Operando X‑ray Absorption Spectroscopic Study on the Influence of Specific Adsorption of the Sulfo Group in the Perfluorosulfonic Acid Ionomer on the Oxygen Reduction Reaction Activity of the Pt/C Catalyst

Abstract

The influence of specific adsorption of the sulfo group in the perfluorosulfonic acid ionomer, Nafion, on the oxygen reduction reaction (ORR) of a carbon-supported Pt/C catalyst using a thin-film rotating disk electrode was investigated. The relationship between the catalyst activity and coating of the Pt/C catalyst with Nafion was quantitatively evaluated through electro chemical measurements, operando X-ray absorption spectroscopy (XAS), and CO stripping voltammetry. Activity of the Pt/C catalyst decreased with increasing ionomer-to-carbon weight ratios. To date, the effect of specific adsorption on a catalyst has been investigated using CO stripping voltammetry. However, quantitative evaluation of specific adsorption at the ORR potential (0.50−1.0 V) has not been performed yet. We quantitatively evaluated the specific adsorption during the ORR by measuring the 5d orbital vacancy of the Pt/C catalyst using operando XAS. The difference in the electronic structures of Pt in the high potential range, with and without the ionomer, was successfully established.