A Unique Quadruple-Site System Integrating Fe-N4 Sites and Zn Atomic Clusters for Oxygen Reduction Reaction and Wide-Temperature Zn–Air Batteries

Fe-N-C single-atom catalysts (SACs) featuring Fe-N 4 configurations face challenges in the simultaneous enhancement of intrinsic oxygen reduction reaction (ORR) activity and long-term stability. Herein, we developed a unique quadruple-site cooperative system through a 90 s ultrafast thermal shock strategy, where most Zn atomic clusters are surrounded by two closely neighboring and a further Fe-N 4 sites (Fe SA /Zn AC -N-C). Density functional theory and molecular dynamics simulations jointly reveal that proximal Fe-N 4 -modified Zn atomic clusters mediate O 2 adsorption/activation/hydrogenation, while distal Fe-N 4 sites facilitate H 2 O formation/desorption. This synergistic dual-active-center configuration achieves a positive half-wave potential of 0.90 V and superb durability. The constructed aqueous Fe SA /Zn AC -N-C-based Zn–air batteries demonstrate a large maximum power density of 161.5 mW cm –2, a high specific discharge capacity of 792.7 mAh g –1, and stable operation over 1500 cycles. In addition, the fabricated quasi-solid-state Zn–air batteries also maintain favorable operation across a wide temperature range (−30 to 60 °C) and at the ampere scale.