FeN3S1─OH Single‐Atom Sites Anchored on Hollow Porous Carbon for Highly Efficient pH‐Universal Oxygen Reduction Reaction

Abstract Regulating the asymmetric active center of a single‐atom catalyst to optimize the binding energy is critical but challenging to improve the overall efficiency of the electrocatalysts. Herein, an effective strategy is developed by introducing an axial hydroxyl (OH) group to the Fe─N 4 center, simultaneously assisting with the further construction of asymmetric configurations by replacing one N atom with one S atom, forming FeN 3 S 1 ─OH configuration. This novel structure can optimize the electronic structure and d ‐band center shift to reduce the reaction energy barrier, thereby promoting oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activities. The optimal catalyst, Fe SA ‐S/N‐C (FeN 3 S 1 ─OH anchored on hollow porous carbon) displays remarkable ORR performance with a half‐wave potential of 0.92, 0.78, and 0.64 V versus RHE in 0.1 m KOH, 0.5 m H 2 SO 4 , and 0.1 m PBS, respectively. The rechargeable liquid Zn–air batteries (LZABs) equipped with Fe SA ‐S/N‐C display a higher power density of 128.35 mW cm −2 , long‐term operational stability of over 500 h, and outstanding reversibility. More importantly, the corresponding flexible solid‐state ZABs (FSZABs@Fe SA ‐S/N‐C) display negligible voltage changes at different bending angles during the charging and discharging processes. This work provides a new perspective for the design and optimization of asymmetric configuration for single‐atom catalysts applied to the area of energy conversion and storage.