Size effects on reactivity of supported Pt nanoparticles in CO monolayer oxidation: Kinetic Monte Carlo simulations

In spite of tremendous efforts in research and development of polymer electrolyte fuel cells (PEFCs), essential properties of the actual catalyst material, supported Pt or Pt-alloy nanoparticles, are not yet well understood. Fundamental understanding of the catalyst structure and the prevailing kinetic mechanisms is, however, of utmost importance for further progress. In the present study, we investigate catalyst activity for CO oxidation from a theoretical point of view. Electrochemical CO oxidation serves as an important test reaction for the study of the fundamental properties of supported Pt nanoparticles. Recent experiments have revealed strong effects of catalyst particle size and supporting material on catalytic activity. It was found, that the activity towards CO oxidation decreases significantly when the particle diameter drops below 2.5 nm. We perform kinetic Monte Carlo simulations of CO oxidation on supported catalyst particles to elucidate this particle-size effect. The simulations are based on the active site concept, highlighting the role of active site formation and finite surface mobility of adsorbed electroactive species for catalyst activity. For comparison with experimental results, potential step experiments were simulated. The Monte Carlo simulations consistently reproduce effects of particle size and electrode potential found experimentally. In comparison with our simulations, analytical mean field models and nucleation and growth models exhibit inferior agreement with experimental data. In summary, our findings support an oxidation mechanism via active site formation. The reason for the slow reaction kinetics on catalyst particles with diameters below 2.5 nm is a rather low CO surface diffusivity. The rates of active site formation, diffusion and CO oxidation via recombination with adsorbed OH can be determined from the simulations.