Theoretical trends in particle size effects for the oxygen reduction reaction

A simple, first principles-based model of the oxygen reduction reaction (ORR) is used to determine ORR kinetics on the (I 11), (100), and (211) facets of eleven transition metals (Au, Ag, Pt, Pd, It, Cu, Rh, Ni, Ru, Co, Fe). For most metals, the unreconstructed (100) facets are found to have an activity comparable to, or slightly higher than, the (I 11) facets. In contrast, (211) steps are found to be significantly less active than the terraces, with the exception of the most noble metals. These results are combined with simple models of the geometries of catalytic nanoparticles to estimate the average ORR activity of Pt and An nanoparticles of various sizes. On Pt, a modest decrease in the activity with decreasing particle size is predicted, while for Au, the opposite trend is found.