygen that emerges upon the charging process. Molecular orbital principles are convenient for an atomic-level understanding of how reversible oxygen-redox reactions occur in bulk, providing a solid foundation toward improved oxygen-redox positive electrode materials for high energy-density batteries.

  15. 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...

  16. New Hypothesis for SOFC Ceramic Oxygen Electrode Mechanisms

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Chatzichristodoulou, Christodoulos; Graves, Christopher R.

    2016-01-01

    A new hypothesis for the electrochemical reaction mechanism in solid oxide cell ceramic oxygen electrodes is proposed based on literature including our own results. The hypothesis postulates that the observed thin layers of SrO-La2O3 on top of ceramic perovskite and other Ruddlesden-Popper...

  17. 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.

  18. 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.

  19. Surface Characterization and Electrocatalytic Properties of the Ti/Ir0.3Ti(0.7-xPbx O2-Coated Electrodes for Oxygen Evolution Reaction in Acidic Media

    Directory of Open Access Journals (Sweden)

    Oliveira-Sousa Adriana de

    2002-01-01

    Full Text Available In this work a systematic investigation was carried out of the surface characterization and electrocatalytic activity of Ti/Ir0.3Ti(0.7-xPb x O2-coated electrodes (0 <= x <= 0.7, using the oxygen evolution reaction (OER in 0.5 mol dm-3 H2SO4 as model. The electrodes were prepared by thermal decomposition of IrCl3, TiCl3 and Pb(NO32 at 600 °C for 1 h using Ti as support. X-ray diffraction shows that the layers are crystalline and that the corresponding metal oxides are present. The surface morphology of the samples, before and after use under extensive oxygen evolution (Tafel experiment, was characterized by Scanning Electron Microscopy and the micrograph analyses show that the OER promotes the dissolution of the oxide layer. The redox processes occurring on the surface were characterized by cyclic voltammetry at 20 mV s-1 in 0.5 mol dm-3 aqueous H2SO4, at room temperature, and were controlled by the Ir3+/Ir4+ couple. The measured anodic voltammetric charge is related to the active area of the electrode showing that the replacement of TiO2 by PbO2 increases the surface area with the higher value being at 50 mol% PbO2. After oxygen evolution, the surface area increases slightly. Tafel slopes are independent of Pb content with the values around 60 mV decade-1, which suggest that only Ir sites are active for OER. The values of normalized current (i/q a show some inhibition of the OER as TiO2 is replaced by PbO2 suggesting that PbO2, can be a good choice, with potential to improve the selectivity of the system. The reaction order with respect to H+ ion is zero at constant overpotential and ionic strength. The values of Tafel slope and reaction order indicate that a single reaction mechanism is operating.

  20. Activated carbon from orange peels as supercapacitor electrode and catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell

    Directory of Open Access Journals (Sweden)

    M. Dhelipan

    2017-05-01

    Full Text Available Activated carbon is synthesized using orange peel as precursor through chemical activation using H3PO4 and its ability as electrocatalyst support for ORR reaction is examined. The prepared material was subjected to various structural, compositional, morphological and electrochemical studies. For ORR activity, the platinum loaded on activated carbon (Pt/OP-AC was investigated by cyclic voltammograms (CVs recorded in N2 and O2 saturated 0.1 M aqueous HClO4. For supercapacitor performance, three electrode systems was tested in aqueous H2SO4 for feasibility determination and showed electrochemical double layer capacitance (EDLC behaviour which is expected for activated carbon like materials. Electrochemical surface area (ECSA of the activated carbon from orange peel is measured using CV. The physical properties of the prepared carbon are studied using SEM (scanning electron microscope, XRD (X-ray diffraction, Fourier transform infrared (FT-IR spectroscopy and Raman spectroscopy. The AC derived from orange peels delivered a high specific capacitance of 275 F g−1 at 10 mV s-1 scan rate. Hence, this study suggested that orange peels may be considered not only as a potential alternative source for synthesizing carbon supported catalyst for fuel cell application but also highlight the production of low-cost carbon for further applications like supercapacitors.

  1. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  2. Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

    Science.gov (United States)

    Guan, Zixuan; Chen, Di; Chueh, William C

    2017-08-30

    The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

  3. System Li2O-MoO3 as a catalyst of oxygen (air) electrode

    International Nuclear Information System (INIS)

    Gavdzik, A.; Gajda, S.; Sofronkov, A.

    2000-01-01

    Potential of electrode on the basis of system Li x Mo 2-x O 6 (x 0.1-0.5) in alkaline solution saturated by oxygen was studied by the method of polarization curves recording. It is ascertained that the value of stationary potential characteristic of the electrode described under the conditions mentioned is determined by reversible reaction between oxygen and water molecules, resulting in formation of hydroxyl and hydrogen peroxide anions. Practicability of using the solid solutions on the basis of molybdenum oxide with additions of lithium oxide as a catalyst of oxygen (air) electrode in electrochemical current sources is demonstrated [ru

  4. Influence of Nafion film on oxygen reduction reaction and hydrogen peroxide formation on Pt electrode for proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Ohma, Atsushi; Fushinobu, Kazuyoshi; Okazaki, Ken

    2010-01-01

    The influence of Nafion film on ORR kinetics and H 2 O 2 formation on a Pt electrode was investigated using RRDE in 0.1 M HClO 4 . It was found that the Nafion-coated Pt system showed lower apparent ORR activity and more H 2 O 2 production than the bare Pt electrode system. From the temperature sensitivity, it was revealed that the apparent activation energies of ORR in the Nafion-coated Pt system were lower than the bare Pt electrode system, and the H 2 O 2 formation was suppressed with the increase of the temperature. In order to analyze the results furthermore, other systems (0.1/1.0 M, HClO 4 /CF 3 SO 3 H) with the bare Pt electrodes were also examined as references. It was exhibited that the ORR kinetic current, the H 2 O 2 formation, and the apparent activation energies of 1.0 M CF 3 SO 3 H system were close to those of the Nafion-coated Pt system. We concluded that the orientation of anion species of Nafion and CF 3 SO 3 H to the Pt surface via water molecules, as well as a fluorocarbon polymer network of Nafion, might block O 2 adsorption, resulting in the smaller effective surface area of the Pt electrode for ORR, the smaller ORR kinetic current, and the more H 2 O 2 production.

  5. Electrode redox reactions with polarizable molecules

    Science.gov (United States)

    Matyushov, Dmitry V.

    2018-04-01

    A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

  6. Toxin detection using a tyrosinase-coupled oxygen electrode.

    Science.gov (United States)

    Smit, M H; Rechnitz, G A

    1993-02-15

    An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

  7. Composite Sr- and V-doped LaCrO3/YSZ sensor electrode operating at low oxygen levels

    DEFF Research Database (Denmark)

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

    2012-01-01

    A porous composite electrode of La0.8Sr0.2Cr0.97V0.03O3 -delta (LSCV) and yttria-stabilised zirconia (YSZ) was evaluated as a possible candidate for high-temperature potentiometric oxygen sensor measuring electrodes. The oxygen processes at the electrode were characterised by performing electroch....... The relatively low response time at 700º C at an oxygen partial pressure of around 5x10-6 bar and an inlet gas flow rate of 8 L h-1 makes the LSCV/YSZ electrode suitable for use as an potentiometric oxygen sensor electrodes.......A porous composite electrode of La0.8Sr0.2Cr0.97V0.03O3 -delta (LSCV) and yttria-stabilised zirconia (YSZ) was evaluated as a possible candidate for high-temperature potentiometric oxygen sensor measuring electrodes. The oxygen processes at the electrode were characterised by performing...... and 400 nm. At oxygen partial pressures around 0.2 bar at 700º C, the oxygen reaction is dominated by solid-state diffusion of oxide ions and surface reaction kinetics. At oxygen partial pressures around 10-5 bar above 800º C, gas phase mass transport processes dominate the impedance spectra...

  8. Improved Internal Reference Oxygen Sensors with Composite Ceramic Electrodes

    DEFF Research Database (Denmark)

    Hu, Qiang; Jacobsen, Torben; Hansen, Karin Vels

    2012-01-01

    Potentiometric oxygen sensors with an internal reference electrode, which uses the equilibrium pO2 of the binary mixture of Ni/NiO as the reference, are demonstrated. The cells employ Pt or composite ceramics as the sensing electrode. The cells are fabricated by a flexible and potentially low cost...... and performance are highly reproducible. The composite ceramics, based on strontium doped manganite and yttria doped zirconia, are proven superior over Pt to serve as the electrode material....

  9. Benchmarking Pt-based electrocatalysts for low temperature fuel cell reactions with the rotating disk electrode

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov; Escribano, Maria Escudero; Velazquez-Palenzuela, Amado Andres

    2015-01-01

    We present up-to-date benchmarking methods for testing electrocatalysts for polymer exchange membrane fuel cells (PEMFC), using the rotating disk electrode (RDE) method. We focus on the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) in the presence of CO. We have chosen...

  10. Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO2 Reduction

    DEFF Research Database (Denmark)

    Cavalca, Filippo Carlo; Ferragut, Rafael; Aghion, Stefano

    2017-01-01

    Oxide-derived copper (OD-Cu) electrodes exhibit higher activity than pristine copper during the carbon dioxide reduction reaction (CO2RR) and higher selectivity towards ethylene. The presence of residual subsurface oxygen in OD-Cu has been proposed to be responsible for such improvements, although...

  11. 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.

  12. The water decomposition reactions on boron-doped diamond electrodes

    International Nuclear Information System (INIS)

    Suffredini, Hugo B.; Machado, Sergio A.S; Avaca, Luis A.

    2004-01-01

    The electrochemical processes occurring at both edges of the wide electrochemical window of the boron doped diamond (BDD) electrode were studied by polarization curves experiments to evaluate the apparent energy of activation for the rate determining step in each reaction. It was found that the hydrogen evolution reaction occurs by a Volmer-Heyrovsky mechanism with the first step being the RDS. Moreover, the apparent energy of activation calculated from the Tafel plots presented a value as high as 150 kJ mol -1 , indicating the formation of the M-H intermediate that is characteristic for the Volmer step. On the other hand, the apparent energy of activation for the oxygen evolution reaction was found to be 106 kJ mol -1 suggesting that the RDS in this mechanism is the initial adsorption step. In this way, it was demonstrated that the interaction between water molecules and the electrode surface is strongly inhibited on BDD thus justifying the extended potential window observed for this material. (author)

  13. The water decomposition reactions on boron-doped diamond electrodes

    Directory of Open Access Journals (Sweden)

    Suffredini Hugo B

    2004-01-01

    Full Text Available The electrochemical processes occurring at both edges of the wide electrochemical window of the boron doped diamond (BDD electrode were studied by polarization curves experiments to evaluate the apparent energy of activation for the rate determining step in each reaction. It was found that the hydrogen evolution reaction occurs by a Volmer-Heyrovsky mechanism with the first step being the RDS. Moreover, the apparent energy of activation calculated from the Tafel plots presented a value as high as 150 kJ mol-1, indicating the formation of the M-H intermediate that is characteristic for the Volmer step. On the other hand, the apparent energy of activation for the oxygen evolution reaction was found to be 106 kJ mol-1 suggesting that the RDS in this mechanism is the initial adsorption step. In this way, it was demonstrated that the interaction between water molecules and the electrode surface is strongly inhibited on BDD thus justifying the extended potential window observed for this material.

  14. Fabrication of high surface area graphene electrodes with high performance towards enzymatic oxygen reduction

    International Nuclear Information System (INIS)

    Di Bari, Chiara; Goñi-Urtiaga, Asier; Pita, Marcos; Shleev, Sergey; Toscano, Miguel D.; Sainz, Raquel; De Lacey, Antonio L.

    2016-01-01

    High surface area graphene electrodes were prepared by simultaneous electrodeposition and electroreduction of graphene oxide. The electrodeposition process was optimized in terms of pH and conductivity of the solution and the obtained graphene electrodes were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy and electrochemical methods (cyclic voltammetry and impedance spectroscopy). Electrodeposited electrodes were further functionalized to carry out covalent immobilization of two oxygen-reducing multicopper oxidases: laccase and bilirubin oxidase. The enzymatic electrodes were tested as direct electron transfer based biocathodes and catalytic currents as high as 1 mA/cm 2 were obtained. Finally, the mechanism of the enzymatic oxygen reduction reaction was studied for both enzymes calculating the Tafel slopes and transfer coefficients.

  15. Diffuse charge and Faradaic reactions in porous electrodes

    NARCIS (Netherlands)

    Biesheuvel, P.M.; Yu, F.; Bazant, M.Z.

    2011-01-01

    Porous electrodes instead of flat electrodes are widely used in electrochemical systems to boost storage capacities for ions and electrons, to improve the transport of mass and charge, and to enhance reaction rates. Existing porous electrode theories make a number of simplifying assumptions: (i) The

  16. 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....

  17. 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.

  18. The electrode kinetics of the evolution and dissolution of oxygen at the urania-zirconia interfaces

    International Nuclear Information System (INIS)

    Badwal, S.P.S.; Bevan, D.J.M.; Bockris, J.O'M.

    1980-01-01

    In order to assess the potential of urania-yttria fluorite-type solid solutions as electrodes for high-temperature electrolysis of steam, oxygen evolution and dissolution reactions have been studied at the (Usub(0.7)Ysub(0.3))Osub (2+x)/YSZ interface. A current-interruption technique was used to separate overpotential and resistive potential drop. In oxygen and air the overpotential-current curves obey the Tafel law, suggesting that a charge-transfer process is rate determining. Activation energies of 120 kJ mole -1 and 165 kJ mole -1 were obtained for the cathodic reaction in oxygen and air respectively. The capacitance obtained from galvanostatic transients varied with potential, temperature, and oxygen partial pressure. The average value of n, the number of electrons involved in the overall charge-transfer reaction, was determined to be 4.01 from reversible potential measurements. The overpotential losses are small for porous electrodes at high psub(O 2 ). A mechanism for the oxygen transfer reaction has been proposed and its limitations discussed. (author)

  19. Electrode-electrolyte BIMEVOX system for moderate temperature oxygen separation

    Energy Technology Data Exchange (ETDEWEB)

    Boivin, J.C.; Pirovano, C.; Nowogrocki, G.; Mairesse, G. [Laboratoire de Cristallochimie et Physicochimie du Solide, URA CNRS 452, USTL-ENSCL BP 108, 59652 Villeneuve d`Ascq (France); Labrune, Ph.; Lagrange, G. [Centre de recherches Claude Delorme, Air Liquide, Jouy en Josas (France)

    1998-12-01

    Electrochemical separation of oxygen from air is a promising application for oxide conductor solid electrolytes. However, several important specifications are required in order to obtain an efficient separation device. First of all, the electrolyte material must exhibit a high conductivity at moderate temperature. From this point of view, a new family of materials called BIMEVOX ideally fulfils this condition. Secondly, a typical separation device must comport two electrodes on opposite faces of the electrolyte. These electrodes must act as electronic collectors but also, at the cathodic side, as an oxygen dissociation catalyst. BIMEVOX electrolytes exhibit ionic conductivity values that can allow work at temperature below 500C. The classical electrode approach, like in solid oxide fuel cells, consists in using a specific mixed oxide, for instance strontium lanthanum manganite or cobaltite. However, the lower the temperature, the lower the efficiency of these electrodes which quickly appears as the limiting factor. In previous work on bismuth lead oxide electrolytes, we proposed a new approach that consists of using the surface of the bismuth-based electrolyte itself as the catalyst, the electron collection being then performed by a co-sintered metallic grid. This `in-situ` electrode system provides many advantages, particularly it eliminates the problem of the chemical compatibility between electrode and electrolyte materials. Taking into account the presence of both catalytic vanadium and bismuth cations in BIMEVOX, we checked under these conditions the separation of oxygen from air for different electrolytes (BICOVOX, BICUVOX, BIZNVOX) at various temperatures in the range 430-600C. For instance, using a BICOVOX pellet with a gold grid inserted on each side makes it possible to separate oxygen with nearly 100% efficiency for current density values up to 1000 mA/cm{sup -2}. For higher intensity values, the faradic efficiency progressively but reversibly decreases

  20. 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

  1. 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.

  2. 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.

  3. The electrochemical Peltier heat of the standard hydrogen electrode reaction

    International Nuclear Information System (INIS)

    Fang Zheng; Wang Shaofen; Zhang Zhenghua; Qiu Guanzhou

    2008-01-01

    A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on φ 0 * = 0 and ΔS 0 * = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN) 6 3- /Fe(CN) 6 4- system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied

  4. Electrochemical Reduction of Oxygen on Anthraquinone/Carbon Nanotubes Nanohybrid Modified Glassy Carbon Electrode in Neutral Medium

    Directory of Open Access Journals (Sweden)

    Zheng Gong

    2013-01-01

    Full Text Available The electrochemical behaviors of monohydroxy-anthraquinone/multiwall carbon nanotubes (MHAQ/MWCNTs nanohybrid modified glassy carbon (MHAQ/MWCNTs/GC electrodes in neutral medium were investigated; also reported was their application in the electrocatalysis of oxygen reduction reaction (ORR. The resulting MHAQ/MWCNTs nanohybrid was characterized by scanning electron microscope (SEM and transmission electron microscope (TEM. It was found that the ORR at the MHAQ/MWCNTs/GC electrode occurs irreversibly at a potential about 214 mV less negative than at a bare GC electrode in pH 7.0 buffer solution. Cyclic voltammetric and rotating disk electrode (RDE techniques indicated that the MHAQ/MWCNTs nanohybrid has high electrocatalytic activity for the two-electron reduction of oxygen in the studied potential range. The kinetic parameters of ORR at the MHAQ/MWCNTs nanohybrid modified GC electrode were also determined by RDE and EIS techniques.

  5. Improvement of Electrochemical Properties of Lithium–Oxygen Batteries Using a Silver Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jin-Bum; Luo, Xiangyi; Lu, Jun; Shin, Chang Dae; Yoon, Chong Seung; Amine, Khalil; Sun, Yang-Kook

    2015-07-09

    Silver (Ag) electrodes are prepared by an electrodeposition method at -0.25 V versus SCE. To evaluate the effect of particle size on Li–air cells, deposition times are 3, 10, 30, and 300 s. When cycled at a current density of 0.032 mA cm–2, the Ag-deposited electrode for 300 s shows very low polarization corresponding to the oxygen evolution reaction potential at 3.6 V. X-ray diffraction studies confirm that the main discharge product is Li2O2, and the results of scanning electron microscopy and transmission electron microscopy of the discharged electrodes show lithium peroxides at different positions due to the limitation of active sites on silver particles.

  6. 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

  7. 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.

  8. A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

    Science.gov (United States)

    Devi, Bandhana; Venkateswarulu, Mangili; Kushwaha, Himmat Singh; Halder, Aditi; Koner, Rik Rani

    2018-05-02

    Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised Fe III -based gel material, synthesised following a solvothermal method and the development of its composite (Fe 3 O 4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm -2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g -1 at a current density of 1 A g -1 . It is expected that this Fe 3 O 4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Electron transfer reactions to probe the electrode/solution interface

    Energy Technology Data Exchange (ETDEWEB)

    Capitanio, F.; Guerrini, E.; Colombo, A.; Trasatti, S. [Milan Univ., Milan (Italy). Dept. of Physical Chemistry and Electrochemistry

    2008-07-01

    The reactions that occur at the interface between an electrode and an electrolyte were examined with particular reference to the interaction of different electrode surfaces with redox couples. A semi-integration or convolution technique was used to study the kinetics of electron transfer on different electrode materials with different hydrophilic behaviour, such as Boron-Doped-Diamond (BDD), Au and Pt. Standard reversible redox couples were also investigated, including (Fe3+/2+, Fe(CN)63-/4-, Ru(NH3)63+/2+, Co(NH3)63+/2+, Ir4+/3+, V4+/5+ and V3+/2+). The proposed method proved to be simple, straightforward and reliable since the obtained kinetic information was in good agreement with data in the literature. It was concluded that the kinetics of the electrode transfer reactions depend on the chemical nature of the redox couple and electrode material. The method should be further extended to irreversible couples and other electrode materials such as mixed oxide electrodes. 3 refs., 2 figs.

  10. 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...

  11. Improved Internal Reference Oxygen Sensors Using Composite Oxides as Electrodes

    DEFF Research Database (Denmark)

    Hu, Qiang

    The thesis describes the research on and development of an internal reference oxygen sensor (IROS). The IROS is potentiometric and uses the equilibrium pO2of the binary mixture of Ni/NiO as the reference pO2. The sensing electrode of the IROS are made from metallic Pt or the composite of (La0.75S...... the application of IROSes are provided. Based on the concepts and fundamentals of the IROS, internal reference sensors that detect other gas species such as hydrogen, chlorine and bromine may be developed.......The thesis describes the research on and development of an internal reference oxygen sensor (IROS). The IROS is potentiometric and uses the equilibrium pO2of the binary mixture of Ni/NiO as the reference pO2. The sensing electrode of the IROS are made from metallic Pt or the composite of (La0.75Sr0...... from 8YSZ is evaluated quantitatively and figures that may be used to design the depletion period of an IROS due to the electronic leak of 8YSZ are provided. One dimensional numerical simulations are performed to study the variation in cell voltage during the process of gas mixing, and the asymmetric...

  12. Simulation of square wave voltammetry of three electrode reactions coupled by two reversible chemical reactions

    OpenAIRE

    Lovrić, Milivoj

    2017-01-01

    Three fast and reversible electrode reactions that are connected by two reversible chemical reactions that are permanently in the equilibrium are analysed theoretically for square wave voltammetry. The dependence of peak potentials on the dimensionless equilibrium constants of chemical reactions is calculated. The influence of the basic thermodynamic parameters on the square wave voltammetric responses is analysed.

  13. The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

    International Nuclear Information System (INIS)

    Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.; Bankston, C.P.; Thakoor, A.P.; Cole, T.

    1986-01-01

    The alkali metal thermoelectric converter is a direct energy conversion device, utilizing a high alkali metal activity gradient to generate electrical power. Its operation is based on the unique ion conductive properties of beta''-alumina solid electrolyte. The major barrier to application of this device is identification of an electrode which can maintain optimum power densities for operation times of >10,000h. Thin, porous molybdenum electrodes have shown the best performance characteristics, but show a variety of time dependent phenomena, including eventual degradation to power densities 3-5 times lower than initial values. Several Na-Mo-O compounds, including Na/sub 2/MoO/sub 4/ and Na/sub 2/Mo/sub 3/O/sub 6/, are formed during AMTEC operation. These compounds may be responsible for enhanced Na transport through Mo electrodes via sodium ion conduction, and eventual performance degradation due to their volatilization and decomposition. No decomposition of beta''-alumina has been observed under simulated AMTEC operating conditions up to 1373 K. In this paper, we present a model for chemical reactions occurring in porous molybdenum electrodes. The model is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, x-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell

  14. A Roadmap for Achieving Sustainable Energy Conversion and Storage: Graphene-Based Composites Used Both as an Electrocatalyst for Oxygen Reduction Reactions and an Electrode Material for a Supercapacitor

    Directory of Open Access Journals (Sweden)

    Peipei Huo

    2018-01-01

    Full Text Available Based on its unique features including 2D planar geometry, high specific surface area and electron conductivity, graphene has been intensively studied as oxygen reduction reaction (ORR electrocatalyst and supercapacitor material. On the one hand, graphene possesses standalone electrocatalytic activity. It can also provide a good support for combining with other materials to generate graphene-based electrocatalysts, where the catalyst-support structure improves the stability and performance of electrocatalysts for ORR. On the other hand, graphene itself and its derivatives demonstrate a promising electrochemical capability as supercapacitors including electric double-layer capacitors (EDLCs and pseudosupercapacitors. A hybrid supercapacitor (HS is underlined and the advantages are elaborated. Graphene endows many materials that are capable of faradaic redox reactions with an outstanding pseudocapacitance behavior. In addition, the characteristics of graphene-based composite are also utilized in many respects to provide a porous 3D structure, formulate a novel supercapacitor with innovative design, and construct a flexible and tailorable device. In this review, we will present an overview of the use of graphene-based composites for sustainable energy conversion and storage.

