Lattice gas model for CO electrooxidation on Pt-Ru bimetallic surfaces

We propose a lattice gas model for the carbon monoxide oxidation on platinum-ruthenium electrode surfaces. The kinetic model includes the main mechanistic "bifunctional" features as they are generally agreed upon in the literature. The CO stripping voltammetry is solved by dynamic Monte Carlo simulations. For a randomly dispersed alloy of Ru and Pt, the model gives a satisfactory semiquantitative agreement with the experimental CO stripping results of Gasteiger et al. [J. Phys. Chem. 1994, 98, 617]. It is shown how the bifunctional mechanism cannot operate if CO is not mobile on the surface, and a simple Tafel-type experiment with a low concentration of active Pt-Ru sites is suggested to check quantitatively the CO mobility rate. On a surface with large Ru islands, the overpotential for CO oxidation increases, and two CO stripping peaks may appear if the CO mobility is sufficiently low. A mean-field model of the system reproduces the DMC results for high CO mobility but breaks down for a system with large Ru islands and a comparatively low CO surface diffusion constant