Thickness effects of a carbon-supported platinum catalyst layer on the electrochemical reduction of oxygen in sulfuric acid solution

The influence of the thickness of a carbon-supported platinum catalyst layer on the oxygen reduction reaction (orr) has been studied in sulfuric acid solution by means of a thin-film rotating disk electrode. Pronounced changes in the Pt utilization, electrode activity and the orr kinetics have been observed upon varying the catalyst layer thickness. The thicker film electrode exhibits a higher Pt utilization efficiency and higher activity, and promotes the orr kinetics at potentials relevant to fuel cell operations. The participation of Pt surfaces not in contact with the electrolyte solution in electrochemical reactions via the spillover of adsorbed hydrogen and oxygen species, is proposed to be responsible for the changes. The thicker catalyst layer is likely to modify the Pt particle–particle distance by providing shared Pt sites between adjacent carbon supports, to improve the surface density of active catalyst particles per single carbon support by sharing adjacent catalyst sites, and to increase the ratio of the particle surfaces free of blocking anions to the catalyst|electrolyte interface surfaces. The carbon-supported platinum catalyst layer becomes active at 0.90 V vs RHE only when the catalyst layer is thicker than 1 μm. To provide reasonable activity, the minimum catalyst layer thickness should be around 2–4 μm. These results should be considered in the design of the cathode catalyst layer of polymer electrolyte membrane fuel cells.