  15. 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.

  16. 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 ...

  17. Proton translocation stoichiometry of cytochrome oxidase: use of a fast-responding oxygen electrode.

    Science.gov (United States)

    Reynafarje, B; Alexandre, A; Davies, P; Lehninger, A L

    1982-01-01

    The mechanistic stoichiometry of vectorial H+ ejection coupled to electron transport from added ferrocytochrome c to oxygen by the cytochrome oxidase (EC 1.9.3.1) of rat liver mitoplasts was determined from measurements of the initial rates of electron flow and H+ ejection in the presence of K+ (with valinomycin). Three different methods of measuring electron flow were used: (a) dual-wavelength spectrophotometry of ferrocytochrome c oxidation, (b) uptake of scalar H+ for the reduction of O2 in the presence of a protonophore, and (c) a fast-responding membraneless oxygen electrode. The reliability of the rate measurements was first established against the known stoichiometry of the scalar reaction of cytochrome oxidase (2ferrocytochrome c + 2H+ + 1/2O2 leads to 2ferricytochrome c + H2O) in the presence of excess protonophore. With all three methods the directly observed vectorial H+/O ejection ratios in the presence of K+ + valinomycin significantly exceeded 3.0. However, because the rate of backflow of the ejected H+ into the mitoplasts is very high and increases with the increasing delta pH generated across the membrane, there is a very rapid decline in the observed H+/O ratio from the beginning of the reaction. Kinetic analysis of ferrocytochrome c oxidation by the mitoplasts, carried out with a fast-responding membraneless oxygen electrode, showed the reaction to be first order in O2 and allowed accurate extrapolation of the rates of O2 uptake and H+ ejection to zero time. At this point, at which there is zero delta pH across the membrane, the H+/O ejection ratio of the cytochrome oxidase reaction, obtained from the rates at zero time, is close to 4.0. PMID:6296824

  18. Free-standing, flexible β-Ni(OH)2/electrochemically-exfoliated graphene film electrode for efficient oxygen evolution

    Science.gov (United States)

    Wang, Lanlan; Zhang, Jian; Jiang, Weitao; Zhao, Hong; Liu, Hongzhong

    2018-03-01

    The oxidation of water into molecular oxygen (oxygen evolution reaction, OER) is a pivotal reaction in many energy conversion devices. The high cost of IrO2, however, seriously hinder its large-scale applications in water oxidation. Here, we have at first reported a free-standing and flexible film electrode consisting of 2D β-Ni(OH)2/electrochemically-exfoliated graphene hybrid nanosheets (NiG-2), which is synthesized by a solvothermal reaction and an assembly process. The as-obtained NiG-2 film electrode exhibited an excellent electrocatalytic OER activity with an extremely low OER onset overpotential of ∼250 mV in a 1 M KOH aqueous solution, which is lower than these of the commercial Ir/C (370 mV at 10 mA cm-2) catalyst.

  19. Electrocatalysis of oxygen reduction on nitrogen-containing multi-walled carbon nanotube modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Vikkisk, Merilin; Kruusenberg, Ivar; Joost, Urmas; Shulga, Eugene; Tammeveski, Kaido

    2013-01-01

    Highlights: ► Pyrolysis in the presence of urea was used for nitrogen doping of carbon nanotubes. ► N-doped carbon nanotubes were used as catalysts for the oxygen reduction reaction. ► N-doped carbon material showed a high catalytic activity for ORR in alkaline media. ► N-containing CNT material is an attractive cathode catalyst for alkaline membrane fuel cells. - Abstract: The electrochemical reduction of oxygen was studied on nitrogen-doped multi-walled carbon nanotube (NCNT) modified glassy carbon (GC) electrodes employing the rotating disk electrode (RDE) method. Nitrogen doping was achieved by simple pyrolysis of the carbon nanotube material in the presence of urea. The surface morphology and composition of the NCNT samples were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed a rather uniform distribution of NCNTs on the GC electrode substrate. The XPS analysis showed a successful doping of carbon nanotubes with nitrogen species. The RDE results revealed that in alkaline solution the N-doped nanotube materials showed a remarkable electrocatalytic activity towards oxygen reduction. At low overpotentials the reduction of oxygen followed a two-electron pathway on undoped carbon nanotube modified GC electrodes, whereas on NCNT/GC electrodes a four-electron pathway of O 2 reduction predominated. The results obtained are significant for the development of nitrogen-doped carbon-based cathodes for alkaline membrane fuel cells.

  20. 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...

  1. Using oxygen plasma treatment to improve the performance of electrodes for capacitive water deionization

    International Nuclear Information System (INIS)

    Hojati-Talemi, Pejman; Zou, Linda; Fabretto, Manrico; Short, Robert D.

    2013-01-01

    An oxygen plasma treatment was employed to modify the surface of carbon electrodes used in capacitive deionization (CDI). X-ray photoelectron spectroscopy analysis of samples showed that oxygen plasma is mainly attaching oxygenated groups on the PTFE binder used in these electrodes. By functionalizing the binder it can increase the hydrophilicity of the electrode surface and increase the available specific surface area. 2.5 min of plasma treatment resulted in the largest improvement of CDI performance of electrodes. Thermodynamic study of CDI performance showed that the modified electrodes followed Langmuir and Freundlich isotherms resulting from the increased interaction between the enhanced electrodes and water. The kinetic study showed that the CDI process followed a pseudo-first order adsorption kinetics. The calculated adsorption rate constants suggested that plasma modification can accelerate ion adsorption of electrodes

  2. 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

  3. 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....

  4. 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

  5. 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)

  6. Oxygen exchange and transport in dual phase ceramic composite electrodes.

    Science.gov (United States)

    Druce, John; Téllez, Helena; Ishihara, Tatsumi; Kilner, John A

    2015-01-01

    Composites consisting of a perovskite-based electronic or mixed conductor with a fluorite-structured ionic conductor are often used as electrodes in solid oxide electrochemical energy conversion devices. After sintering the materials, there is often evidence for inter-reaction between the two phases, or inter-diffusion of cations or impurities between the two phases. We studied the (18)O exchange properties of a composite consisting of CGO and LSCF in a 50 : 50 ratio. High resolution ToF-SIMS mapping reveals that the (18)O fraction at the very outer surface of grains of the CGO phase is much higher than expected from D* and k* values for the single-phase parent material. Surface compositional analysis by ToF-SIMS and low energy ion scattering (LEIS) spectroscopy suggests that the surfaces of the CGO grains in the composite do not show the impurities which typically segregate to the surface in single-phase CGO. Thus, the "cleaning" of impurities from the CGO surface by dissolution into the perovskite phase may be one explanation for the apparent enhanced surface exchange for CGO in these composites.

  7. 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

  8. High performance methanol-oxygen fuel cell with hollow fiber electrode

    Science.gov (United States)

    Lawson, Daniel D. (Inventor); Ingham, John D. (Inventor)

    1983-01-01

    A methanol/air-oxygen fuel cell including an electrode formed by open-ended ion-exchange hollow fibers having a layer of catalyst deposited on the inner surface thereof and a first current collector in contact with the catalyst layer. A second current collector external of said fibers is provided which is immersed along with the hollow fiber electrode in an aqueous electrolyte body. Upon passage of air or oxygen through the hollow fiber electrode and introduction of methanol into the aqueous electrolyte, a steady current output is obtained. Two embodiments of the fuel cell are disclosed. In the first embodiment the second metal electrode is displaced away from the hollow fiber in the electrolyte body while in the second embodiment a spiral-wrap electrode is provided about the outer surface of the hollow fiber electrode.

  9. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson; Yate, Luis; Valencia, Drochss P; Aperador, Willian; Siuzdak, Katarzyna; Torruella, Pau; Azanza, Eduardo; Estrade, Sonia; Iatsunskyi, Igor; Peiró , Francesca; Zhang, Xixiang; Tejada, Javier; Ziolo, Ronald F.

    2017-01-01

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced

  10. Topotactic Consolidation of Monocrystalline CoZn Hydroxides for Advanced Oxygen Evolution Electrodes.

    Science.gov (United States)

    Wang, Jing; Tan, Chuan Fu; Zhu, Ting; Ho, Ghim Wei

    2016-08-22

    We present a room temperature topotactic consolidation of cobalt and zinc constituents into monocrystalline CoZn hydroxide nanosheets, by a localized corrosion of zinc foils with cobalt precursors. By virtue of similar lattice orientation and structure coordination, the hybrid hydroxides amalgamate atomically without phase separation. Importantly, this in situ growth strategy, in combination with configurable percolated nanosheets, renders a high areal density of catalytic sites, immobilized structures, and conductive pathways between the nanosheets and underlying foils-all of which allow monocrystalline CoZn hydroxide nanosheet materials to function as effective electrodes for electrochemical oxygen evolution reactions. This convenient and eco-friendly topotactical transformation approach facilitates high-quality single crystal growth with improved multiphase purity and homogeneity, which can be extended to other transition metals for the fabrication of advanced functional nanocomposites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Hydrogen evolution reaction on electrodes with different PT/C loadings by electrochemical impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ortega-Chavez, L. [Inst. Tecnologico de Chihuahua 2, Chihuahua, Chih (Mexico); Ortega-Chavez, L.; Herrera-Peraza, E. [Centro de Investigacion en Materiales Avanzados, Chiuahua, Chih (Mexico); Verde, Y. [Inst. Tecnologico de Cancun, Cancun, Quintana Roo (Mexico)

    2008-04-15

    One of the most widely studied reactions in electrochemistry is the hydrogen evolution reaction (HER). HER is important for the development of water hydrolysis and fuel cell technologies. Because hydrogen-substrate interaction determines oxygen reduction efficiency, an understanding of the chemical and electronic state of hydrogen adsorbed on the electrocatalyst surface is required. Electrochemical impedance spectroscopy (EIS) is a proven highly efficient technique for interface characterization and kinetic parameter determination for different reactions carried out on interfaces. This article presented a study that utilized EIS for characterizing electrodes under HER by implementing a rotating disc electrode with different carbon supported platinum nanoparticles loadings and different potentials in acidic solutions. The results collected by EIS were analyzed in terms of equivalent circuits to calculate different parameters which were compared by statistical analysis. The study also considered the Volmer, Heyrovsky and Tafel steps in the HER reaction as well as a single electro-absorbed intermediate species. The article discussed the experimental set-up with reference to measurements, simulation and fitting. Parameters analysis using ANOVA were reviewed. It was concluded that an increase in impedance occurs when platinum loading decreases in both high and low frequencies. 22 refs., 1 tab., 5 figs.

  12. 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.

  13. Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

    International Nuclear Information System (INIS)

    Dilimon, V.S.; Venkata Narayanan, N.S.; Sampath, S.

    2010-01-01

    The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH 3 CONH 2 ), urea (NH 2 CONH 2 ) and ammonium nitrate (NH 4 NO 3 ). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step, 2-electron pathways of O 2 to H 2 O 2 and further reduction of H 2 O 2 to H 2 O. The first 2-electron reduction of O 2 to H 2 O 2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO 2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and RDE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BDD) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide.

  14. 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...

  15. 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.

  16. 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...

  17. 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.

  18. Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

    Science.gov (United States)

    Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

    2018-03-01

    Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

  19. Perovskites as electrodes of solid cells in sensitive elements of oxygen ion

    International Nuclear Information System (INIS)

    Gandurska, J.; Sniezynska, I.; Marek, A.; Szwagierczak, D.; Kulawik, J.

    1997-01-01

    The perovskite family comprises many compounds used in electronic applications. In this work perovskite materials based on LaCrO 3 were investigated, destined for electrodes of solid electrolyte oxygen sensors. lanthanum chromite powders modified by calcium, strontium and aluminium were prepared by the coprecipitation-calcination technique. The powders were examined using thermal analysis, x-ray diffraction analysis, scanning electron microscopy and transmission electron microscopy. Introductory studies of electromotive force of oxygen cells with yttria stabilized zirconia as solid electrolyte and perovskite-based electrodes proved that it is possible to replace expensive Pt electrodes by much cheaper perovskite ones. (author)

  20. Electrochemical monitoring of native catalase activity in skin using skin covered oxygen electrode.

    Science.gov (United States)

    Nocchi, Sarah; Björklund, Sebastian; Svensson, Birgitta; Engblom, Johan; Ruzgas, Tautgirdas

    2017-07-15

    A skin covered oxygen electrode, SCOE, was constructed with the aim to study the enzyme catalase, which is part of the biological antioxidative system present in skin. The electrode was exposed to different concentrations of H 2 O 2 and the amperometric current response was recorded. The observed current is due to H 2 O 2 penetration through the outermost skin barrier (referred to as the stratum corneum, SC) and subsequent catalytic generation of O 2 by catalase present in the underlying viable epidermis and dermis. By tape-stripping the outermost skin layers we demonstrate that SC is a considerable diffusion barrier for H 2 O 2 penetration. Our experiments also indicate that skin contains a substantial amount of catalase, which is sufficient to detoxify H 2 O 2 that reaches the viable epidermis after exposure of skin to high concentrations of peroxide (0.5-1mM H 2 O 2 ). Further, we demonstrate that the catalase activity is reduced at acidic pH, as compared with the activity at pH 7.4. Finally, experiments with often used penetration enhancer thymol shows that this compound interferes with the catalase reaction. Health aspect of this is briefly discussed. Summarizing, the results of this work show that the SCOE can be utilized to study a broad spectrum of issues involving the function of skin catalase in particular, and the native biological antioxidative system in skin in general. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. The evaluation of the polarization resistance in a tubular electrode and its application to the hydrogen electrode reaction

    International Nuclear Information System (INIS)

    Montero, M.A.; Marozzi, C.A.; Chialvo, M.R. Gennero de; Chialvo, A.C.

    2007-01-01

    An alternative method for the determination of the kinetic parameters involved in the elementary steps of the reaction mechanism of the hydrogen electrode reaction is proposed. It is based on the determination of the variation of the polarization resistance in a tubular platinum electrode with a laminar flow of electrolyte as a function of the activity of protons of the electrolyte solution. A theoretical expression that relates the experimental variables and the equilibrium polarization resistance is developed, which takes into account the current distribution along the electrode surface. The results are compared with others obtained previously, contributing to the verification of the kinetic mechanism through a completely different experimental procedure

  2. Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

    Science.gov (United States)

    Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

    2011-12-28

    Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

  3. 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

  4. 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

  5. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before. The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability.

  6. 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.

  7. 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) .

  8. 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)

  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. Catalytic EC′ reaction at a thin film modified electrode

    International Nuclear Information System (INIS)

    Gerbino, Leandro; Baruzzi, Ana M.; Iglesias, Rodrigo A.

    2013-01-01

    Numerical simulations of cyclic voltammograms corresponding to a catalytic EC′ reaction taking place at a thin film modified electrode are performed by way of finite difference method. Besides considering the chemical kinetic occurring inside the thin film, the model takes into account the different diffusion coefficients for each species at each of the involved phases, i.e. the thin film layer and bulk solution. The theoretical formulation is given in terms of dimensionless model parameters but a brief discussion of each of these parameters and their relationship to experimental variables is presented. Special emphasis is given to the use of working curve characteristics to quantify diffusion coefficient, homogeneous kinetic constant and thickness of the thin layer in a real system. Validation of the model is made by comparison of experimental results corresponding to the electron charge transfer of Ru(NH 3 ) 6 3+ /Ru(NH 3 ) 6 2+ hemi-couple at a thin film of a cross-linked chitosan film containing an immobilized redox dye

  14. 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...

  15. 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...

  16. 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.

  17. 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.

  18. 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)

  19. 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

  20. 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.)

  1. 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.

  2. In Situ-Grown ZnCo2O4 on Single-Walled Carbon Nanotubes as Air Electrode Materials for Rechargeable Lithium–Oxygen Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin; Xu, Wu; Yan, Pengfei; Bhattacharya, Priyanka; Cao, Ruiguo; Bowden, Mark E.; Engelhard, Mark H.; Wang, Chong M.; Zhang, Jiguang

    2015-10-12

    Although lithium-oxygen (Li-O2) batteries have great potential to be used as one of the next generation energy storage systems due to their ultrahigh theoretical specific energy, there are still many significant barriers before their practical applications. These barriers include electrolyte and electrode instability, poor ORR/OER efficiency and cycling capability, etc. Development of a highly efficient catalyst will not only enhance ORR/OER efficiency, it may also improve the stability of electrolyte because the reduced charge voltage. Here we report the synthesis of nano-sheet-assembled ZnCo2O4 spheres/single walled carbon nanotubes (ZCO/SWCNTs) composites as high performance air electrode materials for Li-O2 batteries. The ZCO catalyzed SWCNTs electrodes delivered high discharge capacities, decreased the onset of oxygen evolution reaction by 0.9 V during charge processes, and led to more stable cycling stability. These results indicate that ZCO/SWCNTs composite can be used as highly efficient air electrode for oxygen reduction and evolution reactions. The highly enhanced catalytic activity by uniformly dispersed ZnCo2O4 catalyst on nanostructured electrodes is expected to inspire

  3. Hydrodynamic voltammetric studies of the oxygen reduction at gold nanoparticles-electrodeposited gold electrodes

    International Nuclear Information System (INIS)

    El-Deab, Mohamed S.; Ohsaka, Takeo

    2002-01-01

    The electrocatalytic reduction of oxygen at Au nanoparticles-electrodeposited Au electrodes has been studied using rotating disk electrode (RDE) voltammetry in 0.5 M H 2 SO 4 . Upon analyzing and comparison of the limiting currents data obtained at various rotation speeds of this RDE with those obtained at the bulk Au electrode, an effective value of the number of electrons, n, involved in the electrochemical reduction of O 2 was estimated to be ca. 4 for the former electrode and ca. 3 for the bulk Au electrode at the same potential of -350 mV versus Ag/AgCl/KCl(sat.). This indicates the higher possibility of further reduction and decomposition of H 2 O 2 at Au nanoparticles-electrodeposited Au electrode in this acidic medium. The reductive desorption of the self-assembled monolayer of cysteine, which was formed on the Au nanoparticles-electrodeposited Au electrode, was used to monitor the change of the specific activity of the bulk Au electrode upon the electrodeposition of the Au nanoparticles

  4. 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

  5. Brain Tissue Oxygen: In Vivo Monitoring with Carbon Paste Electrodes

    Directory of Open Access Journals (Sweden)

    John P. Lowry

    2005-11-01

    Full Text Available In this communication we review selected experiments involving the use ofcarbon paste electrodes (CPEs to monitor and measure brain tissue O2 levels in awakefreely-moving animals. Simultaneous measurements of rCBF were performed using the H2clearance technique. Voltammetric techniques used include both differential pulse (O2 andconstant potential amperometry (rCBF. Mild hypoxia and hyperoxia produced rapidchanges (decrease and increase respectively in the in vivo O2 signal. Neuronal activation(tail pinch and stimulated grooming produced similar increases in both O2 and rCBFindicating that CPE O2 currents provide an index of increases in rCBF when such increasesexceed O2 utilization. Saline injection produced a transient increase in the O2 signal whilechloral hydrate produced slower more long-lasting changes that accompanied the behavioralchanges associated with anaesthesia. Acetazolamide increased O2 levels through an increasein rCBF.

  6. 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.

  7. 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.

  8. SiC-Si as a support material for oxygen evolution electrode in PEM steam electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Tomás García, Antonio Luis; Petrushina, Irina

    2011-01-01

    The need of higher energy efficiency in hydrogen production has promoted the research on improved catalysts for water electrolysis. In this work, a novel supported catalyst for oxygen evolution electrodes was prepared and characterized with different techniques. IrO2 supported on a SiC/Si composite...

  9. High performance electrode for electrochemical oxygen generator cell based on solid electrolyte ion transport membrane

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Wei; Shao, Zongping; Ran, Ran; Chen, Zhihao; Zeng, Pingying; Gu, Hongxia; Jin, Wanqin; Xu, Nanping [College of Chemistry and Chemical Engineering, Nanjing University of Technology, No. 5 Xin Mofan Road, Nanjing 210009, JiangSu (China)

    2007-06-30

    A double-layer composite electrode based on Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} + Sm{sub 0.2}Ce{sub 0.8}O{sub 1.9} (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 {omega} cm{sup 2} was reached at 800 C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm{sup -2} at 700 C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of {proportional_to}100%. (author)

  10. 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.

  11. New highly active oxygen reduction electrode for PEM fuel cell and Zn/air battery applications (NORA). Final report

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, D.; Zuettel, A.

    2008-04-15

    This illustrated final report for the Swiss Federal Office of Energy (SFOE) presents the results of a project concerning a new, highly active oxygen reduction electrode for PEM fuel cell and zinc/air battery applications. The goal of this project was, according to the authors, to increase the efficiency of the oxygen reduction reaction by lowering the activation polarisation through the right choice of catalyst and by lowering the concentration polarisation. In this work, carbon nanotubes are used as support material. The use of these nanotubes grown on perovskites is discussed. Theoretical considerations regarding activation polarisation are discussed and alternatives to the use of platinum are examined. The results of experiments carried out are presented in graphical and tabular form. The paper is completed with a comprehensive list of references.

  12. 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.

  13. 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

  14. Tailoring nanomaterial products through electrode material and oxygen partial pressure in a mini-arc plasma reactor

    International Nuclear Information System (INIS)

    Cui Shumao; Mattson, Eric C.; Lu, Ganhua; Hirschmugl, Carol; Gajdardziska-Josifovska, Marija; Chen Junhong

    2012-01-01

    Nanomaterials with controllable morphology and composition are synthesized by a simple one-step vapor condensation process using a mini-arc plasma source. Through systematic investigation of mini-arc reactor parameters, the roles of carrier gas, electrode material, and precursor on producing diverse nanomaterial products are revealed. Desired nanomaterial products, including tungsten oxide nanoparticles (NPs), tungsten oxide nanorods (NRs), tungsten oxide and tin oxide NP mixtures and pure tin dioxide NPs can thus be obtained by tailoring reaction conditions. The amount of oxygen in the reactor is critical to determining the final nanomaterial product. Without any precursor material present, a lower level of oxygen in the reactor favors the production of W 18 O 49 NRs with tungsten as cathode, while a high level of oxygen produces more round WO 3 NPs. With the presence of a precursor material, amorphous particles are favored with a high ratio of argon:oxygen. Oxygen is also found to affect tin oxide crystallization from its amorphous phase in the thermal annealing. Results from this study can be used for guiding gas phase nanomaterial synthesis in the future.

  15. 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....

  16. 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

  17. Reduction of skin damage from transcutaneous oxygen electrodes using a spray on dressing.

    Science.gov (United States)

    Evans, N J; Rutter, N

    1986-09-01

    A spray on, copolymer acrylic dressing (Op-Site) was used to limit the skin damage caused by a transcutaneous oxygen electrode and its adhesive ring. Two identical electrodes were applied to the abdominal skin of 10 preterm infants, one on untreated skin, the other after application of Op-Site. It was found that Op-Site prevented the epidermal damage (as measured by transepidermal water loss) that occurs when the adhesive ring is removed from untreated skin. It did not interfere with transcutaneous oxygen measurements; absolute values and response times were unchanged. Op-Site is therefore useful in preventing the skin trauma that occurs when transcutaneous oxygen monitoring is being performed in preterm infants below 30 weeks' gestation in the first week of life. Care must be taken, however, to prevent a build up of Op-Site--it should be applied as a single layer, allowed to dry, and removed after use.

  18. 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.

  19. 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

  20. 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.

