On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts

Fe‐N‐C catalysts containing atomic FeNx sites are promising candidates as precious‐metal‐free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The durability of Fe‐N‐C catalysts in fuel cells has been extensively studied using accelerated stress tests (AST). Herein we reveal stronger degradation of the Fe‐N‐C structure and four‐times higher ORR activity loss when performing load cycling AST in O2‐ vs. Ar‐saturated pH 1 electrolyte. Raman spectroscopy results show carbon corrosion after AST in O2, even when cycling at low potentials, while no corrosion occurred after any load cycling AST in Ar. The load‐cycling AST in O2 leads to loss of a significant fraction of FeNx sites, as shown by energy dispersive X‐ray spectroscopy analyses, and to the formation of Fe oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O2 is due to reactive oxygen species produced between H2O2 and Fe sites via Fenton reactions. This corrosion: The stability of Fe‐N‐C electrocatalysts in fuel cells is often studied with accelerated stress tests (ASTs). A new AST performed in O2 not Ar shows reactive oxygen species (ROS) are produced from H2O2 (from the oxygen reduction reaction) and FeNx sites. They cause carbon corrosion and the loss of catalytic FeNx sites, which are transformed into Fe oxides.