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 1.5-5.5 nm 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 4 nm, at which point the activity begins to level off. The reduction in ORR activity for particles below 4 nm 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 3.5 nm. 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.