The Achilles' heel of iron-based catalysts during oxygen reduction in an acidic medium

For catalysing dioxygen reduction, iron–nitrogen–carbon (Fe–N–C) materials are today the best candidates to replace platinum in proton-exchange membrane fuel cell (PEMFC) cathodes. Despite tremendous progress in their activity and site-structure understanding, improved durability is critically needed but challenged by insufficient understanding of their degradation mechanisms during operation. Here, we show that FeNxCy moieties in a representative Fe–N–C catalyst are structurally stable but electrochemically unstable when exposed in an acidic medium to H2O2, the main oxygen reduction reaction (ORR) byproduct. We reveal that exposure to H2O2 leaves iron-based catalytic sites untouched but decreases their turnover frequency (TOF) via oxidation of the carbon surface, leading to weakened O2-binding on iron-based sites. Their TOF is recovered upon electrochemical reduction of the carbon surface, demonstrating the proposed deactivation mechanism. Our results reveal for the first time a hitherto unsuspected key deactivation mechanism during the ORR in an acidic medium. This study identifies the N-doped carbon surface as the Achilles' heel during ORR catalysis in PEMFCs. Observed in acidic but not in alkaline electrolytes, these insights suggest that durable Fe–N–C catalysts are within reach for PEMFCs if rational strategies minimizing the amount of H2O2 or reactive oxygen species (ROS) produced during the ORR are developed.