  1. Oxygen Reduction Kinetics of La2-xSrxNiO 4+delta Electrodes for Solid Oxide Fuel Cells

    Science.gov (United States)

    Guan, Bo

    In the development of intermediate temperature solid oxide fuel cell (IT-SOFC), mixed ionic-electronic conductors (MIEC) have drawn big interests due to their both ionic and electronic species transport which can enlarge the 3-dimension of the cathode network. This thesis presents an investigation of MIEC of Ruddlesden-popper (RP) phases like K2NiF4 type La2NiO4+delta (LNO)-based oxides which have interesting transport, catalytic properties and suitable thermal expansion coefficients. The motivation of this present work is to further understand the fundamental of the effect of Sr doing on the oxygen reduction reaction (ORR) kinetics of LNO cathode. Porous symmetrical cells of La2-xSrxNiO4+delta (0≤x≤0.4) were fabricated and characterized by electrochemical impedance spectroscopy (EIS) in different PO2 from temperature range of 600˜800°C. The spectra were analyzed based on the impedance model introduced by Adler et al. The rate determining steps (RDS) for ORR were proposed and the responsible reasons were discussed. The overall polarization resistances of doped samples increase with Sr level. Surface oxygen exchange and bulk ionic diffusion co-control the ORR kinetics. With high Sr content (x=0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. However for porous symmetrical cells it is hard to associate the resistance from EIS directly to each ORR elementary processes because of the difficulty in describing the microstructure of the porous electrode. The dense electrode configuration was adopted in this thesis. By using the dense electrode, the surface area, the thickness of electrode, the interface between electrode and electrolyte and lastly the 3PB are theoretically well-defined. Through this method, there is a good chance to distinguish the contribution of surface exchange from other processes. Dense and thin electrode layers in thickness of ˜40 mum are fabricated by using a novel spray modified pressing method. Negligible

  2. 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.

  3. Microfabricated Collector-Generator Electrode Sensor for Measuring Absolute pH and Oxygen Concentrations.

    Science.gov (United States)

    Dengler, Adam K; Wightman, R Mark; McCarty, Gregory S

    2015-10-20

    Fast-scan cyclic voltammetry (FSCV) has attracted attention for studying in vivo neurotransmission due to its subsecond temporal resolution, selectivity, and sensitivity. Traditional FSCV measurements use background subtraction to isolate changes in the local electrochemical environment, providing detailed information on fluctuations in the concentration of electroactive species. This background subtraction removes information about constant or slowly changing concentrations. However, determination of background concentrations is still important for understanding functioning brain tissue. For example, neural activity is known to consume oxygen and produce carbon dioxide which affects local levels of oxygen and pH. Here, we present a microfabricated microelectrode array which uses FSCV to detect the absolute levels of oxygen and pH in vitro. The sensor is a collector-generator electrode array with carbon microelectrodes spaced 5 μm apart. In this work, a periodic potential step is applied at the generator producing transient local changes in the electrochemical environment. The collector electrode continuously performs FSCV enabling these induced changes in concentration to be recorded with the sensitivity and selectivity of FSCV. A negative potential step applied at the generator produces a transient local pH shift at the collector. The generator-induced pH signal is detected using FSCV at the collector and correlated to absolute solution pH by postcalibration of the anodic peak position. In addition, in oxygenated solutions a negative potential step at the generator produces hydrogen peroxide by reducing oxygen. Hydrogen peroxide is detected with FSCV at the collector electrode, and the magnitude of the oxidative peak is proportional to absolute oxygen concentrations. Oxygen interference on the pH signal is minimal and can be accounted for with a postcalibration.

  4. Reduction of skin damage from transcutaneous oxygen electrodes using a spray on dressing.

    OpenAIRE

    Evans, N J; Rutter, N

    1986-01-01

    A spray on, copolymer acrylic dressing (Op-Site) was used to limit the skin damage caused by a transcutaneous oxygen electrode and its adhesive ring. Two identical electrodes were applied to the abdominal skin of 10 preterm infants, one on untreated skin, the other after application of Op-Site. It was found that Op-Site prevented the epidermal damage (as measured by transepidermal water loss) that occurs when the adhesive ring is removed from untreated skin. It did not interfere with transcut...

  5. Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction

    Science.gov (United States)

    Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

    2016-07-01

    As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton’s second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

  6. Mechanism of the electrochemical hydrogen reaction on smooth tungsten carbide and tungsten electrodes

    International Nuclear Information System (INIS)

    Wiesener, K.; Winkler, E.; Schneider, W.

    1985-01-01

    The course of the electrochemical hydrogen reaction on smooth tungsten-carbide electrodes in hydrogen saturated 2.25 M H 2 SO 4 follows a electrochemical sorption-desorption mechanism in the potential range of -0.4 to +0.1 V. At potentials greater than +0.1 V the hydrogen oxidation is controlled by a preliminary chemical sorption step. Concluding from the similar behaviour of tungsten-carbide and tungsten electrodes after cathodic pretreatment, different tungsten oxides should be involved in the course of the hydrogen reaction on tungsten carbide electrodes. (author)

  7. In Situ Characterization of Ni and Ni/Fe Thin Film Electrodes for Oxygen Evolution in Alkaline Media by a Raman-Coupled Scanning Electrochemical Microscope Setup.

    Science.gov (United States)

    Steimecke, Matthias; Seiffarth, Gerda; Bron, Michael

    2017-10-17

    We present a spectroelectrochemical setup, in which Raman microscopy is combined with scanning electrochemical microscopy (SECM) in order to provide both spectroscopic and electrochemical information on the very same location of an electrode at the same time. The setup is applied to a subject of high academic and practical interest, namely, the oxygen evolution reaction at Ni and Ni/Fe electrodes. It comprises a transparent substrate electrode, onto which Ni and Ni/Fe thin films are deposited. An ultramicroelectrode (UME) is placed closely above the substrate to obtain electrochemical information, while a Raman microscope probes the same sample spot from below. To obtain information on oxygen evolution activity and structural changes, increasingly positive potentials from 0.1 up to 0.7 V vs Hg|HgO|1 M KOH were applied to the Ni/Fe-electrodes in 0.1 M KOH solution. Evolved oxygen is detected by reduction at a Pt UME, allowing for the determination of onset potentials, while the substrate current, which is recorded in parallel, is due to both overlapping oxygen evolution and the oxidation of Ni(OH) 2 to NiOOH. An optimum of 15% Fe in Ni/Fe films with respect to oxygen evolution activity was determined. At the same time, the potential-dependent formation of γ-NiOOH characterized by the Raman double band at 475 and 557 cm -1 allows for the conclusion that a certain amount of disorder introduced by Fe atoms is necessary to obtain high oxygen evolution reaction (OER) activity.

  8. 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.

  9. 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.

  10. 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.

  11. Electrochemical characteristics of vanadium redox reactions on porous carbon electrodes for microfluidic fuel cell applications

    International Nuclear Information System (INIS)

    Lee, Jin Wook; Hong, Jun Ki; Kjeang, Erik

    2012-01-01

    Microfluidic vanadium redox fuel cells are membraneless and catalyst-free fuel cells comprising a microfluidic channel network with two porous carbon electrodes. The anolyte and catholyte for fuel cell operation are V(II) and V(V) in sulfuric acid based aqueous solution. In the present work, the electrochemical characteristics of the vanadium redox reactions are investigated on commonly used porous carbon paper electrodes and compared to a standard solid graphite electrode as baseline. Half-cell electrochemical impedance spectroscopy is applied to measure the overall ohmic resistance and resistivity of the electrodes. Kinetic parameters for both V(II) and V(V) discharging reactions are extracted from Tafel plots and compared for the different electrodes. Cyclic voltammetry techniques reveal that the redox reactions are irreversible and that the magnitudes of peak current density vary significantly for each electrode. The obtained kinetic parameters for the carbon paper are implemented into a numerical simulation and the results show a good agreement with measured polarization curves from operation of a microfluidic vanadium redox fuel cell employing the same material as flow-through porous electrodes. Recommendations for microfluidic fuel cell design and operation are provided based on the measured trends.

  12. One-dimensional model of oxygen transport impedance accounting for convection perpendicular to the electrode

    Energy Technology Data Exchange (ETDEWEB)

    Mainka, J. [Laboratorio Nacional de Computacao Cientifica (LNCC), CMC 6097, Av. Getulio Vargas 333, 25651-075 Petropolis, RJ, Caixa Postal 95113 (Brazil); Maranzana, G.; Thomas, A.; Dillet, J.; Didierjean, S.; Lottin, O. [Laboratoire d' Energetique et de Mecanique Theorique et Appliquee (LEMTA), Universite de Lorraine, 2, avenue de la Foret de Haye, 54504 Vandoeuvre-les-Nancy (France); LEMTA, CNRS, 2, avenue de la Foret de Haye, 54504 Vandoeuvre-les-Nancy (France)

    2012-10-15

    A one-dimensional (1D) model of oxygen transport in the diffusion media of proton exchange membrane fuel cells (PEMFC) is presented, which considers convection perpendicular to the electrode in addition to diffusion. The resulting analytical expression of the convecto-diffusive impedance is obtained using a convection-diffusion equation instead of a diffusion equation in the case of classical Warburg impedance. The main hypothesis of the model is that the convective flux is generated by the evacuation of water produced at the cathode which flows through the porous media in vapor phase. This allows the expression of the convective flux velocity as a function of the current density and of the water transport coefficient {alpha} (the fraction of water being evacuated at the cathode outlet). The resulting 1D oxygen transport impedance neglects processes occurring in the direction parallel to the electrode that could have a significant impact on the cell impedance, like gas consumption or concentration oscillations induced by the measuring signal. However, it enables us to estimate the impact of convection perpendicular to the electrode on PEMFC impedance spectra and to determine in which conditions the approximation of a purely diffusive oxygen transport is valid. Experimental observations confirm the numerical results. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. 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.

  14. 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.

  15. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    Science.gov (United States)

    Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. Electrode reactions of iron oxide-hydroxide colloids.

    Science.gov (United States)

    Mahmoudi, Leila; Kissner, Reinhard

    2014-11-07

    Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing.

  3. Electrocatalytic performance of Pu(IV)/Pu(III) redox reaction at graphene modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Gupta, Ruma; Gamare, J.S.; Kamat, J.V.; Aggarwal, S.K.

    2014-01-01

    In this paper we explore the analytical perspectives of graphene modified electrode utilising commercially available graphene, which is well characterised, completely free from surfactants and has not been purposely oxidised or treated. We compare and critically contrast the electro-analytical performance of graphene modified glassy carbon electrodes (Gr/GC) with that of unmodified GC electrode towards Pu(IV)/Pu(III) redox reaction, monitoring of which has considerable importance in a plethora of areas where electrochemistry is conveniently and beneficially utilised for determination of nuclear fuels

  4. 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.

  5. 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.

  6. Stability and Performance of Oxygen Electrodes for Reversible Solid Oxide Cells

    Science.gov (United States)

    Railsback, Justin Gary

    Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources requires that large scale energy storage be implemented to ensure grid stability. Pumped hydro storage is currently the only technology available for large scale energy storage; however, pumped hydro remains geographically confined and susceptible to seasonal fluctuations and offers limited discharge hours. Recent system level models predict that reversible solid oxide cells may be a competitive solution, but two key advancements are required to realize the technology: low cell resistance (cell resistance, and when a cell is operated in electrolysis the oxygen electrode is known to degrade quickly. This work focuses on both aspects of the oxygen electrode. A Pr2NiO4 based electrode is developed that has improved phase stability and good polarization resistance ( 0.1 O•cm2 at 650 °C). The electrode is prepared by wet chemical impregnation (infiltration) of Pr2NiO4 precursors into a La0.9Sr 0.1Ga0.8Mg0.2O3 scaffold. Electrochemical data for a number cells is presented and the number of infiltrations is optimized. Preliminary life tests and x-ray data are presented. Pressurization of the oxygen electrode is predicted to decrease its polarization resistance and pressurization of the reversible solid oxide cell system is desirable to achieve high round-trip efficiency. The electrochemical performance of mixed electronic-ionic conducting electrodes has not been reported above 1 atm. Four candidate electrodes are examined under pressurization up to 10 atm: Pr2NiO4 infiltrated La0.9Sr0.1 Ga0.8Mg0.2O3, Sm0.5Sr 0.5CoO3 infiltrated Ce0.9Gd0.1O 2, single phase La0.6Sr0.4Co0.2Fe 0.8O3, and single phase Nd2NiO4. The role of the ion

  7. 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...

  8. Oxygen-deficient hematite nanorods as high-performance and novel negative electrodes for flexible asymmetric supercapacitors.

    Science.gov (United States)

    Lu, Xihong; Zeng, Yinxiang; Yu, Minghao; Zhai, Teng; Liang, Chaolun; Xie, Shilei; Balogun, Muhammad-Sadeeq; Tong, Yexiang

    2014-05-21

    Oxygen-deficient α-Fe2 O3 nanorods with outstanding capacitive performance are developed and demonstrated as novel negative electrodes for flexible asymmetric supercapacitors. The asymmetric-supercapacitor device based on the oxygen-deficient α-Fe2 O3 nanorod negative electrode and a MnO2 positive electrode achieves a maximum energy density of 0.41 mW·h/cm(3) ; it is also capable of charging a mobile phone and powering a light-emitting diode indicator. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Luminescent sensing and imaging of oxygen: fierce competition to the Clark electrode.

    Science.gov (United States)

    Wolfbeis, Otto S

    2015-08-01

    Luminescence-based sensing schemes for oxygen have experienced a fast growth and are in the process of replacing the Clark electrode in many fields. Unlike electrodes, sensing is not limited to point measurements via fiber optic microsensors, but includes additional features such as planar sensing, imaging, and intracellular assays using nanosized sensor particles. In this essay, I review and discuss the essentials of (i) common solid-state sensor approaches based on the use of luminescent indicator dyes and host polymers; (ii) fiber optic and planar sensing schemes; (iii) nanoparticle-based intracellular sensing; and (iv) common spectroscopies. Optical sensors are also capable of multiple simultaneous sensing (such as O2 and temperature). Sensors for O2 are produced nowadays in large quantities in industry. Fields of application include sensing of O2 in plant and animal physiology, in clinical chemistry, in marine sciences, in the chemical industry and in process biotechnology. © 2015 The Author. Bioessays published by WILEY Periodicals, Inc.

  10. FY 1998 annual report on the development of novel, high-activity oxygen electrode by ion-implantation; 1998 nendo ion chunyuho ni yoru shinkina kokassei sanso denkyoku no kaihatsu chosa hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-03-01

    An attempt has been made to develop an electrode material having high activity for oxygen generating reactions by ion-implantation, which is used to form the bulk defects (fine gaps at the atomic level) on the electrode surface, considered to serve as the active sites. It is found that implantation of the Co{sup +} or Zn{sup +} ion into a compound oxide electrode of Ti and Ru is accompanied by decreased overvoltage for oxygen generation by 50 to 100 mV. The Co{sup +} and Zn{sup +} ions, when implanted, cause damage of similar density in the thin film, decreasing its overvoltage to a similar extent, in spite of their different chemical properties, from which it is considered that the effect of ion implantation is not to change chemical properties of the film but to form a structural defect therein. A thin-film electrode of ruthenium dioxide, which is considered to be the oxygen generating electrode of the highest activity at present, is prepared and implanted with the Ru{sup +} ion, to observe the effect. The ion implantation also decreases the overvoltage by 50 to 70 mV, demonstrating its effect. The same principle is expected to be applicable to development of high-activity oxygen reducing electrode (electrode for fuel cell). (NEDO)

  11. Surface oxygenation of polypropylene using an air dielectric barrier discharge: the effect of different electrode-platen combinations

    International Nuclear Information System (INIS)

    Upadhyay, D.J.; Cui, N.-Y.; Anderson, C.A.; Brown, N.M.D.

    2004-01-01

    Polypropylene film has been modified in an air dielectric barrier discharge using two different electrode-platen configurations: stainless steel wire electrode-rubber platen or ceramic electrode-aluminium platen combinations. Modified films were characterised by static contact angle measurements, X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy (ATR-FT-IR). Surface hydrophilic modification appears to be governed by the presence of low-molecular weight oxidised functionalities using XPS and SIMS techniques. Irrespective of the type of electrode-platen combination used to obtain the discharge, oxygenated functionalities of identical nature are formed on the polymer surface. However, the degree of oxidation obtained by the discharge using the wire electrodes with the rubber platen was considerably greater. Further increase in the observed hydrophilicity due to molecular rearrangement and development of stable oxygenated functionalities was evident after 1 month of post-processing analysis

  12. 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.

  13. 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

  14. Oxygen electrodes for energy conversion and storage. Annual report, 1 October 1977-30 September 1978

    Energy Technology Data Exchange (ETDEWEB)

    None

    1980-01-15

    Research on the development of high performance, long life O/sub 2/ cathodes for both alkaline and acid electrolytes for a spectrum of applications including industrial electrolysis, fuel cells, and metal-air batteries is described. Oxygen electrocatalysts studied include platinum, silver, underpotential deposited layers and alloy metal layers on noble metal substrates, intercalated graphite, transition metal macrocyclic complexes, and transition metal oxides. Research on gas fed electrodes is also described. Results are presented and discussed in detail. An appendix on the electrodeposition of platinum crystallites on graphite substrates is included. (WHK)

  15. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

    Science.gov (United States)

    Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

    2016-04-18

    Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

  16. A novel ethanol/oxygen microfluidic fuel cell with enzymes immobilized onto cantilevered porous electrodes

    Science.gov (United States)

    Desmaële, D.; Nguyen-Boisse, T. T.; Renaud, L.; Tingry, S.

    2016-11-01

    This paper introduces a novel design of membraneless microfluidic biofuel cell that incorporates three-dimensional porous electrodes containing immobilized enzymes to catalyze redox reactions occurring in the presence of ethanol/O2 co-laminar flows. In order to maximize the penetration depth of the reactants inside the porous medium, we report on the preliminary evaluation of cantilevered bioelectrodes, namely the fibrous electrodes protrude along the internal walls of the miniature electrochemical chamber. As a first proof-of-concept, we demonstrate the integration of a bioanode and a biocathode into a lamination-based microfluidic cell fabricated via rapid prototyping. With enzymes deposited into the fibrous structure of 25 mm long, 1 mm wide and 0.11 mm thick carbon paper electrodes, the volumetric power density reached 1.25 mW cm-3 at 0.43 V under a flow rate of 50 μL min-1. An advantage of the presented microfluidic biofuel cell is that it can be adapted to include a larger active electrode volume via the vertical stacking of multiple thin bioelectrodes. We therefore envision that our design would be amenable to reach the level of net power required to supply energy to a plurality of low-consumption electronic devices.

  17. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

    International Nuclear Information System (INIS)

    Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.

    2017-01-01

    Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

  18. Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates.

    Science.gov (United States)

    Chadderdon, Xiaotong H; Chadderdon, David J; Matthiesen, John E; Qiu, Yang; Carraher, Jack M; Tessonnier, Jean-Philippe; Li, Wenzhen

    2017-10-11

    Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

  19. 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.

  20. 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

  1. Bubble dynamic templated deposition of three-dimensional palladium nanostructure catalysts: Approach to oxygen reduction using macro-, micro-, and nano-architectures on electrode surfaces

    International Nuclear Information System (INIS)

    Yang Guimei; Chen Xing; Li Jie; Guo Zheng; Liu Jinhuai; Huang Xingjiu

    2011-01-01

    Highlights: → We synthesize the Pd nanostructures by bubbles dynamic templated. → We obtain Pd nanobuds and Pd nanodendrites by changing the reaction precursor. → We obtain Pd macroelectrode voltammertric behavior using small amount of Pd materials. → We proved a ECE process. → The Pd nanostructures/GCE for O 2 reduction is a 2-step 4-electron process. - Abstract: Three-dimensional (3D) palladium (Pd) nanostructures (that is, nano-buds or nano-dendrites) are fabricated by bubble dynamic templated deposition of Pd onto a glassy carbon electrode (GCE). The morphology can be tailored by changing the precursor concentration and reaction time. Scanning electron microscopy images reveal that nano-buds or nano-dendrites consist of nanoparticles of 40-70 nm in diameter. The electrochemical reduction of oxygen is reported at such kinds of 3D nanostructure electrodes in aqueous solution. Data were collected using cyclic voltammetry. We demonstrate the Pd macroelectrode behavior of Pd nanostructure modified electrode by exploiting the diffusion model of macro-, micro-, and nano-architectures. In contrast to bare GCE, a significant positive shift and splitting of the oxygen reduction peak (vs Ag/AgCl/saturated KCl) at Pd nanostructure modified GCE was observed.

  2. 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.

  3. Theoretical study of reactions at the electrode-electrolyte interface

    International Nuclear Information System (INIS)

    Halley, J.W.

    1994-01-01

    Electron transfer rates are predicted by numerical methods, in collaboration with ANL. Emphasis is on electron transfer involving ions known to be important in enhancing stress corrosion cracking in light water reactors and on electron transfer at oxide surfaces. We have completed studies of the ferrous-ferric electron transfer rate in which effects of electric field, entropic effects in the free energy and quantum effects are included for the first time in the calculation of the rate of an electrochemical (heterogeneous) reaction rate. These new results confirm assumptions made in earlier calculations. The ferric ion has been modelled in a dissociable polarizable model showing the six-fold coordination of this ion in aqueous solution is stabilized by the three body interactions arising from the polarizability of water. In our studies of oxides, we have completed a Hartree self consistent calculation of the electronic structure of fayalite. The calculation utilizes a new method which takes phenomenological account of local electron correlations which have plagued electronic structure calculations of oxides for a long time. No electronic structure calculation of fayalite has been previously reported to our knowledge. Similar methods have been used to calculate the electronic structure of a vacancy in rutile (TiO 2 ). Results show that the screening donor electrons are anisotropically distributed around the vacancy

  4. 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

  5. High Electrocatalytic Response of a Mechanically Enhanced NbC Nanocomposite Electrode Towards Hydrogen Evolution Reaction

    KAUST Repository

    Coy, Emerson

    2017-08-22

    Resistant and efficient electrocatalysts for hydrogen evolution reaction (HER) are desired to replace scarce and commercially expensive platinum electrodes. Thin film electrodes of metal-carbides are a promising alternative due to their reduced price and similar catalytic properties. However, most of the studied structures to date neglect long lasting chemical and structural stability, focusing only on electrochemical efficiency. Herein we report on a new approach to easily deposit and control the micro/nanostructure of thin film electrodes based on niobium carbide (NbC) and their electrocatalytic response. We will show that, by improving the mechanical properties of the NbC electrodes, microstructure and mechanical resilience can be obtained whilst maintaining high electro catalytic response. We also address the influence of other parameters such as conductivity and chemical composition on the overall performance of the thin film electrodes. Finally, we show that nanocomposite NbC electrodes are promising candidates towards HER , and furthermore, that the methodology presented here is suitable to produce other transition metal carbides (TM-C) with improved catalytic and mechanical properties.

  6. 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

  7. Complete Decomposition of Li 2 CO 3 in Li–O 2 Batteries Using Ir/B 4 C as Noncarbon-Based Oxygen Electrode

    Energy Technology Data Exchange (ETDEWEB)

    Song, Shidong; Xu, Wu; Zheng, Jianming; Luo, Langli; Engelhard, Mark H.; Bowden, Mark E.; Liu, Bin; Wang, Chong-Min; Zhang, Ji-Guang

    2017-02-10

    Incomplete decomposition of Li2CO3 during charge process is a critical barrier for rechargeable Li-O2 batteries. Here we report complete decomposition of Li2CO3 in Li-O2 batteries using ultrafine iridium-decorated boron carbide (Ir/B4C) nanocomposite as oxygen electrode. The systematic investigation on charging the Li2CO3 preloaded Ir/B4C electrode in an ether-based electrolyte demonstrates that Ir/B4C electrode can decompose Li2CO3 with an efficiency close to 100% at below 4.37 V. In contrast, the bare B4C without Ir electrocatalyst can only decompose 4.7% of preloaded Li2CO3. The reaction mechanism of Li2CO3 decomposition in the presence of Ir/B4C electrocatalyst has been further investigated. A Li-O2 battery using Ir/B4C as oxygen electrode material shows highly enhanced cycling stability than that using bare B4C oxygen electrode. These results clearly demonstrate that Ir/B4C is an effecitive oxygen electrode amterial to completely decompose Li2CO3 at relatively low charge voltages and is of significant importance in improving the cycle performanc of aprotic Li-O2 batteries.

