Oxygen Reduction Reaction at Three‐Phase Interfaces

Abstract

The kinetics of the oxygen reduction reaction (ORR) is studied at metal–supporting electrolyte–Nafion three-phase interfaces. We first demonstrate that the sulfonate anions of Nafion are specifically adsorbed on a wide range of surfaces ranging from Pt(hkl) single-crystal surfaces, Pt-poly, Pt-skin [produced on a Pt₃Ni(111) surface by annealing in ultrahigh vacuum, UHV] to high-surface-area nanostructured thin-film (NSTF) catalysts. The surface coverage by sulfonate and the strength of the Pt–sulfonate interaction are strongly dependent on the geometry and the nature of the Pt surface atoms. Also, they are found to behave analogous to (bi)sulfate anion-specific adsorption on these surfaces, where for the Pt(hkl) surfaces, the trend is Pt(111)>Pt(110)>Pt(100) and for the Pt-skin surface on Pt₃Ni(111), the interaction strength is found to be Pt-skin