Mixed-Metal Pt Monolayer Electrocatalysts for Enhanced Oxygen Reduction Kinetics

We have synthesized a new class of electrocatalysts for the O2 reduction reaction, consisting of a mixed monolayer of Pt and another late transition metal (Ir, Ru, Rh, Re, or Os) deposited on a Pd(111) single crystal or on carbon-supported Pd nanoparticles. Several of these mixed monolayer electrocatalysts exhibited very high activity and increased stability of Pt against oxidation, as well as a 20-fold increase in a Pt mass-specific activity, compared with state-of-the-art all-Pt electrocatalysts. Their superior activity and stability reflect a low OH coverage on Pt, caused by the lateral repulsion between the OH adsorbed on Pt and the OH or O adsorbed on neighboring, other than Pt, late transition metal atoms. The origin of this effect was identified through a combination of experimental and theoretical methods, employing electrochemical techniques, in situ X-ray absorption spectroscopy, and periodic, self-consistent density functional theory calculations. This new class of electrocatalysts promises to alleviate some major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance. Our studies suggest a new way of synthesizing improved ORR catalysts through the modification and control of the surface reactivity of Pt-based mixed monolayers supported on transition metals other than Pt. In addition to improving the ORR catalysts, co-depositing oxophilic metals may be a promising possibility for improving a variety of other catalysts.