  8. 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.

  9. 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.

  10. Influence of the oxygen electrode and inter-diffusion barrier on the degradation of solid oxide electrolysis cells

    DEFF Research Database (Denmark)

    Hjalmarsson, Per; Sun, Xiufu; Liu, Yi-Lin

    2013-01-01

    -diffusion barrier sandwiched between the YSZ electrolyte and an LSCF:CGO oxygen electrode. Impedance Spectroscopy was used during the tests to diagnose the change in electrochemical response of the different components of the SOECs. The results showed a significantly lower degradation rate for the cell with an LSCF......Two Solid Oxide Electrolysis Cells (SOECs) with different oxygen electrodes have been tested in galvanostatic tests carried out at −1.5 Acm−2 and 800 °C converting 60% of a 50:50% mixture of H2O and CO2 (co-electrolysis). One of the cells had an LSM:YSZ oxygen electrode. The other had an CGO inter...

  11. Role of the adsorbed oxygen species in the selective electrochemical reduction of CO{sub 2} to alcohols and carbonyls on copper electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi [School of Chemistry, University of Birmingham, Edgbaston (United Kingdom)

    2017-10-09

    The electrochemical reduction of CO{sub 2} into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO{sub 2} to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO{sub 2} on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO{sub 2} reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Role of the adsorbed oxygen species in the selective electrochemical reduction of CO_2 to alcohols and carbonyls on copper electrodes

    International Nuclear Information System (INIS)

    Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi

    2017-01-01

    The electrochemical reduction of CO_2 into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO_2 to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO_2 on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO_2 reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. 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...

  14. 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

  15. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

    International Nuclear Information System (INIS)

    Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

    2000-01-01

    The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

  16. 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.

  17. Limiting Current of Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells

    DEFF Research Database (Denmark)

    Li, Qingfeng; Gang, Xiao; Hjuler, Hans Aage

    1994-01-01

    on polytetrafluorine-ethyl bonded gas-diffusion electordes in phosphoric acid with and without fluorinated additives. This provides an alternative to estimate the film thickness by combining it with the acid-adsorption measurements and the porosity analysis of the catalyst layer. It was noticed that the limiting......Various models have been devoted to the operation mechanism of porous diffusion electrodes. They are, however, suffering from the lack of accuracy concerning the acid-film thickness on which they are based. In the present paper the limiting current density has been measured for oxygen reduction...... current density can be accomplished either by gas-phase diffusion or liquid-phase diffusion, and it is the latter that can be used in the film-thickness estimation. It is also important to mention that at such a limiting condition, both the thin-film model and the filmed agglomerate model reach the same...

  18. 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.

  19. 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)

  20. 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)

  1. 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

  2. Non-noble metal graphene oxide-copper (II) ions hybrid electrodes for electrocatalytic hydrogen evolution reaction

    KAUST Repository

    Muralikrishna, S.

    2015-08-25

    Non-noble metal and inexpensive graphene oxide-copper (II) ions (GO-Cu2+) hybrid catalysts have been explored for the hydrogen evolution reaction (HER). We were able to tune the binding abilities of GO toward the Cu2+ ions and hence their catalytic properties by altering the pH. We have utilized the oxygen functional moieties such as carboxylate, epoxide, and hydroxyl groups on the edge and basal planes of the GO for binding the Cu2+ ions through dative bonds. The GO-Cu2+ hybrid materials were characterized by cyclic voltammetry in sodium acetate buffer solution. The morphology of the hybrid GO-Cu2+ was characterized by atomic force microscopy. The GO-Cu2+ hybrid electrodes show good electrocatalytic activity for HER with low overpotential in acidic solution. The Tafel slope for the GO-Cu2+ hybrid electrode implies that the primary discharge step is the rate determining step and HER proceed with Volmer step. © 2015 American Institute of Chemical Engineers Environ Prog.

  3. Electrochemical investigations of Pu(IV)/Pu(III) redox reaction using graphene modified glassy carbon electrodes and a comparison to the performance of SWCNTs modified glassy carbon electrodes

    International Nuclear Information System (INIS)

    Gupta, Ruma; Gamare, Jayashree; Sharma, Manoj K.; Kamat, J.V.

    2016-01-01

    Highlights: • First report of aqueous electrochemistry of Plutonium on graphene modified electrode. • Graphene is best electrocatalytic material for Pu(IV)/Pu(III) redox couple among the reported modifiers viz. reduced graphene oxide (rGO) and SWCNT’s. • The electrochemical reversibility of Pu(IV)/Pu(III) redox couple improves significantly on graphene modified electrode compared to previously reported rGO & SWCNTs modified electrodes • Donnan interaction between plutonium species and graphene surface offers a possibility for designing a highly sensitive sensor for plutonium • Graphene modified electrode shows higher sensitivity for the determination of plutonium compared to glassy carbon and single walled carbon nanotube modified electrode - Abstract: The work reported in this paper demonstrates for the first time that graphene modified glassy carbon electrode (Gr/GC) show remarkable electrocatalysis towards Pu(IV)/Pu(III) redox reaction and the results were compared with that of single-walled carbon nanotubes modified GC (SWCNTs/GC) and glassy carbon (GC) electrodes. Graphene catalyzes the exchange of current of the Pu(IV)/Pu(III) couple by reducing both the anodic and cathodic overpotentials. The Gr/GC electrode shows higher peak currents (i p ) and smaller peak potential separation (ΔE p ) values than the SWCNTs/GC and GC electrodes. The heterogeneous electron transfer rate constants (k s ), charge transfer coefficients (α) and the diffusion coefficients (D) involved in the electrocatalytic redox reaction were determined. Our observations show that graphene is best electrocatalytic material among both the SWCNTs and GC to study Pu(IV)/Pu(III) redox reaction.

  4. 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

  5. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed

    2016-11-04

    The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

  6. 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 .

  7. 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.

  8. 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).

  9. 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.

  10. 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.

  11. Hydrogen Oxidation on Gas Diffusion Electrodes for Phosphoric Acid Fuel Cells in the Presence of Carbon Monoxide and Oxygen

    DEFF Research Database (Denmark)

    Gang, Xiao; Li, Qingfeng; Hjuler, Hans Aage

    1995-01-01

    Hydrogen oxidation has been studied on a carbon-supported platinum gas diffusion electrode in a phosphoric acidelectrolyte in the presence of carbon monoxide and oxygen in the feed gas. The poisoning effect of carbon monoxide presentin the feed gas was measured in the temperature range from 80...... to 150°C. It was found that throughout the temperaturerange, the potential loss due to the CO poisoning can be reduced to a great extent by the injection of small amounts ofgaseous oxygen into the hydrogen gas containing carbon monoxide. By adding 5 volume percent (v/o) oxygen, an almost...

  12. New electrodes for hydrogen/oxygen solid polymer electrolyte fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Mosdale, R [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Recherche Fondamentale sur la Matiere Condensee; Stevens, P [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Thermohydraulique et de Physique

    1993-12-31

    A new method of preparation of Electrode/Membrane/Electrode (EME) assemblies for Proton Exchange Membrane Fuel Cells (PEMFC) has been developed. The electrodes are deposited directly onto a Nafion electrolyte membrane from a mixture of platinized carbon, Nafion solution, and PTFE by using a spray technique. By this technique, porous electrodes are obtained with an optimized gas/electrolyte/catalyst interface, and electrode/membrane interface.

  13. Investigation of the Alkaline Electrochemical Interface and Development of Composite Metal/Metal-Oxides for Hydrogen and Oxygen Electrodes

    Science.gov (United States)

    Bates, Michael

    electrolyte. The HER kinetics of numerous binary & ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. Furthermore a model of the double layer interface is proposed, which helps explain the observed ensemble effect in the presence of AEI. In Chapter 3, Ni-Fe and Ni-Fe-Co mixed-metal-oxide (MMO) films were investigated for oxygen evolution reaction (OER) activity in 0.1M KOH on high surface area Raney-Nickel supports. During investigations of MMO activity, aniline was identified as a useful "capping agent" for synthesis of high-surface area MMO-polyaniline (PANI) composite materials. A Ni-Fe-Co/PANI-Raney-Ni catalyst was developed which exhibits enhanced mass-activity compared to state-of-the-art Ni-Fe OER electrocatalysts reported to date. The morphology of the MMO catalyst film on PANI/Raney-Ni support provides excellent dispersion of active-sites and should maintain high active-site utilization for catalyst loading on gas-diffusion electrodes. In Chapter 4, the de-activation of reversible-hydrogen electrode catalysts was investigated and the development of a Pt-Ir-Nx/C catalyst is reported, which exhibits significantly increased stability in the HBr/Br 2 electrolyte. In contrast a Pt-Ir/C catalyst exhibited increased tolerance to high-voltage cycling and in particular showed recovery of electrocatalytic activity after reversible de-activation (presumably from bromide adsorption and subsequent oxidative bromide stripping). Under the harshest testing conditions of high-voltage cycling or exposure to Br2 the Pt-based catalyst showed a trend in stability: Pt < Pt-Ir < Pt-Ir-Nx. (Abstract shortened by UMI.).

  14. Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

    Science.gov (United States)

    Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

    2016-06-20

    Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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.

  16. Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

    KAUST Repository

    Ziani, Ahmed; Shinagawa, Tatsuya; Stegenburga, Liga; Takanabe, Kazuhiro

    2016-01-01

    of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a

  17. Theory of potentiostatic current transients for coupled catalytic reaction at random corrugated fractal electrode

    International Nuclear Information System (INIS)

    Jha, Shailendra K.; Kant, Rama

    2010-01-01

    We developed a mathematical model for the first order homogeneous catalytic chemical reaction coupled with an electron transfer (EC') on a rough working electrode. Results are obtained for the various roughness models of electrode corrugations, viz., (i) roughness as an exact periodic function, (ii) roughness as a random function with known statistical properties, and (iii) roughness as a random function with statistical self-affine fractality over a finite range of length scales. Method of Green's function is used in the formulation to obtain second-order perturbation (in roughness profile) expressions for the concentration, the local current density and the current transients. A general operator structure between these quantities and arbitrary roughness profile is emphasized. The statistically averaged (randomly rough) electrode response is obtained by an ensemble averaging over all possible surface configurations. An elegant mathematical formula between the average electrochemical current transient and surface structure factor or power-spectrum of roughness is obtained. This formula is used to obtain an explicit equation for the current on an approximately self-affine (or realistic) fractal electrode with a limited range of length scales of irregularities. This description of realistic fractal is obtained by cutoff power law power-spectrum of roughness. The realistic fractal power-spectrum consists of four physical characteristics, viz., the fractal dimension (D H ), lower (l) and upper (L) cutoff length scales of fractality and a proportionality factor (μ), which is related to the topothesy or strength of fractality. Numerical calculations are performed on final results to understand the effect of catalytic reaction and fractal morphological characteristics on potentiostatic current transients.

  18. 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.

  19. 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.

  20. Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In-Situ Electrochemical Process

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin; Xu, Wu; Tao, Jinhui; Yan, Pengfei; Zheng, Jianming; Engelhard, Mark H.; Lu, Dongping; Wang, Chongmin; Zhang, Jiguang

    2018-04-16

    Although the rechargeable lithium-oxygen (Li-O2) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon-based air-electrode, Li metal anode, and electrolytes towards reduced oxygen species. Here we demonstrate a simple one-step in-situ electrochemical pre-charging strategy to generate thin protective films on both carbon nanotubes (CNTs) air-electrode and Li metal anode simultaneously under an inert atmosphere. Li-O2 cells after such pre-treatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity-limited protocol of 1000 mAh g-1 and 500 mAh g-1, respectively, which is far more than those without pre-treatment. The thin-films formed from decomposition of electrolyte during in-situ electrochemical pre-charging process in an inert environment can protect both CNTs air-electrode and Li metal anode prior to conventional Li-O2 discharge/charge cycling where reactive reduced oxygen species are formed. This work provides a new approach for protections of carbon-based air-electrode and Li metal anode in practical Li-O2 batteries, and may also be applied to other battery systems.

  1. Evaluation of the behavior of PtPd/MWCNT electrocatalysts as ethylene glycol-tolerant electrodes for oxygen oxidation reaction (ORR); Evaluacion del comportamiento de electrocatalizadores tipo PtPd/MWCNT como electrodos para la reaccion de oxidacion del oxigeno (ORR) tolerantes al etilenglicol

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Acosta, D.; Arriaga, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)]. E-mail: dmorales@cideteq.mx; Alvarez-Contreras, L. [Centro de Investigacion en Materiales Avanzados S. C., Chihuahua, Chihuahua (Mexico); Fraire Luna, S.; Rodriguez Varela, F.J. [Cinvestav, Unidad Saltillo, Ramos Arizpe, Coahuila, (Mexico)

    2009-09-15

    Pt-Pd/MWCNTs (atomic ratio Pt:Pd 43:57) and Pt/MWCNTs electrocatalysts were synthesized and evaluated as cathodes for oxygen reduction reaction (ORR) with the application of direct ethylene glycol fuel cells (DEGFC). A commercial PtC material was also evaluated as a reference. It was found that Pt-Pd/MWCNT has a capability for high tolerance to ethylene glycol (EG) and higher selectivity for ORR compared to a single Pt- cathode. As a result, the change in onset potential of the ORR, Eonset, in Pt-Pd/MWCNTs was considerably less than the change in Pt/MWCNTs or Pt/C. The average particle size (XRD) was 3.5nm and 4nm for Pt/MWCNTs and Pt-Pd/MWCNTs, respectively. A moderate degree of alloying was determined for the material. The application of Pt-Pd electrocatalysts in DEGFCs should be advantageous. [Spanish] Electrocatalizadores Pt-Pd/MWCNTs (relacion atomic Pt:Pd 43:57) y Pt/MWCNTs fueron sintetizados y evaluados como catodos para la reaccion de reduccion del oxigeno (ORR) con aplicacion del celdas de consumo directo de etilenglicol (Direct Ethylene Glycol Fuel Cells, o DEGFC). Como referencia, un material comercial tipo Pt/C fue tambien evaluado. Se encontro que Pt-Pd/MWCNTs tiene una alta capacidad de tolerancia al etilenglicol (EG) y una selectividad mayor hacia la ORR comparado con el catodo basado en Pt-solo. Como resultado, el cambio en potencial de inicio de la ORR, Eonset, en Pt-Pd/MWCNTs fue considerablemente menor que el cambio en Pt/MWCNTs o Pt/C. La talla de particula promedio (de XRD) fue 3.5 nm y 4 nm para Pt/MWCNTs y Pt-Pd/MWCNTs, respectivamente. Un moderado grado de aleacion fue determinado para el material. Una aplicacion ventajosa para electrocatalizadores tipo Pt-Pd debe ser en DEGFCs.

  2. 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...

  3. 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.

  4. 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 ...

  5. 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.

  6. Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

    Directory of Open Access Journals (Sweden)

    Nicola H. Perry

    2016-10-01

    Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Synthesis and characterization of the WxRuySez from the electrochemical reduction of oxygen and their possible application as electrode in fuel cell

    International Nuclear Information System (INIS)

    Ramirez R, S.D.

    1995-01-01

    In this communication the synthesis of the W 0.03 RuSe 0.47 O 0.3 from the transition metal carbonyl compounds and the chalcogenide in m Xylene, the chemical characterization of the novel material was performed by neutron activation analysis (NAA), using the TRIGA Mark III Reactor from the Nuclear Center of Mexico. The oxygen present in the material was determined by Rutherford Backscattering Spectrometry (RBS). Also the RuSe 5.7 y WSe 2 were synthesized and characterized by NAA. The electro kinetic oxygen reduction behaviour of the W 0.03 RuSe 0.47 O 0.3 deposited in glassy carbon was investigated in aqueous H 2 SO 4 0.5M. The rotating disk electrode electrochemical technique was used for determining the kinetic parameters: The reaction was of first order which implied that the rate determining step is the transfer of one electron, the Tafel slope was 0.115 V/decade; the electron transfer coefficient found was of 0.5, and the activation energy in the oxygen reduction reaction was 0.47 eV. (Author)

  12. 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.

  13. Solid electrolytes in thermodynamic investigations. Investigation of oxygen pressure effect in Ar + O2 type mixtures on cell potentials with CaF2 electrolyte and oxide electrodes

    International Nuclear Information System (INIS)

    Levitskij, V.A.; Narchuk, N.B.; Kashkarova, S.L.

    1982-01-01

    An experimental test of the P'sub(Osub(2))=P''sub(Osub(2)) condition (P'sub(Osub(2)) and P''sub(Osub(2)) - oxygen pressure above the first and the second electrodes) necessary for reversible work of the cells is carried out with the (-)O 2 , Pt (CaZrO 3 , 0.18CaOx0.82ZrO 2 )CaF 2 CaF 2 CaHfO 3 , HfO 2 , CaF 2 Pt, O 2 (+) cell as an example. The equilibrium potentials of the given cell are shown to be independent from Psub(Osub(2)) value above both electrodes up to the O 2 pressure equal to approximately 1 Pa at Psub(gen.)=Psub(Osub(2))+Psub(Ar)=10sup(5) Pa. Thermodynamic parameters of the CaO+HfO 2 =CaHfO 3 reaction obtained from the E=f(T) dependence in argon atmosphere under Psub(Osub(2))=1-10sup(2) Pa well agree with analogous values determined for the same cell under Psub(Osub(2)) = 10 5 Pa. Comparison of the results obtained by the e. m. f. method with F - - ion electrolyte both in pure oxygen and in argon atmosphere under low Psub(Osub(2)) with the present literature data testify to perspectives of using the cells of this type under controlled low Psub(Osub(2)) values for thermodynamic investigations

  14. 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...

  15. REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

    Directory of Open Access Journals (Sweden)

    JIŘÍ MATĚJ

    2012-09-01

    Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

  16. 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.

  17. 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.

  18. 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)

  19. 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.

  20. Use of a combined oxygen and carbon dioxide transcutaneous electrode in the estimation of gas exchange during exercise.

    OpenAIRE

    Sridhar, M K; Carter, R; Moran, F; Banham, S W

    1993-01-01

    BACKGROUND--Accurate and reliable measurement of gas exchange during exercise has traditionally involved arterial cannulation. Non-invasive devices to estimate arterial oxygen (O2) and carbon dioxide (CO2) tensions are now available. A method has been devised and evaluated for measuring gas exchange during exercise with a combined transcutaneous O2 and CO2 electrode. METHODS--Symptom limited exercise tests were carried out in 24 patients reporting effort intolerance and breathlessness. Exerci...

  1. 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.

  2. Decoupling Hydrogen and Oxygen Production in Acidic Water Electrolysis Using a Polytriphenylamine-Based Battery Electrode.

    Science.gov (United States)

    Ma, Yuanyuan; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

    2018-03-05

    Hydrogen production through water splitting is considered a promising approach for solar energy harvesting. However, the variable and intermittent nature of solar energy and the co-production of H 2 and O 2 significantly reduce the flexibility of this approach, increasing the costs of its use in practical applications. Herein, using the reversible n-type doping/de-doping reaction of the solid-state polytriphenylamine-based battery electrode, we decouple the H 2 and O 2 production in acid water electrolysis. In this architecture, the H 2 and O 2 production occur at different times, which eliminates the issue of gas mixing and adapts to the variable and intermittent nature of solar energy, facilitating the conversion of solar energy to hydrogen (STH). Furthermore, for the first time, we demonstrate a membrane-free solar water splitting through commercial photovoltaics and the decoupled acid water electrolysis, which potentially paves the way for a new approach for solar water splitting. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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

  4. 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

  5. Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

    NARCIS (Netherlands)

    Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

    2000-01-01

    We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

  6. A glassy carbon electrode modified with an iron N4-macrocycle and reduced graphene oxide for voltammetric sensing of dissolved oxygen

    International Nuclear Information System (INIS)

    Silva, Saimon M.; Aguiar, Lucas F.; Carvalho, Rita M. S.; Tanaka, Auro A.; Damos, Flavio S.; Luz, Rita C. S.

    2016-01-01

    The authors describe a platform for the electrochemical reduction of oxygen. It is based on the use of a glassy carbon electrode (GCE) that was modified in a single-step microwave assisted reaction with a N4-macrocycle containing iron(III) (FeN4) and with reduced graphene oxide. The FeN4/rGO composite was characterized by cyclic voltammetry, differential pulse voltammetry, and scanning electrochemical microscopy (SECM). Cyclic voltammetry showed the composite to enable efficient reduction of O_2 at a very low overpotential (−0.05 V vs. Ag/AgCl). SECM measurements were carried out to map (in the redox competition mode) the activity of a GCE microelectrode modified with FeN4/rGO. Under optimized conditions, the response to dissolved O_2 ranges from 0.8 up to 25 mg⋅L"-"1, and the limit of detection is 0.2 mg⋅L"-"1. (author)

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Influence of oxygen on hydrogen storage and electrode properties for micro-designed V-based battery alloys

    Energy Technology Data Exchange (ETDEWEB)

    Tsukahara, M.; Takahashi, K.; Isomura, A. [Mater. R and D Co., Ltd., Aichi (Japan). IMRA; Sakai, T. [Osaka National Research Institute, Midorigaoka, Ikeda-shi, Osaka, 563 (Japan)

    1998-01-30

    The influence of oxygen on micro-structure, hydrogen storage and electrode properties were investigated for the alloy V{sub 3}TiNi{sub 0.56}Co{sub 0.14}Nb{sub 0.047}Ta{sub 0.047}. Since titanium in the alloy worked as a deoxidizer to form the oxide phase, the alloy preserved a large hydrogen capacity in the oxygen concentration range below 5000 mass ppm. More oxygen than 6000 mass ppm caused a remarkable contraction of the unit cell of the vanadium-based main phase and then a decrease in the hydrogen storage capacity. The contraction was accompanied by the precipitation of the Ti-based oxide phase. (orig.) 15 refs.

  12. Efficient oxidative dissolution of V2O3 by the in situ electro-generated reactive oxygen species on N-doped carbon felt electrodes

    International Nuclear Information System (INIS)

    Xue, Yudong; Wang, Yunting; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

    2017-01-01

    Highlights: • Novel alkaline electro-Fenton-like was applied for V 2 O 3 oxidative dissolution. • N-doped carbon felt electrode was fabricated for the two-electron ORR. • ROS including ·OH and HO 2 − was in-situ generated from the electrochemical system. • A significant enhancement of V 2 O 3 dissolution was achieved due to the ROS. - Abstract: Oxidative dissolution is a critical step for the efficient remediation of heavy metal oxides in large-scale solid wastes. In the present study, a novel electro-oxidative dissolution process of V 2 O 3 to VO 4 3− is achieved by the in-situ generated reactive oxygen species on the N-doped carbon felt cathode in alkaline media. The electro-catalytic HO 2 − generation and hydrophilic behavior were significantly enhanced by the introduction of nitrogen-containing functional groups. Besides, the mechanism of electrochemical vanadium conversion is systematically illustrated, and a vanadium self-induced electro-Fenton-like reaction is proposed. By employing the radical quenching and ESR measurements, the contributions for V(III) dissolution is determined to be 43.5% by HO 2 − and 56.5% by hydroxyl radicals, respectively. It should be noted that the V 2 O 3 solid particles can be efficiently dissolved via adsorption-reaction scheme on the carbon felt electrode. This novel electrochemical strategy provides a promising solution for the heavy metal oxide treatment and further understanding for the in situ reactive oxygen species.

