Circumventing Radical Generation on Fe–V Atomic Pair Catalyst for Robust Oxygen Reduction and Zinc–Air Batteries

Abstract Iron–nitrogen–carbon (Fe–N–C) catalysts are considered the most active platinum‐free alternative for oxygen reduction reaction (ORR), yet the generated reactive oxygen species (ROS) from general mechanistic pathway rapidly impair the ORR activity and stability of Fe–N–C. Herein, we establish and report an ORR pathway‐switching strategy to circumvent ROS generation and fundamentally improve the activity and stability of Fe–N–C via DFT guided catalyst design. The constructed Fe–V atomic pair catalyst (Fe 1 V 1 ‐NC) with N 2 Fe‐N 2 ‐VN 2 configuration enables side‐on adsorption of O 2 and subsequent direct‐breaking of the O═O bond to form O*, thereby avoiding the formation of ROS radicals. Importantly, there is intersite electron interaction between FeN 4 and VN 4 , which further boosts the ORR activity. Consequently, Fe 1 V 1 ‐NC exhibits outstanding ORR activity with onset and half‐wave (E 1/2 ) potentials at 1.02 and 0.89 V versus RHE, respectively, in 0.1 M KOH. Record‐high stability is achieved on Fe 1 V 1 ‐NC with a minimal decay in E 1/2 by 16 mV over 50000 cycles, surpassing Fe–N–C counterpart and most of the catalysts reported to date. The Fe 1 V 1 ‐NC‐based zinc‐air battery reported here demonstrates exceptional durability up to 400 h at 10 mA·cm −2 . This work identifies the intrinsic correlation between ORR pathway, activity, and stability, advancing development of stable catalytic systems.