Oxygen reduction on platinum : an EIS study

Abstract

The oxygen reduction reaction (ORR) on platinum over yttria-stabilized zirconia (YSZ) is examined via electrochemical impedance spectroscopy (EIS) for oxygen partial pressures between 10-4 and 1 atm and at temperatures between 475 and 700°C. Use of photolithographic techniques in electrode fabrication renders a precise geometry of the Pt electrodes. Circular electrode design leads to cylindrical symmetry so that models may be applied exactly to the experimental geometry. Interpretation of EIS spectra is carried out by reducing and then extending existing models, and is consistent with the postulate that ORR is rate-limited jointly by two surface chemical processes, namely, sorption/dissociation of molecular O₂ into O[delta]- a over Pt, as well as surface diffusion. Further, the novel experimental design, in conjunction with streamlined analysis techniques, provides accurate surface characterization within the electrochemical environment and allows for a more transparent comparison to relevant literature data. An adsorption coverage isotherm is extracted, and the surface diffusion coefficient is obtained for a number of experimental conditions. Extracted diffusivities fell between 2 x 10-2 and 2 x 10-7 cm2/s, in agreement with literature values for the indicated temperature range.