  13. Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

    Science.gov (United States)

    Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

    2018-01-23

    The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

  14. Reaction and nucleation mechanisms of copper electrodeposition on disposable pencil graphite electrode

    Energy Technology Data Exchange (ETDEWEB)

    Majidi, M.R. [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, 29th Bahman Bolvard, Tabriz 51664 (Iran, Islamic Republic of)], E-mail: sr.majidi@gmail.com; Asadpour-Zeynali, K.; Hafezi, B. [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, 29th Bahman Bolvard, Tabriz 51664 (Iran, Islamic Republic of)

    2009-01-01

    The reaction and nucleation mechanism of copper electrodeposition on disposable pencil graphite electrode (PGE) in acidic sulphate solution were investigated using cyclic voltammetry (CV) and chronoamperometry (CA) techniques, respectively. Electrochemical experiments were followed by morphological studies with scanning electron microscopy (SEM). The effect of some experimental parameters, namely copper concentration, pH, scan rate, background electrolyte, deposition potential, and conditioning surface of the electrode were described. At the surface of PGE, Cu{sup 2+} ions were reduced at -250 mV vs. SCE. It was found that electrodeposition of copper is affected by rough surface of PGE. The nucleation mechanisms were examined by fitting the experimental CA data into Scharifker-Hills nucleation models. The nuclei population densities were also determined by means of two common fitting models developed for three-dimensional nucleation and growth (Scharifker-Mostany and Mirkin-Nilov-Herrman-Tarallo). It was found that deposition potential and background electrolyte affect the distribution of the deposited copper. The morphology of the deposited copper is affected by background electrolyte.

  15. 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)

  16. 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.

  17. 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.

  18. Oxygen-Vacancy Abundant Ultrafine Co3O4/Graphene Composites for High-Rate Supercapacitor Electrodes.

    Science.gov (United States)

    Yang, Shuhua; Liu, Yuanyue; Hao, Yufeng; Yang, Xiaopeng; Goddard, William A; Zhang, Xiao Li; Cao, Bingqiang

    2018-04-01

    The metal oxides/graphene composites are one of the most promising supercapacitors (SCs) electrode materials. However, rational synthesis of such electrode materials with controllable conductivity and electrochemical activity is the topical challenge for high-performance SCs. Here, the Co 3 O 4 /graphene composite is taken as a typical example and develops a novel/universal one-step laser irradiation method that overcomes all these challenges and obtains the oxygen-vacancy abundant ultrafine Co 3 O 4 nanoparticles/graphene (UCNG) composites with high SCs performance. First-principles calculations show that the surface oxygen vacancies can facilitate the electrochemical charge transfer by creating midgap electronic states. The specific capacitance of the UCNG electrode reaches 978.1 F g -1 (135.8 mA h g -1 ) at the current densities of 1 A g -1 and retains a high capacitance retention of 916.5 F g -1 (127.3 mA h g -1 ) even at current density up to 10 A g -1 , showing remarkable rate capability (more than 93.7% capacitance retention). Additionally, 99.3% of the initial capacitance is maintained after consecutive 20 000 cycles, demonstrating enhanced cycling stability. Moreover, this proposed laser-assisted growth strategy is demonstrated to be universal for other metal oxide/graphene composites with tuned electrical conductivity and electrochemical activity.

  19. 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

  20. 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...

  1. 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.

  2. 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.

  3. 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.

  4. 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)

  5. 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.

  6. 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.

  7. Tunable Reaction Potentials in Open Framework Nanoparticle Battery Electrodes for Grid-Scale Energy Storage

    KAUST Repository

    Wessells, Colin D.

    2012-02-28

    The electrical energy grid has a growing need for energy storage to address short-term transients, frequency regulation, and load leveling. Though electrochemical energy storage devices such as batteries offer an attractive solution, current commercial battery technology cannot provide adequate power, and cycle life, and energy efficiency at a sufficiently low cost. Copper hexacyanoferrate and nickel hexacyanoferrate, two open framework materials with the Prussian Blue structure, were recently shown to offer ultralong cycle life and high-rate performance when operated as battery electrodes in safe, inexpensive aqueous sodium ion and potassium ion electrolytes. In this report, we demonstrate that the reaction potential of copper-nickel alloy hexacyanoferrate nanoparticles may be tuned by controlling the ratio of copper to nickel in these materials. X-ray diffraction, TEM energy dispersive X-ray spectroscopy, and galvanostatic electrochemical cycling of copper-nickel hexacyanoferrate reveal that copper and nickel form a fully miscible solution at particular sites in the framework without perturbing the structure. This allows copper-nickel hexacyanoferrate to reversibly intercalate sodium and potassium ions for over 2000 cycles with capacity retentions of 100% and 91%, respectively. The ability to precisely tune the reaction potential of copper-nickel hexacyanoferrate without sacrificing cycle life will allow the development of full cells that utilize the entire electrochemical stability window of aqueous sodium and potassium ion electrolytes. © 2012 American Chemical Society.

  8. 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.

  9. Mathematical modeling of the lithium deposition overcharge reaction in lithium-ion batteries using carbon-based negative electrodes

    International Nuclear Information System (INIS)

    Arora, P.; Doyle, M.; White, R.E.

    1999-01-01

    Two major issues facing lithium-ion battery technology are safety and capacity grade during cycling. A significant amount of work has been done to improve the cycle life and to reduce the safety problems associated with these cells. This includes newer and better electrode materials, lower-temperature shutdown separators, nonflammable or self-extinguishing electrolytes, and improved cell designs. The goal of this work is to predict the conditions for the lithium deposition overcharge reaction on the negative electrode (graphite and coke) and to investigate the effect of various operating conditions, cell designs and charging protocols on the lithium deposition side reaction. The processes that lead to capacity fading affect severely the cycle life and rate behavior of lithium-ion cells. One such process is the overcharge of the negative electrode causing lithium deposition, which can lead to capacity losses including a loss of active lithium and electrolyte and represents a potential safety hazard. A mathematical model is presented to predict lithium deposition on the negative electrode under a variety of operating conditions. The Li x C 6 vertical bar 1 M LiPF 6 , 2:1 ethylene carbonate/dimethyl carbonate, poly(vinylidene fluoride-hexafluoropropylene) vert b ar LiMn 2 O 4 cell is simulated to investigate the influence of lithium deposition on the charging behavior of intercalation electrodes. The model is used to study the effect of key design parameters (particle size, electrode thickness, and mass ratio) on the lithium deposition overcharge reaction. The model predictions are compared for coke and graphite-based negative electrodes. The cycling behavior of these cells is simulated before and after overcharge to understand the hazards and capacity fade problems, inherent in these cells, can be minimized

  10. Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

    Science.gov (United States)

    Sánchez, Carolina Ramírez; Taurino, Antonietta; Bozzini, Benedetto

    2016-01-01

    This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR) electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy) nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE) method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i) morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscope (AFM); (ii) local electrical conductivity, as measured by Scanning Probe Microscopy (SPM); and (iii) molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt). Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement. PMID:28042491

  11. Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

    Directory of Open Access Journals (Sweden)

    Patrizia Bocchetta

    2016-01-01

    Full Text Available This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM and Atomic Force Microscope (AFM; (ii local electrical conductivity, as measured by Scanning Probe Microscopy (SPM; and (iii molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt. Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement.

  12. 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...

  13. 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...

  14. 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...

  15. 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

  16. 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...

  17. 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

  18. 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

  19. Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells by a Potential Decay Method

    DEFF Research Database (Denmark)

    Li, Qingfeng; Gang, Xiao; Hjuler, Hans Aage

    1995-01-01

    The reduction of gaseous oxygen on carbon supported platinum electrodes has been studied at 150 degrees C with polarization and potential decay measurements. The electrolyte was either 100 weight percent phosphoric acid or that acid with a fluorinated additive, potassium perfluorohexanesulfonate ......6F13SO3K). The pseudo-Tafel curves of the overpotential vs. log (ii(L)/(i(L) - i)) show a two-slope behavior, probably due to different adsorption mechanisms. The potential relaxations as functions of log (t + tau) and log (-d eta/dt) have been plotted. The variations of these slopes...

  20. 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)

  1. 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.

  2. Zinc deposition and dissolution in methanesulfonic acid onto a carbon composite electrode as the negative electrode reactions in a hybrid redox flow battery

    International Nuclear Information System (INIS)

    Leung, P.K.; Ponce-de-Leon, C.; Low, C.T.J.; Walsh, F.C.

    2011-01-01

    Highlights: → Use methanesulfonic acid to avoid dendrite formation during a long (>4 h) zinc electrodeposition. → Electrochemical characterization of Zn(II) deposition and its morphology using methanesulfonic acid solutions. → Use of additives to improve the efficiency of zinc deposition and dissolution as the half cell reaction of a redox flow battery. - Abstract: Electrodeposition and dissolution of zinc in methanesulfonic acid were studied as the negative electrode reactions in a hybrid redox flow battery. Cyclic voltammetry at a rotating disk electrode was used to characterize the electrochemistry and the effect of process conditions on the deposition and dissolution rate of zinc in aqueous methanesulfonic acid. At a sufficiently high current density, the deposition process became a mass transport controlled reaction. The diffusion coefficient of Zn 2+ ions was 7.5 x 10 -6 cm 2 s -1 . The performance of the zinc negative electrode in a parallel plate flow cell was also studied as a function of Zn 2+ ion concentration, methanesulfonic acid concentration, current density, electrolyte flow rate, operating temperature and the addition of electrolytic additives, including potassium sodium tartarate, tetrabutylammonium hydroxide, and indium oxide. The current-, voltage- and energy efficiencies of the zinc-half cell reaction and the morphologies of the zinc deposits are also discussed. The energy efficiency improved from 62% in the absence of additives to 73% upon the addition of 2 x 10 -3 mol dm -3 of indium oxide as a hydrogen suppressant. In aqueous methanesulfonic acid with or without additives, there was no significant dendrite formation after zinc electrodeposition for 4 h at 50 mA cm -2 .

  3. 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)

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Enhancement of oxygen diffusion process on a rotating disk electrode for the electro-Fenton degradation of tetracycline

    International Nuclear Information System (INIS)

    Zhang, Yan; Gao, Ming-Ming; Wang, Xin-Hua; Wang, Shu-Guang; Liu, Rui-Ting

    2015-01-01

    An electro-Fenton process was developed for wastewater treatment in which hydrogen peroxide was generated in situ with a rotating graphite disk electrode as cathode. The maximum H 2 O 2 generation rate for the RDE reached 0.90 mg/L/h/cm 2 under the rotation speed of 400 rpm at pH 3, and −0.8 V vs SCE. The performance of this electro-Fenton reactor was assessed by tetracycline degradation in an aqueous solution. Experimental results showed the rotation of disk cathode resulted in the efficient production of H 2 O 2 without oxygen aeration, and excellent ability for degrading organic pollutants compared to the electro-Fenton system with fixed cathode. Tetracycline of 50 mg/L was degraded completely within 2 h with the addition of ferrous ion (1.0 mM). The chronoamperometry analysis was employed to investigate the oxygen diffusion on the rotating cathode. The results demonstrated that the diffusion coefficients of dissolved oxygen is 19.45 × 10 −5 cm 2 /s, which is greater than that reported in the literature. Further calculation indicated that oxygen is able to diffuse through the film on the rotating cathode within the contact time in each circle. This study proves that enhancement of oxygen diffusion on RDE is benefit for H 2 O 2 generation, thus provides a promising method for organic pollutants degradation by the combination of RDE with electro-Fenton reactor and offers a new insight on the oxygen transform process in this new system.

  11. 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.

  12. 2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction

    Science.gov (United States)

    Rowley-Neale, Samuel J.; Brownson, Dale A. C.; Smith, Graham C.; Sawtell, David A. G.; Kelly, Peter J.; Banks, Craig E.

    2015-10-01

    We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode

  13. 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%

  14. Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

    Science.gov (United States)

    Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

    2013-07-01

    We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

  15. Parallel oxygen and chlorine evolution on Ru1-xNixO2-y nanostructured electrodes

    Czech Academy of Sciences Publication Activity Database

    Macounová, Kateřina; Makarova, Marina; Jirkovský, Jakub; Franc, Jiří; Krtil, Petr

    2008-01-01

    Roč. 53, č. 5 (2008), s. 6126-6134 ISSN 0013-4686 R&D Projects: GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : OER * CER * DEMS * ruthenium electrode Subject RIV: CG - Electrochemistry Impact factor: 3.078, year: 2008

  16. New process of the preparation of catalyzed gas diffusion electrode for PEM fuel cells based on ultrasonic direct solution spray reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Oishi, K.; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

    2008-07-01

    This paper reported on a newly developed process for in-situ catalyst deposition on gas diffusion electrodes (GDE) for polymer electrolyte fuel cells. This process has the potential to reduce the number of steps for catalyzed GDE fabrication. In addition, the process offers economic advantages for the fuel cell commercialization. In this study, a home-made catalyst maker with ultrasonic spray method was used to prepare a solution of the carbon supported platinum catalyst on the GDL. The sprayed catalyst powder consisted of carbon support. The catalyst particles did not prevent gas flow channels on the GDL. The catalyst layer was shown to be located only on the top surface of the GDL and was not packed into its flow channel. Results of Cross-section SEM image, crystallization, micro structure and electro-catalytic activity for the oxygen reduction reaction were also discussed. 1 ref., 1 fig.

  17. 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.

  18. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    Science.gov (United States)

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

  19. Electrochemical reduction of oxygen on small platinum particles supported on carbon in concentrated phosphoric acid. 2. Effects of teflon content in the catalyst layer and baking temperature of the electrode

    Energy Technology Data Exchange (ETDEWEB)

    Maoka, T.

    1988-03-01

    A relation between hydrophobicity (or wettability) of a porous gas diffusion electrode for use in a phosphoric acid fuel cell and its cathode performance (activity toward electrochemical oxygen reduction) was examined. The hydrophobicity of the gas diffusion electrode was regulated by changing either the amount of Teflon (PTFE) content in the catalyst layer or baking temperature of the electrode. The Tafel slope or electrochemical oxygen reduction became twice as high as that of the ordinary electrode when the wettability of electrode toward phosphoric acid was high. This fact supports a flooded agglomerate model as the mode of this type of porous gas diffusion electrode.

  20. 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)

  1. Development of a Novel Cu(II Complex Modified Electrode and a Portable Electrochemical Analyzer for the Determination of Dissolved Oxygen (DO in Water

    Directory of Open Access Journals (Sweden)

    Salvatore Gianluca Leonardi

    2016-04-01

    Full Text Available The development of an electrochemical dissolved oxygen (DO sensor based on a novel Cu(II complex-modified screen printed carbon electrode is reported. The voltammetric behavior of the modified electrode was investigated at different scan rates and oxygen concentrations in PBS (pH = 7. An increase of cathodic current (at about −0.4 vs. Ag/AgCl with the addition of oxygen was observed. The modified Cu(II complex electrode was demonstrated for the determination of DO in water using chronoamperometry. A small size and low power consumption home-made portable electrochemical analyzer based on custom electronics for sensor interfacing and operating in voltammetry and amperometry modes has been also designed and fabricated. Its performances in the monitoring of DO in water were compared with a commercial one.

  2. 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.

  3. 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...

  4. 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)

  5. 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.

  6. 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.

  7. 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)

  8. 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...

  9. 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.

  10. 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

  11. Hybrid capacitors utilizing halogen-based redox reactions at interface between carbon positive electrode and aqueous electrolytes

    Science.gov (United States)

    Yamazaki, Shigeaki; Ito, Tatsuya; Murakumo, Yuka; Naitou, Masashi; Shimooka, Toshiharu; Yamagata, Masaki; Ishikawa, Masashi

    2016-09-01

    We propose novel hybrid capacitors (HCs) with electrolyte-involved redox reactions of bromide or iodide species by pretreatment of an activated carbon positive electrode. The treatment is simple; impregnation of pores at an activated carbon fiber cloth (ACFC) as a positive electrode with bromine- or iodine-containing water before cell assembly. The treated positive electrode is applied to a HC cell with a non-treated negative electrode of ACFC and its electrochemical performance is investigated by galvanostatic cycling and leakage current tests. Few studies on such "electrolytic" charge storage systems have provided acceptable capacitor performance because of inevitable self-discharge caused by diffusion of charged species form an electrode to the other one through an electrolyte. Nevertheless, our electrolyte-redox-based HCs show excellent performance without undesirable diffusion of charged species. Moreover, the present HC utilizing a bromide redox system fulfills a practical cell voltage of 1.8 V in spite of an aqueous electrolyte system. This high voltage provides excellent energy density, which is 5 times higher than that in a conventional aqueous electric double-layer capacitor (EDLC), and 1.2 times higher even than that in a 2.7 V-class non-aqueous EDLC, while keeping high charge-discharge rate capability.

  12. 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.

  13. 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...

  14. 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.

  15. 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.

  16. 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.

  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. 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.

  19. 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.)

  20. 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...

  1. 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.

  2. Screen-Printed Graphite Electrodes as Low-Cost Devices for Oxygen Gas Detection in Room-Temperature Ionic Liquids.

    Science.gov (United States)

    Lee, Junqiao; Hussain, Ghulam; Banks, Craig E; Silvester, Debbie S

    2017-11-26

    Screen-printed graphite electrodes (SPGEs) have been used for the first time as platforms to detect oxygen gas in room-temperature ionic liquids (RTILs). Up until now, carbon-based SPEs have shown inferior behaviour compared to platinum and gold SPEs for gas sensing with RTIL solvents. The electrochemical reduction of oxygen (O₂) in a range of RTILs has therefore been explored on home-made SPGEs, and is compared to the behaviour on commercially-available carbon SPEs (C-SPEs). Six common RTILs are initially employed for O₂ detection using cyclic voltammetry (CV), and two RTILs ([C₂mim][NTf₂] and [C₄mim][PF₆]) chosen for further detailed analytical studies. Long-term chronoamperometry (LTCA) was also performed to test the ability of the sensor surface for real-time gas monitoring. Both CV and LTCA gave linear calibration graphs-for CV in the 10-100% vol. range, and for LTCA in the 0.1-20% vol. range-on the SPGE. The responses on the SPGE were far superior to the commercial C-SPEs; more instability in the electrochemical responses were observed on the C-SPEs, together with some breaking-up or dissolution of the electrode surface materials. This study highlights that not all screen-printed ink formulations are compatible with RTIL solvents for longer-term electrochemical experiments, and that the choice of RTIL is also important. Overall, the low-cost SPGEs appear to be promising platforms for the detection of O₂, particularly in [C₄mim][PF₆].

  3. Screen-Printed Graphite Electrodes as Low-Cost Devices for Oxygen Gas Detection in Room-Temperature Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Junqiao Lee

    2017-11-01

    Full Text Available Screen-printed graphite electrodes (SPGEs have been used for the first time as platforms to detect oxygen gas in room-temperature ionic liquids (RTILs. Up until now, carbon-based SPEs have shown inferior behaviour compared to platinum and gold SPEs for gas sensing with RTIL solvents. The electrochemical reduction of oxygen (O2 in a range of RTILs has therefore been explored on home-made SPGEs, and is compared to the behaviour on commercially-available carbon SPEs (C-SPEs. Six common RTILs are initially employed for O2 detection using cyclic voltammetry (CV, and two RTILs ([C2mim][NTf2] and [C4mim][PF6] chosen for further detailed analytical studies. Long-term chronoamperometry (LTCA was also performed to test the ability of the sensor surface for real-time gas monitoring. Both CV and LTCA gave linear calibration graphs—for CV in the 10–100% vol. range, and for LTCA in the 0.1–20% vol. range—on the SPGE. The responses on the SPGE were far superior to the commercial C-SPEs; more instability in the electrochemical responses were observed on the C-SPEs, together with some breaking-up or dissolution of the electrode surface materials. This study highlights that not all screen-printed ink formulations are compatible with RTIL solvents for longer-term electrochemical experiments, and that the choice of RTIL is also important. Overall, the low-cost SPGEs appear to be promising platforms for the detection of O2, particularly in [C4mim][PF6].

  4. 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.

  5. Improvement of Transparent Conducting Performance on Oxygen-Activated Fluorine-Doped Tin Oxide Electrodes Formed by Horizontal Ultrasonic Spray Pyrolysis Deposition.

    Science.gov (United States)

    Koo, Bon-Ryul; Oh, Dong-Hyeun; Riu, Doh-Hyung; Ahn, Hyo-Jin

    2017-12-27

    In this study, highly transparent conducting fluorine-doped tin oxide (FTO) electrodes were fabricated using the horizontal ultrasonic spray pyrolysis deposition. In order to improve their transparent conducting performances, we carried out oxygen activation by adjusting the ratio of O 2 /(O 2 +N 2 ) in the carrier gas (0%, 20%, and 50%) used during the deposition process. The oxygen activation on the FTO electrodes accelerated the substitution concentration of F (F O • ) into the oxygen sites in the FTO electrode while the oxygen vacancy (V O • • ) concentration was reduced. In addition, due to growth of pyramid-shaped crystallites with (200) preferred orientations, this oxygen activation caused the formation of a uniform surface structure. As a result, compared to others, the FTO electrode prepared at 50% O 2 showed excellent electrical and optical properties (sheet resistance of ∼4.0 ± 0.14 Ω/□, optical transmittance of ∼85.3%, and figure of merit of ∼5.09 ± 0.19 × 10 -2 Ω -1 ). This led to a superb photoconversion efficiency (∼7.03 ± 0.20%) as a result of the improved short-circuit current density. The photovoltaic performance improvement can be defined by the decreased sheet resistance of FTO used as a transparent conducting electrode in dye-sensitized solar cells (DSSCs), which is due to the combined effect of the high carrier concentration by the improved F O • concentration on the FTO electrodes and the fasted Hall mobility by the formation of a uniform FTO surface structure and distortion relaxation on the FTO lattices resulting from the reduced V O • • • concentration.

  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. Novel solid oxide cells with SrCo0.8Fe0.1Ga0.1O3-δ oxygen electrode for flexible power generation and hydrogen production

    Science.gov (United States)

    Meng, Xiuxia; Shen, Yichi; Xie, Menghan; Yin, Yimei; Yang, Naitao; Ma, Zi-Feng; Diniz da Costa, João C.; Liu, Shaomin

    2016-02-01

    This work investigates the performance of solid oxide cells as fuel cells (SOFCs) for power production and also as electrolysis cells (SOECs) for hydrogen production. In order to deliver this dual mode flexible operation system, a novel perovskite oxide based on Ga3+ doped SrCo0.8Fe0.1Ga0.1O3-δ (SCFG) is synthesized via a sol-gel method. Its performance for oxygen electrode catalyst was then evaluated. Single solid oxide cell in the configuration of Ni-YSZ|YSZ|GDC|SCFG is assembled and tested in SOFC or SOEC modes from 550 to 850 °C with hydrogen as the fuel or as the product, respectively. GDC is used to avoid the reaction between the electrolyte YSZ and the cobalt-based electrode. Under SOFC mode, a maximum power density of 1044 mW cm-2 is obtained at 750 °C. Further, the cell delivers a stable power output of 650 mW cm-2 up to 125 h at 0.7 V. In the electrolysis mode, when the applied voltage is controlled at 2 V, the electrolysis current density reaches 3.33 A cm-2 at 850 °C with the hydrogen production rate up to 22.9 mL min-1 cm-2 (STP). These results reveal that SCFG is a very promising oxygen electrode material for application in both SOFC and SOEC.

  8. Oxygen-rich hierarchical porous carbon made from pomelo peel fiber as electrode material for supercapacitor

    Science.gov (United States)

    Li, Jing; Liu, Wenlong; Xiao, Dan; Wang, Xinhui

    2017-09-01

    Oxygen-rich hierarchical porous carbon has been fabricated using pomelo peel fiber as a carbon source via an improved KOH activation method. The morphology and chemical composition of the obtained carbon materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), electron microscopy (EM), Raman spectra and elemental analysis. The unique porous structure with abundant oxygen functional groups is favorable to capacitive behavior, and the as-prepared carbon material exhibits high specific capacitance of 222.6 F g-1 at 0.5 A g-1 in 6 M KOH and superior stability over 5000 cycles. This work not only describes a simple way to prepare high-performance carbon material from the discarded pomelo peel, but also provides a strategy for its disposal issue and contributes to the environmental improvement.

