Rotating disk electrode analysis of oxygen reduction at platinum particles under limiting diffusion conditions

Abstract

An analysis is carried out of oxygen reduction under limiting diffusion conditions on a rotating disk electrode partially covered with platinum particles (‘particulate electrode’). First a model is developed for the current response at a rotating particulate electrode, because Levich equation, used for the classical continuous disk electrodes, is not applicable in this case. The model allows for the calculation of the limiting diffusion current by an iterative algorithm, as a function of the density and size of the particles, and the constants for the adsorption/desorption and diffusion of reactants over non-covered areas of the substrate. The model is valid when there is no overlapping of surface diffusion areas around the particles. In a second part, the oxygen reduction on platinum particles electrodeposited on a glassy carbon disk is studied. Platinum particulate electrodes with a variable density and size of particles are prepared by single pulse electrodeposition technique. Limiting diffusion currents for oxygen reduction are analysed on the light of the proposed model. Values for the oxygen surface diffusivity and the equilibrium adsorption/desorption constant on the glassy carbon substrate are obtained from the analysis.