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At least 19 records

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

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

Parthasarathy, Arvind↗

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Parthasarathy, Arvind↗

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

Parthasarathy, Arvind↗

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

Miller, R. O.↗

Apparatus for Screening Multiple Oxygen-Reduction Catalysts

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

Whitacre, Jay↗

Assembly of Modified Ferritin Proteins on Carbon Nanotubes and its Electrocatalytic Activity for Oxygen Reduction

Highly effective dispersions of carbon nanotubes (CNTs) can be made using a commercially available buffer solution. Buffer solutions of 3-(N-morpholino)-propanesulfonic acid (MOPS), which consists of a cyclic ring with nitrogen and oxygen heteroatoms, a charged group, and an alkyl chain greatly enhance the dispersibility and stability of CNTs in aqueous solutions. Additionally, the ability of biomolecules, especially cationized Pt-cored ferritins, to adhere onto the well-dispersed CNTs in the aqueous buffer solution is also improved. This was accomplished without the use of surfactant molecules, which are detrimental to the electrical, mechanical, and other physical properties of the resulting products. The assembled Pt-cored ferritin proteins on the CNTs were used as an electrocatalyst for oxygen reduction

Kim, Jae-Woo↗

Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

Srinivasan, Vakula S.↗

Electrocatalyst for oxygen reduction

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

Swette, L. L.↗

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

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

Jalan, V.↗

Cadmium poisoning of oxygen reduction on platinum electrode in potassium hydroxide

Experiment with a rotating disk and ring apparatus showed no poisoning by cadmium in 8.5 M KOH, alone or with Cl(-) or CO3(=). Poisoning does not occur either in 0.1 M KOH supernatant at CdO, but a partially reversible poisoning results from .0001 M CdCl2 and traces of fatty acid are present. Evidence indicates that the catastrophic poisoning affects the four-electron O2 reduction more than it does the one-electron H3O(+) discharge.

Miller, R. O.↗

Electrode kinetics of oxygen reduction - A theoretical and experimental analysis of the rotating ring-disc electrode method

In order to calculate most of the rate constants for the intermediate formation of H2O2 in the electroreduction of O2 to H2O, the theoretical treatments of the rotating ring-disc electrode method by Damjanovic et al. (1966, 1967), Bagotskii et al. (1968, 1969), and Wroblowa et al. (1976) are modified. Rotating ring-disc electrode experimental data obtained for O2 reduction in Pt in 0.55 M H2SO4 are used to illustrate the calculations of rate constants according to the above theoretical treatments. A simple reaction model as proposed by the first author is consistent with the experimental data. The results indicate that O2 (97 percent) reduces to H2O in a direct four-electron transfer reaction. The adsorption of O2 is probably the rate-determining step in the potential region more negative than 0.5 V vs. reversible hydrogen electrode.

Hsueh, K.-L.↗

Power System Mass Analysis for Hydrogen Reduction Oxygen Production on the Lunar Surface

The production of oxygen from the lunar regolith requires both thermal and electrical power in roughly similar proportions. This unique power requirement is unlike most applications on the lunar surface. To efficiently meet these requirements, both solar PV array and solar concentrator systems were evaluated. The mass of various types of photovoltaic and concentrator based systems were calculated to determine the type of power system that provided the highest specific power. These were compared over a range of oxygen production rates. Also a hybrid type power system was also considered. This system utilized a photovoltaic array to produce the electrical power and a concentrator to provide the thermal power. For a single source system the three systems with the highest specific power were a flexible concentrator/Stirling engine system, a rigid concentrator/Stirling engine system and a tracking triple junction solar array system. These systems had specific power values of 43, 34, and 33 W/kg, respectively. The hybrid power system provided much higher specific power values then the single source systems. The best hybrid combinations were the triple junction solar array with the flexible concentrator and the rigid concentrator. These systems had a specific power of 81 and 68 W/kg, respectively.

Colozza, Anthony J.↗

Several new catalysts for reduction of oxygen in fuel cells

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

Cattabriga, R. A.↗