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

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.

Automated summary

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 was investigated 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. Additionally, quantitative evaluation of specific adsorption at the ORR potential was performed by measuring the 5d orbital vacancy of the Pt/C catalyst using operando XAS.