  9. 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)

  10. 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)

  11. Influence of oxygen gas on characteristics of self-organized luminous pattern formation observed in an atmospheric dc glow discharge using a liquid electrode

    International Nuclear Information System (INIS)

    Shirai, Naoki; Uchida, Satoshi; Tochikubo, Fumiyoshi

    2014-01-01

    Self-organized luminous pattern formation is observed in the liquid surface of an atmospheric dc glow discharge using a liquid electrode with a miniature helium flow. The factors affecting pattern formation are the gap length, discharge current, helium mass flow rate and polarity. The pattern shape depends on the conductivity and temperature of the liquid electrode. A variety of patterns were observed by changing the conductivity and temperature of the liquid. We clarified that the self-organized pattern formation depends on the amount of electronegative gas, such as oxygen, in the gas in the electrode gap. When an oxygen gas flow was fed to the liquid surface from the outside in an obliquely downward direction, namely, the amount of oxygen gas on the liquid surface was increased locally, self-organized pattern formation was observed in the region with the increased amount of oxygen gas. When the amount of oxygen in the gas in the gap was changed by using a sheath flow system, the appearance of the pattern changed. The presence of oxygen gas strongly affected the self-organized pattern formation of the atmospheric dc discharge using a liquid anode. (paper)

  12. 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.

  13. 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.

  14. O2-enhanced methanol oxidation reaction at novel Pt-Ru-C co-sputtered electrodes

    International Nuclear Information System (INIS)

    Umeda, Minoru; Matsumoto, Yosuke; Inoue, Mitsuhiro; Shironita, Sayoko

    2013-01-01

    Highlights: ► Novel Pt-Ru-C electrodes were prepared by a co-sputtering technique. ► Co-sputtered electrodes with C result in highly efficient O 2 -enhanced methanol oxidation. ► Pt–Ru-alloy-based co-sputtered electrode induces a negative onset potential of methanol oxidation. ► The Pt-Ru-C electrodes allow a negative onset potential of O 2 -enhanced methanol oxidation. ► The optimum atomic ratios of Pt-Ru-C are Pt: 0.24–0.80, Ru: 0.14–0.61, C: 0.06–0.37. -- Abstract: A Pt-Ru-C electrode has been developed using a co-sputtering technique for use as the anode catalyst of a mixed-reactant fuel cell. The physical and electrochemical characteristics of the electrodes demonstrate that co-sputtered Pt and Ru form a Pt–Ru alloy. The crystallite sizes of the catalysts investigated in this study are reduced by the addition of C to the Pt–Ru alloy. Cu stripping voltammograms suggest that the sputtering of C and the formation of the Pt–Ru alloy synergically increase the electrochemical surface area of the electrodes. The methanol oxidation performances of the prepared electrodes were evaluated in N 2 and O 2 atmospheres; the Pt-Ru-C electrodes achieve an O 2 -induced negative shift in the onset potential of the methanol oxidation (E onset ) and enhance the methanol oxidation current density in the O 2 atmosphere. The mechanism of O 2 -enhanced methanol oxidation with a negative E onset at the Pt-Ru-C electrodes is attributed to a change in the electronic structure of Pt due to the formation of Pt–Ru alloy and the generation of O-based adsorption species by the reduction of O 2 . Finally, the composition of the Pt-Ru-C electrode for the O 2 -enhanced methanol oxidation with a negative E onset was found to be optimal at an atomic ratio of Pt: 0.24–0.80, Ru: 0.14–0.61, and C: 0.06–0.37

  15. A study of the electrode/solution interface during electrochemical reactions by digital holography

    Directory of Open Access Journals (Sweden)

    SHENHAO CHEN

    2006-10-01

    Full Text Available Digital holography was used to study in situ the dynamic changes of the electrode/solution interface and the solution near the electrode during the anodic process of iron in a sulfuric acid solution. The effects of chloride, bromide and iodine ions on this process were also investigated. The magnetic field also has effects on the process. The effects are discussed in combination with SEM results.

  16. On the impedance of galvanic cells XXVII. The temperature-dependence of the kinetic parameters of the hydrogen electrode reaction on mercury in concentrated HI

    NARCIS (Netherlands)

    Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1969-01-01

    The impedance of a dropping mercury electrode in 57% HI (7.6 M) was measured at temperatures between −35° and +25°C. In a certain potential and temperature region, two reactions were found to be proceeding simultaneously: the reversible Hg/HgI4−2 reaction and the irreversible H+/H2(Hg) reaction.

  17. Imprint and oxygen deficiency in (Pb,La)(Zr,Ti)O3 thin-film capacitors with La-Sr-Co-O electrodes

    International Nuclear Information System (INIS)

    Lee, J.; Ramesh, R.; Keramidas, V.G.; Warren, W.L.; Pike, G.E.; Evans, J.T. Jr.

    1995-01-01

    La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O thin-film capacitors have been grown in various oxygen ambients by pulsed laser deposition. As the oxygen ambient became more reducing, the capacitors developed more voltage asymmetry in hysteresis loops and a more preferred polarization state directed towards the top electrode. PLZT capacitors cooled in a fully oxidizing atmosphere (i.e., 1 atm oxygen pressure) exhibited nominally symmetric hysteresis loops and also showed little imprint both with and without fully saturating bias fields. We find that ambient oxygen pressure is an important process parameter and the imprint behavior is closely related with ambient oxygen induced effects such as oxygen vacancies, its related defect-dipole complexes and trapping of free charges. The different imprint behavior under negative and positive bias also suggests that the dipolar-defect complexes tend to cause imprint in PLZT capacitors

  18. 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.

  19. Pt Electrodes Enable the Formation of μ4-O Centers in MOF-5 from Multiple Oxygen Sources.

    Science.gov (United States)

    Li, Minyuan M; Dincă, Mircea

    2017-10-04

    The μ 4 -O 2- ions in the Zn 4 O(O 2 C-) 6 secondary building units of Zn 4 O(1,4-benzenedicarboxylate) 3 (MOF-5) electrodeposited under cathodic bias can be sourced from nitrate, water, and molecular oxygen when using platinum gauze as working electrodes. The use of Zn(ClO 4 ) 2 ·6H 2 O, anhydrous Zn(NO 3 ) 2 , or anhydrous Zn(CF 3 SO 3 ) 2 as Zn 2+ sources under rigorous control of other sources of oxygen, including water and O 2 , confirm that the source of the μ 4 -O 2- ions can be promiscuous. Although this finding reveals a relatively complicated manifold of electrochemical processes responsible for the crystallization of MOF-5 under cathodic bias, it further highlights the importance of hydroxide intermediates in the formation of the Zn 4 O(O 2 C-R) secondary building units in this iconic material and is illustrative of the complicated crystallization mechanisms of metal-organic frameworks in general.

  20. Quantitative Analysis of Homogeneous Electrocatalytic Reactions at IDA Electrodes: The Example of [Ni(PPh2NBn2)2]2+

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fei; Parkinson, B. A.; Divan, Ralu; Roberts, John; Liang, Yanping

    2016-12-01

    Interdigitated array (IDA) electrodes have been applied to study the EC’ (electron transfer reaction followed by a catalytic reaction) reactions and a new method of quantitative analysis of IDA results was developed. In this new method, currents on IDA generator and collector electrodes for an EC’ mechanism are derived from the number of redox cycles and the contribution of non-catalytic current. And the fractions of bipotential recycling species and catalytic-active species are calculated, which helps understanding the catalytic reaction mechanism. The homogeneous hydrogen evolution reaction catalyzed by [Ni(PPh2NBn2)2]2+ (where PPh2NBn2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) electrocatalyst was examined and analyzed with IDA electrodes. Besides, the existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. This quantitative analysis of IDA electrode cyclic voltammetry currents can be used as a simple and straightforward method for determining reaction mechanism in other catalytic systems as well.

  1. Quantitative Analysis of Homogeneous Electrocatalytic Reactions at IDA Electrodes: The Example of [Ni(PPh2NBn2)2]2+

    International Nuclear Information System (INIS)

    Liu, Fei; Parkinson, B.A.; Divan, Ralu; Roberts, John; Liang, Yanping

    2016-01-01

    Interdigitated array (IDA) electrodes have been applied to study the EC’ (electron transfer reaction followed by a catalytic reaction) reactions and a new method of quantitative analysis of IDA results was developed. In this new method, currents on IDA generator and collector electrodes for an EC’ mechanism are derived from the number of redox cycles and the contribution of non-catalytic current. And the fractions of bipotential recycling species and catalytic-active species are calculated, which helps understanding the catalytic reaction mechanism. The homogeneous hydrogen evolution reaction catalyzed by [Ni(P Ph 2 N Bn 2 ) 2 ] 2+ (where P Ph 2 N Bn 2 is 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) electrocatalyst was examined and analyzed with IDA electrodes. Besides, the existence of reaction intermediates in the catalytic cycle is inferred from the electrochemical behavior of a glassy carbon disk electrodes and carbon IDA electrodes. This quantitative analysis of IDA electrode cyclic voltammetry currents can be used as a simple and straightforward method for determining reaction mechanism in other catalytic systems as well.

  2. Self-Supported Biocarbon-Fiber Electrode Decorated with Molybdenum Carbide Nanoparticles for Highly Active Hydrogen-Evolution Reaction.

    Science.gov (United States)

    Xiao, Jian; Zhang, Yan; Zhang, Zheye; Lv, Qiying; Jing, Feng; Chi, Kai; Wang, Shuai

    2017-07-12

    Devising and facilely synthesizing an efficient noble metal-free electrocatalyst for the acceleration of the sluggish kinetics in the hydrogen-evolution reaction (HER) is still a big challenge for electrolytic water splitting. Herein, we present a simple one-step approach for constructing self-supported biocarbon-fiber cloth decorated with molybdenum carbide nanoparticles (BCF/Mo 2 C) electrodes by a direct annealing treatment of the Mo oxyanions loaded cotton T-shirt. The Mo 2 C nanoparticles not only serve as the catalytic active sites toward the HER but also enhance the hydrophilicity and conductivity of resultant electrodes. As an integrated three-dimensional HER cathode catalyst, the BCF/Mo 2 C exhibits outstanding electrocatalytic performance with extremely low overpotentials of 88 and 115 mV to drive a current density of 20 mA cm -2 in alkaline and acidic media, respectively. In addition, it can continuously work for 50 h with little decrease in the cathodic current density in both alkaline and acidic solutions. Even better, self-supported tungsten carbide and vanadium carbide based electrodes also can be prepared by a similar synthesis process. This work will illuminate an entirely new avenue for the preparation of various self-supported three-dimensional electrodes made of transition-metal carbides for various applications.

  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. Bifunctional electrodes for unitised regenerative fuel cells

    International Nuclear Information System (INIS)

    Altmann, Sebastian; Kaz, Till; Friedrich, Kaspar Andreas

    2011-01-01

    Research highlights: → Different oxygen electrode configurations for the operation in a unitised reversible fuel cell were tested. → Polarisation curves and EIS measurements were recorded. → The mixture of catalysts performs best for the present stage of electrode development. → Potential improvements for the different compositions are discussed. - Abstract: The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.

  5. 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.

  6. Investigation of a Spinel-forming Cu-Mn Foam as an Oxygen Electrode Contact Material in a Solid Oxide Cell Single Repeating Unit

    DEFF Research Database (Denmark)

    Zielke, Philipp; Wulff, Anders Christian; Sun, Xiufu

    2017-01-01

    A critical issue in state-of-the-art solid oxide cell stacks is the contacting of the oxygen electrode. The commonly used ceramic contact layers are applied in a green state and cannot be sintered properly, due to compliance limitations arising from other stack components like sealing glasses...

  7. 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....

  8. 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.

  9. 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

  10. 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

  11. Suppression of interfacial reactions between Li4Ti5O12 electrode and electrolyte solution via zinc oxide coating

    International Nuclear Information System (INIS)

    Han, Cuiping; He, Yan-Bing; Li, Hongfei; Li, Baohua; Du, Hongda; Qin, Xianying; Kang, Feiyu

    2015-01-01

    Graphical abstract: The Li 4 Ti 5 O 12 (LTO) based batteries have severe gassing behavior due to the strong interfacial reactions between LTO and the electrolyte solution, which hampers the practical application of LTO in high power LIBs. The ZnO coating on LTO particles as a barrier layer can effectively suppress the interfacial reactions between LTO and the electrolyte solution. Simultaneously, the ZnO coating significantly reduces the charge-transfer resistance and increases the lithium ion diffusion coefficient, which leads to great improvement of rate and cyclic performance of LTO electrode. - Highlights: • A ZnO coating layer was constructed on the LTO particles by a chemical process as a barrier layer between LTO and surrounding electrolyte solution. • The ZnO coating can effectively stabilize the electrode/electrolyte interface and suppress interfacial reactions between LTO and electrolyte solution. • The ZnO coating can improve the electronic conductivity and lithium ion diffusion coefficient, which contributes to a great improvement in cyclic and high rate capabilities of LTO electrode. • The ZnO coating on LTO may be an effective method to solve the gassing behavior of LTO based battery and promote its wide application in lithium ion power battery. - Abstract: Li 4 Ti 5 O 12 (LTO) based batteries have severe gassing behavior during charge/discharge and storage process. The interfacial reactions between LTO and electrolyte solution may be the main reason. In this work, the LTO spinel particles are modified with ZnO coating using a chemical process to reduce the surface reactivity of LTO particles. Results show that the ZnO coating can effectively stabilize the electrode/electrolyte interface and suppress the formation of a solid electrolyte interface (SEI) film. Simultaneously, this ZnO modification can improve the electronic conductivity and lithium ion diffusion coefficient, which contributes to a great improvement in cyclic and high rate

  12. Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

    International Nuclear Information System (INIS)

    Valarselvan, S.; Manisankar, P.

    2011-01-01

    Graphical abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . Highlights: → Hydroxyl derivatives of anthraquinones as electrocatalysts for dioxygen reduction. → AQ/PPy composite film on GC electrode exhibits potent electrocatalytic activity. → Substituent groups influence electrocatalytic dioxygen reduction. → Surface coverage varies the rate of electrocatalytic dioxygen reduction. - Abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O 2 reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.

  13. Stoichiometric and Oxygen-Deficient VO2 as Versatile Hole Injection Electrode for Organic Semiconductors.

    Science.gov (United States)

    Fu, Keke; Wang, Rongbin; Katase, Takayoshi; Ohta, Hiromichi; Koch, Norbert; Duhm, Steffen

    2018-03-28

    Using photoemission spectroscopy, we show that the surface electronic structure of VO 2 is determined by the temperature-dependent metal-insulator phase transition and the density of oxygen vacancies, which depends on the temperature and ultrahigh vacuum (UHV) conditions. The atomically clean and stoichiometric VO 2 surface is insulating at room temperature and features an ultrahigh work function of up to 6.7 eV. Heating in UHV just above the phase transition temperature induces the expected metallic phase, which goes in hand with the formation of oxygen defects (up to 6% in this study), but a high work function >6 eV is maintained. To demonstrate the suitability of VO 2 as hole injection contact for organic semiconductors, we investigated the energy-level alignment with the prototypical organic hole transport material N, N'-di(1-naphthyl)- N, N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB). Evidence for strong Fermi-level pinning and the associated energy-level bending in NPB is found, rendering an Ohmic contact for holes.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Analyzing the anodic reactions for iron surface with a porous Al2O3 cluster with the scanning vibrating electrode

    Science.gov (United States)

    Eliyan, Faysal Fayez

    2017-09-01

    The Scanning Vibrating Electrode Technique (SVET) was used to analyze the anodic reactions inside and around a porous Al2O3 cluster embedded onto an iron foil. The tests were carried out at -0.7 V vs. Saturated Calomel Electrode, in naturally aerated solutions of 0.1, 0.2, 0.35, and 0.5 M bicarbonate concentration. During 10 h of testing, the SVET showed evidence for a formation of a passive film in and around the cluster, in the scanning area shown in the graphical abstract. In the dilute 0.1 and 0.2 M solutions, the passive films formed slower than those in 0.35 and 0.5 M solutions. In the SVET maps, the passive films showed that they could suppress dissolution to currents comparable to those of slower dissolution under the porous Al2O3 cluster.

  19. 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.

  20. 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.

  1. 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...

  2. 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

  3. 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

  4. Multi frequency phase fluorimetry (MFPF) for oxygen partial pressure measurement: ex vivo validation by polarographic clark-type electrode.

    Science.gov (United States)

    Boehme, Stefan; Duenges, Bastian; Klein, Klaus U; Hartwich, Volker; Mayr, Beate; Consiglio, Jolanda; Baumgardner, James E; Markstaller, Klaus; Basciani, Reto; Vogt, Andreas

    2013-01-01

    Measurement of partial pressure of oxygen (PO2) at high temporal resolution remains a technological challenge. This study introduces a novel PO2 sensing technology based on Multi-Frequency Phase Fluorimetry (MFPF). The aim was to validate MFPF against polarographic Clark-type electrode (CTE) PO2 measurements. MFPF technology was first investigated in N = 8 anaesthetised pigs at FIO2 of 0.21, 0.4, 0.6, 0.8 and 1.0. At each FIO2 level, blood samples were withdrawn and PO2 was measured in vitro with MFPF using two FOXY-AL300 probes immediately followed by CTE measurement. Secondly, MFPF-PO2 readings were compared to CTE in an artificial circulatory setup (human packed red blood cells, haematocrit of 30%). The impacts of temperature (20, 30, 40°C) and blood flow (0.8, 1.6, 2.4, 3.2, 4.0 L min(-1)) on MFPF-PO2 measurements were assessed. MFPF response time in the gas- and blood-phase was determined. Porcine MFPF-PO2 ranged from 63 to 749 mmHg; the corresponding CTE samples from 43 to 712 mmHg. Linear regression: CTE = 15.59+1.18*MFPF (R(2) = 0.93; P0.05). MFPF response-time (monoexponential) was 1.48±0.26 s for the gas-phase and 1.51±0.20 s for the blood-phase. MFPF-derived PO2 readings were reproducible and showed excellent correlation and good agreement with Clark-type electrode-based PO2 measurements. There was no relevant impact of temperature and blood flow upon MFPF-PO2 measurements. The response time of the MFPF FOXY-AL300 probe was adequate for real-time sensing in the blood phase.

  5. Oxygen tension in human tumours measured with polarographic needle electrodes and its relationship to vascular density, necrosis and hypoxia

    International Nuclear Information System (INIS)

    Lyng, Heidi; Sundfoer, Kolbein; Rofstad, Einar K.

    1997-01-01

    Background and purpose: The use of polarographic needle electrodes for measurement of oxygen tension (pO 2 ) in tumours requires documentation of the validity of the method. In the present work the pO 2 values measured polarographically with the Eppendorf pO 2 histograph in human tumours were compared with the histological appearance of the tumour tissue, i.e. vascular density, fraction of necrosis and fraction of hypoxic tissue, to investigate whether the measurements reflected the expected pO 2 . Materials and methods: The pO 2 was measured in cervix tumours in patients and in human melanoma xenografted tumours in athymic mice. Vascular density was determined in the cervix tumours by histological analysis of biopsies from the pO 2 measurement tracks. Fraction of necrosis and fraction of hypoxic tissue, i.e. tissue binding the hypoxia marker pimonidazole, were determined in the melanomas by analysis of histological sections from the tumour planes in which the pO 2 measurements were performed. Results: The pO 2 distributions showed large intratumour heterogeneity. In cervix tumours, tumour regions with vascular density (vascular length per unit tissue volume) in the range of 47-77 mm/mm 3 showed higher pO 2 than tumour regions with vascular density in the range of 20-47 mm/mm 3 , which in turn showed higher pO 2 than tumour regions with vascular density in the range of 0-20 mm/mm 3 . In melanomas, tumour regions in which necrosis and hypoxia constituted more than 50% of the tissue showed lower pO 2 than other tumour regions. Conclusions: The pO 2 measured in the tumours was consistent with the histological appearance of the tissue in which the measurements were performed, suggesting that reliable pO 2 distributions of tumours can be obtained with polarographic needle electrodes

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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)

  13. 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.

  14. Reaction products and corrosion of molybdenum electrode in glass melt containing antimony oxides and sodium sulfate

    Czech Academy of Sciences Publication Activity Database

    Matěj, J.; Langrová, Anna

    2012-01-01

    Roč. 56, č. 3 (2012), s. 280-285 ISSN 0862-5468 Institutional support: RVO:67985831 Keywords : antimony oxides * corrosion * glass melt * Molybdenum electrode * sulfate Subject RIV: DD - Geochemistry Impact factor: 0.418, year: 2012 http://www.ceramics-silikaty.cz/2012/pdf/2012_03_280.pdf

  15. Amphiphilic ligand exchange reaction-induced supercapacitor electrodes with high volumetric and scalable areal capacitances

    Science.gov (United States)

    Nam, Donghyeon; Heo, Yeongbeom; Cheong, Sanghyuk; Ko, Yongmin; Cho, Jinhan

    2018-05-01

    We introduce high-performance supercapacitor electrodes with ternary components prepared from consecutive amphiphilic ligand-exchange-based layer-by-layer (LbL) assembly among amine-functionalized multi-walled carbon nanotubes (NH2-MWCNTs) in alcohol, oleic acid-stabilized Fe3O4 nanoparticles (OA-Fe3O4 NPs) in toluene, and semiconducting polymers (PEDOT:PSS) in water. The periodic insertion of semiconducting polymers within the (OA-Fe3O4 NP/NH2-MWCNT)n multilayer-coated indium tin oxide (ITO) electrode enhanced the volumetric and areal capacitances up to 408 ± 4 F cm-3 and 8.79 ± 0.06 mF cm-2 at 5 mV s-1, respectively, allowing excellent cycling stability (98.8% of the initial capacitance after 5000 cycles) and good rate capability. These values were higher than those of the OA-Fe3O4 NP/NH2-MWCNT multilayered electrode without semiconducting polymer linkers (volumetric capacitance ∼241 ± 4 F cm-3 and areal capacitance ∼1.95 ± 0.03 mF cm-2) at the same scan rate. Furthermore, when the asymmetric supercapacitor cells (ASCs) were prepared using OA-Fe3O4 NP- and OA-MnO NP-based ternary component electrodes, they displayed high volumetric energy (0.36 mW h cm-3) and power densities (820 mW cm-3).

  16. Comparative Photoelectrochemical Study of PEC Solar Cell Fabricated with n-TiO2 Photo-electrodes at Different Temperatures and under Different Oxygen Flow Rates

    International Nuclear Information System (INIS)

    Mishra, P.R.; Srivastava, O.N.; Shukla, P.K.

