Diatomic Iron with a Pseudo-Phthalocyanine Coordination Environment for Highly Efficient Oxygen Reduction over 150,000 Cycles

Atomically dispersed Fe–N–C catalysts emerged as promising alternatives to commercial Pt/C for the oxygen reduction reaction. However, the majority of Fe–N–C catalysts showed unsatisfactory activity and durability due to their inferior O–O bond-breaking capability and rapid Fe demetallization. Herein, we create a pseudo-phthalocyanine environment coordinated diatomic iron (Fe2-pPc) catalyst by grafting the core domain of iron phthalocyanine (Fe–Nα–Cα–Nβ) onto defective carbon. In situ characterizations and theoretical calculation confirm that Fe2-pPc follows the fast-kinetic dissociative pathway, whereby Fe2-pPc triggers bridge-mode oxygen adsorption and catalyzes direct O–O radical cleavage. Compared to traditional Fe–N–C and FePc-based catalysts exhibiting superoxo-like oxygen adsorption and an *OOH-involved pathway, Fe2-pPc delivers a superior half-wave potential of 0.92 V. Furthermore, the ultrastrong Nα–Cα bonds in the pPc environment endow the diatomic iron active center with high tolerance for reaction-induced geometric stress, leading to significantly promoted resistance to demetallization. Upon an unprecedented harsh accelerated degradation test of 150,000 cycles, Fe2-pPc experiences negligible Fe loss and an extremely small activity decay of 17 mV, being the most robust candidate among previously reported Fe–N–C catalysts. Zinc–air batteries employing Fe2-pPc exhibit a power density of 255 mW cm–2 and excellent operation stability beyond 440 h. This work brings new insights into the design of atomically precise metallic catalysts.