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submitted on 22.05.2018 and posted on 23.05.2018by Chang Hyuck Choi, Hyung-Kyu Lim, Gajeon Chon, Min Wook Chung, Abdulrahman Altin, Nastaran Ranjbar Sahraie, Moulay-Tahar Sougrati, Lorenzo Stievano, Hyun Seok Oh, Eun Soo Park, Fang Luo, Peter Strasser, Goran Drazic, Karl J. J. Mayrhofer, Hyungjun Kim, Frederic Jaouen
Fuel cells efficiently convert chemical into electric energy, with promising application for clean transportation. In proton-exchange membrane fuel cells (PEMFCs), rare platinum metal catalyzes today the oxygen reduction reaction (ORR) while iron(cobalt)-nitrogen-carbon materials (Fe(Co)-N-C) are a promising alternative. Their active sites can be classified as atomically dispersed metal-ions coordinated to nitrogen atoms (MeNxCy moieties) or nitrogen functionalities (possibly influenced by sub-surface metallic particles). While their durability is a recognized challenge, its rational improvement is impeded by insufficient understanding of operando degradation mechanisms. Here, we show that FeNxCy moieties in a representative Fe-N-C catalyst are structurally stable but electrochemically unstable when exposed in acidic medium to H2O2, the main 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 a hitherto unsuspected deactivation mechanism during ORR in acidic medium. This study identifies the N-doped carbon surface as Achilles' heel during ORR catalysis in PEMFCs. Observed in acidic but not in alkaline electrolyte, these insights suggest that durable iron-nitrogen-carbon catalysts are within reach for PEMFCs if rational strategies minimizing the amount of H2O2 or reactive oxygen species (ROS) produced during ORR are developed.