    2006-01-01

    Photoelectrochemical splitting of water induced by solar energy for hydrogen production has been studied in the present investigation. PEC solar cell was fabricated with n-TiO 2 photo-electrodes synthesized at different oxidation temperatures e.g. 700 C, 750 C, 800 C and 850 C under oxygen flow rate 200 ml/min, 350 ml/min and 500 ml/min. The optimum oxygen flow rate for all the temperatures was found to be 350 ml/min. This is therefore kept invariant for synthesis of electrodes at different temperatures. The photo-electrochemical characterization of the PEC cell was done in the three-electrode configuration, i.e Ti/n-TiO 2 /1M-NaOH/Pt. It has been observed that the optimum values of the PEC solar cell parameters are exhibited by the solar cell employing the photo-electrodes prepared at ∼7500 C. The XRD and SEM explorations revealed that the TiO 2 prepared at ∼7500 C is in the nano-metric range (∼100-150 nm). The TiO 2 films formed at this temperature has been found to exhibit optimum PEC solar cell parameters. The PEC parameters, like photocurrent density, photo-conversion efficiency and hydrogen production rate, with this photo-electrode correspond to 0.93 mA/cm 2 , 0.472% and 4.00 l/hm 2 respectively. (authors)

  17. Fast and stable redox reactions of MnO2/CNT hybrid electrodes for dynamically stretchable pseudocapacitors

    Science.gov (United States)

    Gu, Taoli; Wei, Bingqing

    2015-07-01

    Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics.Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid

  18. In situ57Fe Moessbauer Investigation of Solid-State Redox Reactions of Lithium Insertion Electrodes for Advanced Batteries

    International Nuclear Information System (INIS)

    Sakai, Yoichi; Ariyoshi, Kingo; Ohzuku, Tsutomu

    2002-01-01

    A novel in situ electrochemical cell for 57 Fe Moessbauer measurements was developed in order to clarify the mechanisms of solid-state redox reactions in lithium insertion materials containing iron. Our in situ Moessbauer technique was successfully applied to the determination as to which transition metal ion was a redox center in the insertion electrodes, such as LiFe 0.5 Mn 1.5 O 4 , LiFeTiO 4 , or LiFe 0.25 Ni 0.75 O 2 , for the lithium-ion batteries.

  19. 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

  20. 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.

  1. Preliminary study on zinc-air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction

    Science.gov (United States)

    Wen, Yue-Hua; Cheng, Jie; Ning, Shang-Qi; Yang, Yu-Sheng

    A zinc-air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction is reported in this paper. It possesses functions of both zincate reduction and electrochemical preparation, showing the potential for increasing the electronic energy utilization. Charge/discharge tests and scanning electron microscopy (SEM) micrographs reveal that when a nickel sheet plated with the high-H 2-overpotential metal, cadmium, was used as the negative substrate electrode, the dendritic formation and hydrogen evolution are suppressed effectively, and granular zinc deposits become larger but relatively dense with the increase of charge time. The performance of batteries is favorable even if the charge time is as long as 5 h at the current density of 20 mA cm -2. Better discharge performance is achieved using a 'cavity-opening' configuration for the discharge cell rather than a 'gas-introducing' configuration. The highest energy efficiency is up to 59.2%. That is, the energy consumed by organic electro-synthesis can be recovered by 59.2%. Cyclic voltammograms show that the sintered nickel electrode exhibits a good electro-catalysis activity for the propanol oxidation. The increase of propanol concentration conduces to an enhancement in the organic electro-synthesis efficiency. The organic electro-synthesis current efficiency of 82% can be obtained.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  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. NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires with surface rich high valence state metal oxide as an efficient electrocatalyst for oxygen evolution reaction

    Science.gov (United States)

    Yang, Liting; Chen, Lin; Yang, Dawen; Yu, Xu; Xue, Huaiguo; Feng, Ligang

    2018-07-01

    High valence transition metal oxide is significant for anode catalyst of proton membrane water electrolysis technique. Herein, we demonstrate NiMn layered double hydroxide nanosheets/NiCo2O4 nanowires hierarchical nanocomposite catalyst with surface rich high valence metal oxide as an efficient catalyst for oxygen evolution reaction. A low overpotential of 310 mV is needed to drive a 10 mA cm-2 with a Tafel slope of 99 mV dec-1, and a remarkable stability during 8 h is demonstrated in a chronoamperometry test. Theoretical calculation displays the change in the rate-determining step on the nanocomposite electrode in comparison to NiCo2O4 nanowires alone. It is found high valence Ni and Mn oxide in the catalyst system can efficiently facilitate the charge transport across the electrode/electrolyte interface. The enhanced electrical conductivity, more accessible active sites and synergistic effects between NiMn layered double hydroxide nanosheets and NiCo2O4 nanowires can account for the excellent oxygen evolution reaction. The catalytic performance is comparable to most of the best non-noble catalysts and IrO2 noble catalyst, indicating the promising applications in water-splitting technology. It is an important step in the development of hierarchical nanocomposites by surface valence state tuning as an alternative to noble metals for oxygen evolution reaction.

  9. A chip-type thin-layer electrochemical cell coupled with capillary electrophoresis for online separation of electrode reaction products

    Energy Technology Data Exchange (ETDEWEB)

    He, Jian-Bo, E-mail: jbhe@hfut.edu.cn; Cui, Ting; Zhang, Wen-Wen; Deng, Ning

    2013-07-05

    Graphical abstract: -- Highlights: •A new coupling of thin-layer electrolysis with capillary electrophoresis (CE). •Rapid electrolysis, direct sampling followed by online CE separation. •At least 13 products of quercetin oxidation were separated. •Thermodynamic and kinetic parameters were determined from CE peak areas. -- Abstract: A coupling technique of thin-layer electrolysis with high-performance capillary electrophoresis/UV–vis technique(EC/HPCE/UV–vis) is developed for online separation and determination of electrode reaction products. A chip-type thin-layer electrolytic (CTE) cell was designed and fabricated, which contains a capillary channel and a background electrolyte reservoir, allowing rapid electrolysis, direct sampling and online electrophoretic separation. This chip-type setup was characterized based on an electrophoresis expression of Nernst equation that was applied to the redox equilibrium of o-tolidine at different potentials. The utility of the method was demonstrated by separating and determining the electro-oxidation products of quercetin in different pH media. Two main products were always found in the studied time, potential and pH ranges. The variety of products increased not only with increasing potential but also with increasing pH value, and in total, at least 13 products were observed in the electropherograms. This work illustrates a novel example of capillary electrophoresis used online with thin-layer electrolysis to separate and detect electrode reaction products.

  10. A chip-type thin-layer electrochemical cell coupled with capillary electrophoresis for online separation of electrode reaction products

    International Nuclear Information System (INIS)

    He, Jian-Bo; Cui, Ting; Zhang, Wen-Wen; Deng, Ning

    2013-01-01

    Graphical abstract: -- Highlights: •A new coupling of thin-layer electrolysis with capillary electrophoresis (CE). •Rapid electrolysis, direct sampling followed by online CE separation. •At least 13 products of quercetin oxidation were separated. •Thermodynamic and kinetic parameters were determined from CE peak areas. -- Abstract: A coupling technique of thin-layer electrolysis with high-performance capillary electrophoresis/UV–vis technique(EC/HPCE/UV–vis) is developed for online separation and determination of electrode reaction products. A chip-type thin-layer electrolytic (CTE) cell was designed and fabricated, which contains a capillary channel and a background electrolyte reservoir, allowing rapid electrolysis, direct sampling and online electrophoretic separation. This chip-type setup was characterized based on an electrophoresis expression of Nernst equation that was applied to the redox equilibrium of o-tolidine at different potentials. The utility of the method was demonstrated by separating and determining the electro-oxidation products of quercetin in different pH media. Two main products were always found in the studied time, potential and pH ranges. The variety of products increased not only with increasing potential but also with increasing pH value, and in total, at least 13 products were observed in the electropherograms. This work illustrates a novel example of capillary electrophoresis used online with thin-layer electrolysis to separate and detect electrode reaction products

  11. Novel thin/tunable gas diffusion electrodes with ultra-low catalyst loading for hydrogen evolution reactions in proton exchange membrane electrolyzer cells

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Zhenye; Yang, Gaoqiang; Mo, Jingke; Li, Yifan; Yu, Shule; Cullen, David A.; Retterer, Scott T.; Toops, Todd J.; Bender, Guido; Pivovar, Bryan S.; Green, Johney B.; Zhang, Feng-Yuan

    2018-05-01

    Proton exchange membrane electrolyzer cells (PEMECs) have received great attention for hydrogen/oxygen production due to their high efficiencies even at low-temperature operation. Because of the high cost of noble platinum-group metal (PGM) catalysts (Ir, Ru, Pt, etc.) that are widely used in water splitting, a PEMEC with low catalyst loadings and high catalyst utilizations is strongly desired for its wide commercialization. In this study, the ultrafast and multiscale hydrogen evolution reaction (HER) phenomena in an operating PEMEC is in-situ observed for the first time. The visualization results reveal that the HER and hydrogen bubble nucleation mainly occur on catalyst layers at the rim of the pores of the thin/tunable liquid/gas diffusion layers (TT-LGDLs). This indicates that the catalyst material of the conventional catalyst-coated membrane (CCM) that is located in the middle area of the LGDL pore is underutilized/inactive. Based on this discovery, a novel thin and tunable gas diffusion electrode (GDE) with a Pt catalyst thickness of 15 nm and a total thickness of about 25 um has been proposed and developed by taking advantage of advanced micro/nano manufacturing. The novel thin GDEs are comprehensively characterized both ex-situ and in-situ, and exhibit excellent PEMEC performance. More importantly, they achieve catalyst mass activity of up to 58 times higher than conventional CCM at 1.6 V under the operating conditions of 80 degrees C and 1 atm. This study demonstrates a promising concept for PEMEC electrode development, and provides a direction of future catalyst designs and fabrications for electrochemical devices.

  12. High performance cermet electrodes

    Science.gov (United States)

    Isenberg, Arnold O.; Zymboly, Gregory E.

    1986-01-01

    Disclosed is a method of increasing the operating cell voltage of a solid oxide electrochemical cell having metal electrode particles in contact with an oxygen-transporting ceramic electrolyte. The metal electrode is heated with the cell, and oxygen is passed through the oxygen-transporting ceramic electrolyte to the surface of the metal electrode particles so that the metal electrode particles are oxidized to form a metal oxide layer between the metal electrode particles and the electrolyte. The metal oxide layer is then reduced to form porous metal between the metal electrode particles and the ceramic electrolyte.

  13. Characterization and Electrocatalytic Properties of Titanium-Based Ru0.3Co0.7−xCex Mixed Oxide Electrodes for Oxygen Evolution in Alkaline Solution

    Directory of Open Access Journals (Sweden)

    Hongjun Wu

    2011-01-01

    Full Text Available Ti-supported RuO2-Co3O4-CeO2 (Ru0.3Co0.7−xCex oxide, 0≤x≤0.7 electrodes were prepared by sol-gel process. The phase structure, surface morphology, and microstructure of the oxide layer were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Electrocatalytic activity and oxygen evolution reaction (OER kinetics on these electrodes in 1.0 mol⋅dm−3 KOH solution were studied by recording open-circuit potential, cyclic voltammetry, and polarisation curves. The results showed that the appropriate content of CeO2 could reduce the grain size and increase active surface area. The electrocatalytic activity shows a strong dependence on the CeO2 content in the film. Catalytic performance of mixed oxide electrodes with 40 mol % CeO2 was the best, with the greatest voltammetric charge, 86.23 mC⋅cm−2, and the smallest apparent activation energy for OER at 0.60 V was 22.76 kJ⋅mol−1.

  14. 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.

  15. 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

  16. 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.

  17. 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...

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Oxygen Electrode Kinetics and Surface Composition of Dense (La0.75Sr0.25)0.95MnO3 on YSZ

    DEFF Research Database (Denmark)

    Wu, Yuehua; Hansen, Karin Vels; Norrman, Kion

    2013-01-01

    in situ at temperatures from 660 to 860 C using a controlled atmosphere high temperature scanning probe microscope (CAHT-SPM) setup for measurements of impedance spectroscopy and potential sweep. The oxygen partial pressure, pO2, was varied. Further, ex situ surface analysis by time of flight secondary...... ion mass spectrometry (TOF-SIMS) and structure examination by scanning electron microscopy (SEM) were performed. Segregation of Sr and La oxides to LSM surfaces and Mn rich oxide to the three phase boundary (TPB) was observed. YSZ and LSM attract different oxides/impurities. The oxygen electrode...

  5. Multi Frequency Phase Fluorimetry (MFPF) for Oxygen Partial Pressure Measurement: Ex Vivo Validation by Polarographic Clark-Type Electrode

    Science.gov (United States)

    Boehme, Stefan; Duenges, Bastian; Klein, Klaus U.; Hartwich, Volker; Mayr, Beate; Consiglio, Jolanda; Baumgardner, James E.; Markstaller, Klaus; Basciani, Reto; Vogt, Andreas

    2013-01-01

    Background Measurement of partial pressure of oxygen (PO2) at high temporal resolution remains a technological challenge. This study introduces a novel PO2 sensing technology based on Multi-Frequency Phase Fluorimetry (MFPF). The aim was to validate MFPF against polarographic Clark-type electrode (CTE) PO2 measurements. Methodology/Principal Findings MFPF technology was first investigated in N = 8 anaesthetised pigs at FIO2 of 0.21, 0.4, 0.6, 0.8 and 1.0. At each FIO2 level, blood samples were withdrawn and PO2 was measured in vitro with MFPF using two FOXY-AL300 probes immediately followed by CTE measurement. Secondly, MFPF-PO2 readings were compared to CTE in an artificial circulatory setup (human packed red blood cells, haematocrit of 30%). The impacts of temperature (20, 30, 40°C) and blood flow (0.8, 1.6, 2.4, 3.2, 4.0 L min−1) on MFPF-PO2 measurements were assessed. MFPF response time in the gas- and blood-phase was determined. Porcine MFPF-PO2 ranged from 63 to 749 mmHg; the corresponding CTE samples from 43 to 712 mmHg. Linear regression: CTE = 15.59+1.18*MFPF (R2 = 0.93; PPO2 ranged from 20 to 567 mmHg and CTE samples from 11 to 575 mmHg. Linear regression: CTE = −8.73+1.05*MFPF (R2 = 0.99; PPO2 due to variations of temperature were less than 6 mmHg (range 0–140 mmHg) and less than 35 mmHg (range 140–750 mmHg); differences due to variations in blood flow were less than 15 mmHg (all P-values>0.05). MFPF response-time (monoexponential) was 1.48±0.26 s for the gas-phase and 1.51±0.20 s for the blood-phase. Conclusions/Significance MFPF-derived PO2 readings were reproducible and showed excellent correlation and good agreement with Clark-type electrode-based PO2 measurements. There was no relevant impact of temperature and blood flow upon MFPF-PO2 measurements. The response time of the MFPF FOXY-AL300 probe was adequate for real-time sensing in the blood phase. PMID:23565259

  6. 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).

  7. 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.

  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. Mn valence state and electrode performance of perovskite-type ...

    Indian Academy of Sciences (India)

    increase in the oxidation state of Mn ions was due to the formation of Mn4+ ions and oxygen vacancies. The addition of Cu ions to LSM systems could lead to enhanced electrode performance for oxygen reduction reactions originating from the change in valence of Mn ions. Keywords. Cu-doped LSM; electrical conductivity; ...

  11. Ultramicroelectrode studies of oxygen reduction 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

    A study on the oxygen reduction reaction in a solid state electrochemical cell was presented. The oxygen reduction reaction is a rate limiting reaction in the operation of solid polymer electrolyte fuel cells which use H{sub 2} and O{sub 2}. Interest in the oxygen reduction reaction of platinum electrodes in contact with Nafion electrolytes stems from its role in fuel cell technology. The kinetics of the oxygen reduction reaction in different polyelectrolyte membranes, such as Nafion and non-Nafion membranes, were compared. The electrode kinetics and mass transport parameters of the oxygen reduction reaction in polyelectrolyte membranes were measured by ultramicroelectrode techniques. The major difference found between these two classes of membrane was the percentage of water, which is suggestive of superior electrochemical mass transport properties of the non-Nafion membranes. 2 refs. 1 fig.

  12. Inkjet printing of nanoporous gold electrode arrays on cellulose membranes for high-sensitive paper-like electrochemical oxygen sensors using ionic liquid electrolytes.

    Science.gov (United States)

    Hu, Chengguo; Bai, Xiaoyun; Wang, Yingkai; Jin, Wei; Zhang, Xuan; Hu, Shengshui

    2012-04-17

    A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.

  13. Oxygen reduction activities compared in rotating-disk electrode and proton exchange membrane fuel cells for highly active Fe-N-C catalysts

    International Nuclear Information System (INIS)

    Jaouen, F.; Goellner, V.; Lefèvre, M.; Herranz, J.; Proietti, E.; Dodelet, J.P.

    2013-01-01

    In the past three years, two novel synthesis methods for non-precious metal catalysts resulting in a breakthrough of their activity and performance at the cathode of the proton-exchange membrane fuel cell (PEMFC) have been reported by the group of Prof. Dodelet. While the activity of these novel Fe-based catalysts for the oxygen reduction reaction is very high in PEMFC, our preliminary activity measurements with the rotating disk electrode (RDE) technique on one of them showed an activity being a factor 30–100 lower than the one measured in PEMFC at 80 °C. The present work explains to a large extent this huge difference. Two Fe-N-C catalysts synthesized via our novel approaches and one Fe-N-C catalyst synthesized via our classical approach were investigated in RDE and PEMFC. In both systems, the effect of the ink formulation (Nafion-to-catalyst ratio) was investigated. Optimization of the RDE ink formulation explains a factor between 5 and 10 in the two-decade gap mentioned above. Then, the effect of temperature in the RDE system was investigated. An increase from 20 to 80 °C was found to result in a theoretical maximum twofold increase in activity. However, in practice, decreased O 2 solubility with increased temperature cancels this effect. After taking into account these two parameters, a difference in ORR activity between RDE and PEMFC of ca a factor five still remained for one of the two novel Fe-N-C catalysts investigated here. The lower initial activity measured in RDE for this catalyst is shown to be due to the fast adsorption of anions (HSO 4 − ) from the liquid H 2 SO 4 electrolyte on protonated nitrogen atoms (NH + ) found on its surface. The phenomenon of anion adsorption and associated decreased ORR activity also applies to the other novel Fe-N-C catalyst, but is slower and does not immediately occur in RDE.

  14. Electrode reactions of ruthenium–bipyridine complex in amide-type ionic liquids

    International Nuclear Information System (INIS)

    Toshimitsu, Yuichi; Katayama, Yasushi; Miura, Takashi

    2012-01-01

    The electrode kinetics of [Ru(bpy) 3 ] 3+ /[Ru(bpy) 3 ] 2+ (bpy = 2,2′-bipyridine) on a platinum electrode was investigated in room-temperature ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMITFSA), and 1-butyl-1-methylpyrrolidinium bis(perfluoroethylsulfonyl)amide (BMPBETA) over the temperature range from 25 to 45 °C. The diffusion coefficients of [Ru(bpy) 3 ] 2+ and [Ru(bpy) 3 ] 3+ were found to be affected not only by the viscosity of ionic liquids but also by the charge density of the complex. The activation energy for the diffusion coefficients of these complexes in the ionic liquids were close to that for the viscosity of the ionic liquids. The standard rate constants of [Ru(bpy) 3 ] 3+ /[Ru(bpy) 3 ] 2+ in BMPTFSA, EMITFSA and BMPBETA were estimated by electrochemical impedance spectroscopy. The standard rate constants in the ionic liquids were estimated to be smaller than those in aqueous and organic electrolytes, probably due to the slow dynamics of the ionic liquids.

  15. 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...

  16. 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.

  17. 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.

  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. Investigation of reaction mechanisms during electroreduction of carbon dioxide on lead electrode for the production of organic compounds

    International Nuclear Information System (INIS)

    Innocent, B.

    2008-09-01

    The aim of this work was to promote the reduction of CO 2 through its electrochemical conversion (electro-synthesis) on a lead electrode into high added value products. Depending on the nature of electrolyte, the electro-reduction of carbon dioxide leads to different products. Various electrolytes (aqueous or organic, protic or aprotic) were used to study two mechanisms: hydrogenation (formation of formate) and electro-dimerization (synthesis of oxalate). Cyclic voltammetry studies have been carried out for electrochemically characterizing CO 2 reduction on Pb. The electrochemical investigation of the electrode electrolyte interface has shown that the process of CO 2 electro-reduction is a mass transfer control both in the organic and aqueous media. Electrochemical experiments (cyclic voltammetry, chrono-amperometry) coupled with in situ infrared reflectance spectroscopic techniques (SPAIRS, SNIFTIRS) have also shown that in aqueous medium (7 ≤pH≤9) hydrogeno-carbonate ions were reduced to formate. The modification of solvent (propylene carbonate) leads selectively to oxalate as the main reaction product. Long-term electrolyses were performed in a filter-press cell to deal large volumes. In aqueous medium, the reduction of HCO 3 - to HCOO - (R F = 89% at -2.5 mA cm -2 and 4 C) is always accompanied by the production of H 2 . (author)

  2. Self-assembled dopamine nanolayers wrapped carbon nanotubes as carbon-carbon bi-functional nanocatalyst for highly efficient oxygen reduction reaction and antiviral drug monitoring

    Science.gov (United States)

    Khalafallah, Diab; Akhtar, Naeem; Alothman, Othman Y.; Fouad, H.; Abdelrazek khalil, Khalil

    2017-09-01

    Oxygen reduction reaction (ORR) catalysts are the heart of eco-friendly energy resources particularly low temperature fuel cells. Although valuable efforts have been devoted to synthesize high performance catalysts for ORR, considerable challenges are extremely desirable in the development of energy technologies. Herein, we report a simple self-polymerization method to build a thin film of dopamine along the tubular nanostructures of multi-walled carbon nanotubes (CNT) in a weak alkaline solution. The dopamine@CNT hybrid (denoted as DA@CNT) reveals an enhanced electrocatalytic activity towards ORR with highly positive onset potential and cathodic current as a result of their outstanding features of longitudinal mesoporous structure, high surface area, and ornamentation of DA layers with nitrogen moieties, which enable fast electron transport and fully exposed electroactive sites. Impressively, the as-obtained hybrid afford remarkable electrochemical durability for prolonged test time of 60,000 s compared to benchmark Pt/C (20 wt%) catalyst. Furthermore, the developed DA@CNT electrode was successfully applied to access the quality of antiviral drug named Valacyclovir (VCR). The DA@CNT electrode shows enhanced sensing performance in terms of large linear range (3-75 nM), low limit of detection (2.55 nM) than CNT based electrode, indicating the effectiveness of the DA coating. Interestingly, the synergetic effect of nanostructured DA and CNT can significantly boost the electronic configuration and exposure level of active species for ORR and biomolecule recognition. Therefore, the existing carbon-based porous electrocatalyst may find numerous translational applications as attractive alternative to noble metals in polymer electrolyte membrane fuel cells and quality control assessment of pharmaceutical and therapeutic drugs.

  3. 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.

  4. 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.

  5. 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

  6. Electrochemistry of single nanobubbles. Estimating the critical size of bubble-forming nuclei for gas-evolving electrode reactions.

    Science.gov (United States)

    German, Sean R; Edwards, Martin A; Chen, Qianjin; Liu, Yuwen; Luo, Long; White, Henry S

    2016-12-12

    In this article, we address the fundamental question: "What is the critical size of a single cluster of gas molecules that grows and becomes a stable (or continuously growing) gas bubble during gas evolving reactions?" Electrochemical reactions that produce dissolved gas molecules are ubiquitous in electrochemical technologies, e.g., water electrolysis, photoelectrochemistry, chlorine production, corrosion, and often lead to the formation of gaseous bubbles. Herein, we demonstrate that electrochemical measurements of the dissolved gas concentration, at the instant prior to nucleation of an individual nanobubble of H 2 , N 2 , or O 2 at a Pt nanodisk electrode, can be analyzed using classical thermodynamic relationships (Henry's law and the Young-Laplace equation - including non-ideal corrections) to provide an estimate of the size of the gas bubble nucleus that grows into a stable bubble. We further demonstrate that this critical nucleus size is independent of the radius of the Pt nanodisk employed (gas. For example, the measured critical surface concentration of H 2 of ∼0.23 M at the instant of bubble formation corresponds to a critical H 2 nucleus that has a radius of ∼3.6 nm, an internal pressure of ∼350 atm, and contains ∼1700 H 2 molecules. The data are consistent with stochastic fluctuations in the density of dissolved gas, at or near the Pt/solution interface, controlling the rate of bubble nucleation. We discuss the growth of the nucleus as a diffusion-limited process and how that process is affected by proximity to an electrode producing ∼10 11 gas molecules per second. Our study demonstrates the advantages of studying a single-entity, i.e., an individual nanobubble, in understanding and quantifying complex physicochemical phenomena.

