Dual‐Active Synergy of Fe–V Alloy and Fe─N─C Sites for Enhanced Oxygen Reduction Reaction

ABSTRACT Tailoring the electronic properties and coordination structure of single‐atom sites via metal nanocluster integration offers a promising strategy to increase the ORR activity of Fe─N─C catalysts. In this work, an FeV─NC catalyst was constructed by embedding Fe─V alloy nanoclusters within a stable Fe─N─C matrix. It achieves outstanding ORR catalytic activity under alkaline conditions, delivering a half‐wave potential of 0.94 V (vs. RHE) and a peak power density of 191.04 mWcm − 2 in zinc–air batteries. Notably, it surpasses commercial Pt/C and maintains excellent durability for over 420 h. Theoretical calculations demonstrate that the synergistic effect of Fe─V alloy species with FeN 4 sites effectively tunes the electronic structure and redistributes charge density at the FeN 4 active center, leading to significantly enhanced ORR activity and durability. The observed increase in ORR catalytic activity emphasizes the promise of this method for tuning M─N─C catalysts and developing new optimization strategies.