The Particle Size Dependence of the Oxygen Reduction Reaction for Carbon-Supported Platinum and Palladium

Model carbon supported Pt and Pd electrocatalysts have been prepared using a high-throughput physical vapor deposition method. For Pt, metal particle sizes are controlled between 1.5-5.5nm over 100 electrodes of an electrochemical screening chip, allowing the oxygen reduction reaction (ORR) activity of the catalysts to be determined simultaneously. The ORR-specific current density is observed to increase with increasing particle diameter up to approximately 4nm, at which point the activity begins to level off. The reduction in ORR activity for particles below 4nm is accompanied by a concomitant increase in the overpotential for surface reduction. The resulting mass activity exhibits a maximum for particles with diameters of approximately 3.5nm. These results are consistent with results published recently for high area carbon-supported Pt catalysts. For Pd particles, both the specific current density and the mass-specific activity for the ORR are observed to increase with increasing particle diameter, with no distinct optimum observed. The implications for the optimization of Pt- or Pd-based ORR catalysts for proton exchange membrane fuel cell (PEMFC) applications are discussed.