Electrostatic Potential–Guided Synergy in Atomic Pairs Enables Highly Efficient Oxygen Bifunctional Catalysis

Abstract Improving the bifunctional performance of oxygen reduction and evolution reactions (ORR/OER) at the air cathode is critical for the development of rechargeable zinc–air batteries (RZABs). Dual‐atom catalysts (DACs), consisting of diatomic pairs, present a promising solution, but establishing a clear correlation between their electronic structure synergy and bifunctional ORR/OER activities remains challenging. Herein, it is uncovered that the strength of the electronic structure interaction between Fe and M sites (where M═Mn, Fe, Co, Ni, and Cu) embedded in a nitrogen‐doped carbon (Fe─M─NC) can be effectively quantified using electrostatic potential (ESP). This interaction exhibits a volcano‐type relationship when plotted against the binding free energy differences of * OOH and * O intermediates (ΔG *O –ΔG *OOH for ORR; ΔG *OOH –ΔG *O for OER), which aligns with the overpotential trend. Specifically, the Fe─Ni─NC catalyst, exhibiting the highest ESP, occupies the peak position of the volcano curve, accelerating the * OOH─ * O interconversion and thereby minimizing the ORR/OER energy barrier. Experimental results confirm that the Fe─Ni─NC demonstrates the lowest potential gap (Δ E = 0.57 V), outperforming the commercial Pt/C+RuO 2 (Δ E = 0.66 V) and other Fe─M─NC. Furthermore, aqueous and solid‐state RZABs with Fe─Ni─NC show exceptionally low charge/discharge voltage fluctuations of 50 and 350 µV h −1 , respectively, after continuous operation for 600 and 300 h.