  7. MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Biaohua [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; He, Xiaobo [Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China; Yin, Fengxiang [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou 213164 P. R. China; Wang, Hao [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Beijing Key Laboratory of Energy Environmental Catalysis, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Liu, Di-Jia [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Shi, Ruixing [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Chen, Jinnan [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China; Yin, Hongwei [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 P. R. China

    2017-06-14

    A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-x and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO2.

  8. 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.

  9. Sensor employing internal reference electrode

    DEFF Research Database (Denmark)

    2013-01-01

    The present invention concerns a novel internal reference electrode as well as a novel sensing electrode for an improved internal reference oxygen sensor and the sensor employing same.......The present invention concerns a novel internal reference electrode as well as a novel sensing electrode for an improved internal reference oxygen sensor and the sensor employing same....

  10. 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.

  11. electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to ...

  12. Electrocatalytic reduction of oxygen at vapor phase polymerized ...

    African Journals Online (AJOL)

    We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

  13. 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...

  14. 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...

  15. 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.

  16. 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).

  17. 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

  18. 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.

  19. 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)

  20. 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.

  1. 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

  2. Main alloy elements in covered electrodes in terms of the amount of oxygen in weld metal deposits (WMD

    Directory of Open Access Journals (Sweden)

    T. Węgrzyn

    2012-04-01

    Full Text Available There were investigated properties of WMD, especially metallographic structure, toughness and fatigue strength of welds with various oxygen amount. The connection between the properties of welds with the content of oxygen in WMD were carried out. The research results indicate that it should be limited oxygen content in steel welds. Subsequent researchers could find more precisely the most beneficial oxygen amount in the welds in terms of the amount of acicular ferrite in welds.

  3. 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.

  4. 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.

  5. 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.

  6. 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)

  7. 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.

  8. 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.

  9. 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.

  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. 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.

  13. 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.

  14. 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.

  15. 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)

  16. 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.

  17. Effect of samaria-doped ceria (SDC) interlayer on the performance of La0.6Sr0.4Co0.2Fe0.8O3-δ/SDC composite oxygen electrode for reversible solid oxide fuel cells

    International Nuclear Information System (INIS)

    Shimura, Kazuki; Nishino, Hanako; Kakinuma, Katsuyoshi; Brito, Manuel E.; Uchida, Hiroyuki

    2017-01-01

    In order to establish clear criteria for designing highly active and highly durable oxygen electrode for reversible solid oxide fuel cells, we have focused on the effect of samaria-doped ceria (SDC) interlayers prepared on YSZ solid electrolyte surface on the performances of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF)-SDC composite oxygen electrode. Symmetrical cells with the configuration, LSCF-SDC|SDC interlayer|YSZ|SDC interlayer|LSCF-SDC, were constructed. We prepared two kinds of SDC interlayers, one from a mixed solution of cerium 2-ethylhexanoate (denoted as octoate) and samarium octoates (o-interlayer) and another from a mixed solution of cerium and samarium nitrates (n-interlayer). The LSCF-SDC electrodes with o-interlayer and n-interlayer exhibited very similar performances in both the anodic and cathodic reactions at 900 °C. When temperature was decreased to 800 °C, an increase in overpotentials was observed. However, the LSCF-SDC electrode with o-interlayer exhibited superior performance to that with n-interlayer. It was found that the entire surface of the YSZ electrolyte disk was well covered with a dense o-interlayer of uniform thickness. Such an interlayer enables uniform transport of oxide ions to and from the LSCF-SDC electrode, resulting in an enlarged effective reaction zone (ERZ). The I-E performance of the LSCF-SDC|o-interlayer|YSZ cell was found to be comparable to that of the identical electrode prepared on a dense SDC sintered electrolyte disk (as a reference). This observation supports our views regarding the essential role of a dense interlayer with uniform thickness in enhancing the performance of reversible solid oxide cells.

  18. Report on the FY 1999 investigational survey on the activation of oxygen electrode by ion implantation; 1999 nendo ion chunyuho ni yoru sanso denkyoku no kasseika ni kansuru kenkyu chosa hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2000-03-01

    The oxygen electrode is important as the base electrode for water electrolysis and fuel cell, but to move it, overvoltage (activated energy) in addition to equilibrium voltage is necessary, which leads to the lowering of energy efficiency. By forming the active spot by ion implantation, the lowering of overvoltage was studied. The implantation of Ru{sup +} ion in Ruthenium dioxide thin film electrode reduced the oxygen generating overvoltage by 15-20mV. Even in the oxygen reduction, activity was also increased. The chemical composition of thin film does not change by ion implantation. The increase in activity is based on a physical change which is called the surface defect formation. The layer of ion implantation is composed of microcrystals, which is thought to contribute to the formation of any active spot. Ions were implanted in Pt electrode as a practical use material, and even in the oxygen reduction of Pt, a possibility of heightening activity by ion implantation was admitted even in the oxygen reduction of Pt. The generation of high activity oxygen by ion plantation and development of oxygen reduction electrode were established as one method as a rule. (NEDO)

  19. 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.

  20. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); Stolte, Stefan [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); UFT-Centre of Environmental Research and Sustainable Technology, University of Bremen, Leobener Straße UFT, D-28359 Bremen (Germany); Siedlecka, Ewa Maria, E-mail: ewa.siedlecka@ug.edu.pl [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland)

    2014-09-15

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.

  1. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    International Nuclear Information System (INIS)

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr; Stolte, Stefan; Siedlecka, Ewa Maria

    2014-01-01

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na 2 SO 4 . The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test

  2. 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.

  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. Control of oxygen octahedral rotation in BiFeO3 films using modulation of SrRuO3 bottom electrode layer

    Science.gov (United States)

    Lee, Sungsu; Jo, Ji Young

    2015-03-01

    Oxygen octahedral rotation of multiferroic BiFeO3 (BFO) has attracted great attention due to changes of electrical and magnetic properties. Coupling of octahedral rotation in BFO-bottom electrode layer interface remains unexplored. Recently, there have been reported the control of octahedral rotation in SrRuO3 (SRO) film on SrTiO3 (001) substrate by coherently controlling the oxygen pressure during growth and interfacial coupling. Here we demonstrate that the octahedral rotation of BFO film is changed using tetragonal a0a0c- tilted-SRO bottom electrodes. In this work, BFO/SRO heterostructure is fabricated to SrTiO3 (001) single crystal substrates by pulsed laser deposition at different oxygen partial pressures. The rotation pattern of FeO6 and the structural symmetry are identified from half-integer reflections using high-resolution X-ray diffraction. The effects depending on octahedral tilting of BFO films on the magnetic and ferroelectric properties will be presented.

  5. 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.

  6. Transport phenomena in solid oxide fuel cell electrodes focusing on heat transfer related to chemical reactions

    International Nuclear Information System (INIS)

    Navasa, M; Andersson, M; Yuan, J; Sundén, B

    2012-01-01

    Solid oxide fuel cells (SOFCs) are widely studied for their advantages especially at high temperatures. However, operating at high temperatures represents a high cost due to the strict requirements the materials are expected to fulfill. Thus, the main goal in SOFC research has been to decrease the operating temperature so that the range of available materials is widened and hence, the operating cost can be reduced. In this paper, the different heat sources that contribute to the cell energy balance are presented with strong emphasis on the chemical reactions that take place in SOFCs. The knowledge of which heat sources or sinks taking place and their locations within the SOFC can provide useful information for further design and efficiency improvements.

  7. 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.

  8. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  9. Interplay of tumor vascular oxygenation and tumor pO2 observed using near-infrared spectroscopy, an oxygen needle electrode, and 19F MR pO2 mapping.

    Science.gov (United States)

    Kim, Jae G; Zhao, Dawen; Song, Yulin; Constantinescu, Anca; Mason, Ralph P; Liu, Hanli

    2003-01-01

    This study investigates the correlation of tumor blood oxygenation and tumor pO(2) with respect to carbogen inhalation. After having refined and validated the algorithms for calculating hemoglobin concentrations, we used near-infrared spectroscopy (NIRS) to measure changes of oxygenated hemoglobin concentration (delta[HbO(2)]) and used an oxygen needle electrode and (19)F MRI for pO(2) measurements in tumors. The measurements were taken from Dunning prostate R3327 tumors implanted in rats, while the anesthetized rats breathed air or carbogen. The NIRS results from tumor measurements showed significant changes in tumor vascular oxygenation in response to carbogen inhalation, while the pO(2) electrode results showed an apparent heterogeneity for tumor pO(2) response to carbogen inhalation, which was also confirmed by (19)F MR pO(2) mapping. Furthermore, we developed algorithms to estimate hemoglobin oxygen saturation, sO(2), during gas intervention based on the measured values of delta[HbO(2)] and pO(2). The algorithms have been validated through a tissue-simulating phantom and used to estimate the values of sO(2) in the animal tumor measurement based on the NIRS and global mean pO(2) values. This study demonstrates that the NIRS technology can provide an efficient, real-time, noninvasive approach to monitoring tumor physiology and is complementary to other techniques, while it also demonstrates the need for an NIR imaging technique to study spatial heterogeneity of tumor vasculature under therapeutic interventions. Copyright 2003 Society of Photo-Optical Instrumentation Engineers

  10. 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...

  11. Fabrication and characterization of nanostructured mechanically alloyed Pt-Co catalyst for oxygen gas-diffusion-electrode

    International Nuclear Information System (INIS)

    Pharkya, P.; Farhat, Z.; Czech, E.; Hawthorne, H.; Alfantazi, A.

    2003-01-01

    The use of PEM fuel cells depends largely upon the cost of materials, processing and fabrication. The cost of Pt catalyst is a significant cost of a fuel cell. Alternative low cost catalyst that promotes high rate of oxygen reduction is needed. To achieve this, a mechanochemical technique was employed to refine the catalyst layer structure (i.e. increasing the effective catalyst surface area) and reducing the amount of Pt used, by alloying with a cheaper element. An investigation is carried out to study the relationship between the new catalyst structure refinement, morphology, microstructure and its electrocatalytic behaviour. Nanostructured Pt, Co and Pt 0.2 5 Co 0.75 alloy was fabricated from high purity Pt (99.9%) and Co (99.5%) powders using a Laboratory Planetary Ball Mill 'Pulverisette 6'. Optimum milling conditions, that produce fine, uniform and mechanically alloyed microstructure, were determined during fabrication, by varying process parameters (i.e., rpm, milling time, ball to powder ratio, milling atmosphere, surface-agents and milling/cooling cycle). Mechanically induced chemical and physical reactions and thermal effects were monitored 'in-situ' using a GTM system, which recorded temperature and pressure changes during milling. The alloy catalysts were characterized using TEM, SEM, EDX, XRD and BET techniques. Electrochemical tests were carried out on prepared powders. Exchange currents were determined from a potentiodynamic polarization tests and used to compare relative electrocatalytic behaviour of the new catalyst. Structure/property relationships were discussed and conclusions were drawn on the production of improved low cost catalyst. (author)

  12. 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)

  13. 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.

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

    DEFF Research Database (Denmark)

    Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

    2012-01-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction...

  15. 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.

  16. The oxygen sensitivity of a multipoint antimony electrode for tissue pH measurements. A study of the sensitivity for in vivo PO2 variations below 6 kPa.

    Science.gov (United States)

    Sjöberg, F; Edwall, G; Lund, N

    1987-02-01

    Monocrystalline micro antimony electrodes in a multipoint arrangement as described by Lund et al. were placed on the skeletal muscle surface of the rabbit. Tissue oxygen levels were measured simultaneously with the MDO (Mehrdraht Dortmund Oberfläche) oxygen electrode. The sensitivity for variations in tissue PO2 (PO2(t)) was evaluated for the antimony metal-metal oxide sensor. The sensitivity (delta E/delta log10 PO2)+/- SE was found to be 21.8 +/- 1.2 mV in the interval between 0.1 kPa and 1 kPa and 53 +/- 5 mV in the interval between 1 kPa and 6 kPa. These results are not consistent with the oxygen sensitivity of monocrystalline antimony described in vitro, but are in agreement with the findings of Nilsson & Edwall. A plausible explanation for the S-shaped oxygen sensitivity curve of antimony at oxygen levels below 10 kPa could be an interaction, at the electrode surface, between the dissolved oxygen and the oxygen bound to haemoglobin. If this is the case, the use of an antimony electrode would make possible the determination of the dissociation of oxyhaemoglobin in tissues.

  17. 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.

  18. 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

  19. 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.

  20. Silicon carbide-silicon as a support material for oxygen evolution reaction in PEM steam electrolysers

    DEFF Research Database (Denmark)

    Nikiforov, Aleksey; Petrushina, Irina; Christensen, Erik

    cells. In the present work a commercial SiC-Si, produced by the Acheson process, with a fraction of free silicon around 20% wt. was investigated as a catalyst support for anode electrocatalyst in PEM steam electrolysers. This electrocatalyst system was characterized using several techniques such as XRD......, cyclic voltammetry, SEM, EDX and steady state electrochemical polarisation in a working PEM steam electrolyser. Several SiC-Si-IrO2 electrodes have been prepared and tested. The iridium oxide content at the electrode active layer varied from x=0.2 to x=1, corresponding to the general formula (1-x...... for phosphoric acid doped membrane steam electrolysers....

  1. Nitrogen and sulfur co-doped porous carbon – is an efficient electrocatalyst as platinum or a hoax for oxygen reduction reaction in acidic environment PEM fuel cell?

    International Nuclear Information System (INIS)

    Sahoo, Madhumita; Ramaprabhu, S.

    2017-01-01

    Non-precious, heteroatom doped carbon is reported to replace commercial Pt/C in both alkaline and acidic half-cell rotating disc electrode study; however the real world full cell measurements with the metal-free electrocatalysts overcoming the practical troubles in acidic environment proton exchange membrane fuel cell (PEMFC) are almost negligible to confirm the claim. Nitrogen and sulfur co-doped porous carbon (DPC) was synthesized in a one step, high yield process from single source ionic liquid precursor using eutectic salt as porogens to achieve porosity. Structural characterization confirms 7.03% nitrogen and 1.68% sulfur doping into the high surface area, porous carbon structure. As the cathode oxygen reduction reaction (ORR) catalyst, metal-free DPC and Pt nanoparticles decorated DPC (Pt/DPC) shows stable and high exchange current density by four electron transfer pathway in acidic half–cell liquid environment due to the synergistic effect of nitrogen and sulfur doping and porous nature of DPC. In an actual solid state full cell measurement, Pt/DPC shows higher performance comparable to commercial Pt/C; however DPC failed to reciprocate the half-cell performance due to blockage of active sites in the membrane electrode assembly fabrication process. - Highlights: • Synthesis of N and S co-doped porous carbon (DPC) in simple one-pot technique. • High surface area DPC shows comparable activity for ORR in half-cell acidic PEMFC study. • Real-world performance of DPC gives 20 mW/cm 2 peak power density at 60 °C. • Homogeneous Pt nanoparticles decorated DPC (Pt/DPC) outperforms commercial Pt/C. • Pt/DPC shows maximum power density of 718 mW/cm 2 with lower 0.3 mg/cm 2 total Pt loading.

  2. 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....

  3. 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.

  4. 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

  5. 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.

  6. Influence of zirconium doping in ceria lattice as an active electrode in amperometric electrochemical ammonia gas sensor using oxygen pumping current

    International Nuclear Information System (INIS)

    Sharan, R.; Dutta, Atanu; Roy, Mainak

    2016-01-01

    An amperometric electrochemical sensor using Ce-Zr system as ammonia gas detecting electrode is reported. Using lanthanum gallate based electrolyte La_0_._8Sr_0_._2Ga_0_._8Mg_0_._1Ni_0_._1O_3 (LSGMN) and lanthanum strontium cobaltite La_0_._5Sr_0_._5CoO_3 (LSC) as oxygen reduction electrode, the sensor was found to be highly sensitive to NH_3 gas down to few ppm level, when operated in the temperature range 300-450°C. Keeping LSC electrodecomposition same, when sensing properties were studied with the variation of Zr concentration in ceria for active electrode, sensor with 30 mol % Zr doped ceria showed highest sensitivity of 28μA/ decade at 400°C. For all active electrodecompositions Ce_1_-_xZr_xO_2 (x = 0 to 0.7) highest sensitivity was observed at 400°C. All the sensors performed reproducibly with time response and recovery time 40 and 120 seconds respectively. (author)

  7. Nitrogen and oxygen co-doped carbon nanofibers with rich sub-nanoscale pores as self-supported electrode material of high-performance supercapacitors

    International Nuclear Information System (INIS)

    Li, Qun; Xie, Wenhe; Liu, Dequan; Wang, Qi; He, Deyan

    2016-01-01

    Self-supported porous carbon nanofibers (CNFs) network has been prepared by electrospinning technology assisted with template method. The as-prepared material is rich in sub-nanoscale pores and nitrogen and oxygen functional groups, which can serve as a fast conductive network with abundant electrochemical active sites and greatly facilitates the transport of electrons and ions. When the porous CNFs network is used as an electrode for supercapacitor in a three electrode system, it displays a high capacitance of 233.1 F/g at 0.2 A/g, and a capacitance of 130.2 F/g even at 14 A/g. It maintains a capacitance of 154.0 F/g with 90.17% retention after 4000 cycles at 2 A/g. Moreover, the assembled symmetric supercapacitor not only exhibits excellent rate capability and cycle performance, but also delivers an energy density of 4.17 Wh/kg and a power density of 2500 W/kg. The experimental results demonstrate that the prepared N, O co-doped carbon nanofibers with rich sub-nanoscale pores are a promising electrode material for high-performance supercapacitors.

  8. Rhodium nanoparticle-modified screen-printed graphite electrodes for the determination of hydrogen peroxide in tea extracts in the presence of oxygen.

    Science.gov (United States)

    Gatselou, Vasiliki A; Giokas, Dimothenis L; Vlessidis, Athanasios G; Prodromidis, Mamas I

    2015-03-01

    In this work we describe the fabrication of nanostructured electrocatalytic surfaces based on polyethyleneimine (PEI)-supported rhodium nanoparticles (Rh-NP) over graphite screen-printed electrodes (SPEs) for the determination of hydrogen peroxide in the presence of oxygen. Rh-NP, electrostatically stabilized by citrate anions, were immobilized over graphite SPEs, through coulombic attraction on a thin film of positively charged PEI. The functionalized sensors, polarized at 0.0 V vs. Ag/AgCl/3 M KCl, exhibited a linear response to H2O2 over the concentration range from 5 to 600 μmol L(-1) H2O2 in the presence of oxygen. The 3σ limit of detection was 2 μmol L(-1) H2O2, while the reproducibility of the method at the concentration level of 10 μmol L(-1) H2O2 (n=10) and between different sensors (n=4) was lower than 3 and 5%, respectively. Most importantly, the sensors showed an excellent working and storage stability at ambient conditions and they were successfully applied to the determination of H2O2 produced by autooxidation of polylphenols in tea extracts with ageing. Recovery rates ranged between 97 and 104% suggesting that the as-prepared electrodes can be used for the development of small-scale, low-cost chemical sensors for use in on-site applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. OXYGEN BUBBLE DEVELOPMENT ON A PLATINUM ELECTRODE IN BOROSILICATE GLASS MELT BY THE EFFECT OF ALTERNATING CURRENT

    Directory of Open Access Journals (Sweden)

    Jiri Matej

    2014-10-01

    or on alternating reduction and re-forming of oxidic layer on the electrode in the transition range, has been suggested. Start of bubble evolution at low alternating current density has also been observed in simple sodium-calcium-silicate glass melt. A relation between bubble release and platinum corrosion caused by reduced silicon has been suggested

  10. Hysteresis in the solid oxide fuel cell cathode reaction

    DEFF Research Database (Denmark)

    Jacobsen, Torben; Zachau-Christiansen, Birgit; Bay, Lasse

    2001-01-01

    The oxygen electrode reaction at the Pt/yttria-stabilised zirconia (YSZ) interface is investigated at 1000degreesC on Pt point electrodes on YSZ and YSZ point contacts on Pt. Linear potential sweeps show a pronounced non-linear current-voltage relation and inductive hysteresis, in particular at l...

  11. Microwave exposure as a fast and cost-effective alternative of oxygen plasma treatment of indium-tin oxide electrode for application in organic solar cells

    Science.gov (United States)

    Soultati, Anastasia; Kostis, Ioannis; Papadimitropoulos, Giorgos; Zeniou, Angelos; Gogolides, Evangelos; Alexandropoulos, Dimitris; Vainos, Nikos; Davazoglou, Dimitris; Speliotis, Thanassis; Stathopoulos, Nikolaos A.; Argitis, Panagiotis; Vasilopoulou, Maria

    2017-12-01

    Pre-treatment methods are commonly employed to clean as well as to modify electrode surfaces. Many previous reports suggest that modifying the surface properties of indium tin oxide (ITO) by oxygen plasma treatment is a crucial step for the fabrication of high performance organic solar cells. In this work, we propose a fast and cost-effective microwave exposure step for the modification of the surface properties of ITO anode electrodes used in organic solar cells. It is demonstrated that a short microwave exposure improves the hydrophilicity and reduces the roughness of the ITO surface, as revealed by contact angle and atomic force microscopy (AFM) measurements, respectively, leading to a better quality of the PEDOT:PSS film coated on top of it. Similar results were obtained with the commonly used oxygen plasma treatment of ITO suggesting that microwave exposure is an effective process for modifying the surface properties of ITO with the benefits of low-cost, easy and fast processing. In addition, the influence of the microwave exposure of ITO anode electrode on the performance of an organic solar cell based on the poly(3-hexylthiophene):[6,6]-phenyl C70 butyric acid methyl ester (P3HT:PC70BM) blend is investigated. The 71% efficiency enhancement obtained in the microwave annealed-ITO based device as compared to the device with the as-received ITO was mainly attributed to the improvement in the short circuit current (J sc) and decreased leakage current caused by the reduced series and the increased shunt resistances and also by the higher charge generation efficiency, and the reduced recombination losses.

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

    DEFF Research Database (Denmark)

    Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf

    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 lo...

  13. In situ Fourier transform infrared spectroscopy and on-line differential electrochemical mass spectrometry study of the NH3BH3 oxidation reaction on gold electrodes

    International Nuclear Information System (INIS)

    Belén Molina Concha, M.; Chatenet, Marian; Lima, Fabio H.B.; Ticianelli, Edson A.

    2013-01-01

    The ammonia borane (NH 3 BH 3 ) oxidation reaction (ABOR) was studied on gold electrodes using the rotating disk electrode (RDE) setup and coupled physical techniques: on-line differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR). Non-negligible heterogeneous hydrolysis in the low-potential region was asserted via molecular H 2 detection. As a consequence, the number of electron exchanged per BH 3 OH − species is ca. 3 at low potential, and only reaches ca. 6 above 0.6 V vs. RHE. These figures were confirmed by Levich and Koutecki–Levich calculations using the RDE experiments data. The nature of the ABOR intermediates and products was determined using in situ FTIR. While BH 2 species were detected during the ABOR, it seems that its adsorption onto the Au electrode proceeds via the O atom, in opposition to what happens during the borohydride oxidation reaction (BOR). Therefore, it is likely that the mechanism of the ABOR differs from that of the BOR. From the whole set of data (RDE, DEMS, FTIR), a relevant reaction pathway was proposed, including competition between the BH 3 OH − heterogeneous hydrolysis and oxidation at low potential, and preponderant oxidation at higher potential. Finally, a simplified kinetic modeling accounting with this reaction pathway was proposed, which nicely fits the stationary (i vs. E) ABOR plot

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.