Simultaneous Operando Time-Resolved XAFS–XRD Measurements of a Pt/C Cathode Catalyst in Polymer Electrolyte Fuel Cell under Transient Potential Operations

Abstract

We have succeeded in simultaneous operando time-resolved quick X-ray absorption fine structure (QXAFS)–X-ray diffraction (XRD) measurements at each acquisition time of 20 ms for a Pt/C cathode catalyst in a polymer electrolyte fuel cell (PEFC), while measuring the current/charge of the PEFC during the transient voltage cyclic processes (0.4 VRHE → 1.4 VRHE → 0.4 VRHE) under H2(anode)–N2(cathode). The rate constants for Pt–O bond formation/dissociation, Pt charging/discharging, Pt–Pt bond dissociation/reformation, and decrease/increase of Pt metallic-phase core size under the transient potential operations were determined by the combined time-resolved QXAFS–XRD technique. The present study provides a new insight into the transient-response reaction mechanism and structural transformation in the Pt surface layer and bulk, which are relevant to the origin of PEFC activity and durability as key issues for the development of next-generation PEFCs.