X-Ray Absorption Spectroscopy Characterizations on PGM-Free Electrocatalysts: Justification, Advantages, and Limitations.

Transition metals embedded in nitrogen-doped carbon matrices (denoted as M-N-C) are the leading platinum group metal (PGM)-free electrocatalysts for the oxygen reduction reaction (ORR) in acid, and are the most promising candidates for replacing platinum in practical devices such as fuel cells. Two of the long-standing puzzles in the field are the nature of active sites for the ORR and the reaction mechanism. Poor understanding of the structural and mechanistic basis for the exceptional ORR activity of M-N-C electrocatalysts impedes rational design for further improvements. Recently, synchrotron-based X-ray absorption spectroscopy (XAS) has been successfully implemented to shed some light on these two issues. In this context, a critical review is given to detail the contribution of XAS to the advancement of the M-N-C electrocatalysis to highlight its advantages and limitations.