Tuning the Bonding Behavior of d‐p Orbitals to Enhance Oxygen Reduction through Push–Pull Electronic Effects

Abstract The regulation of electronic structure is intricately linked to the intrinsic activity of oxygen reduction. Herein, a strategy for electronic structure modulation induced by bimetallic push–pull electronic effects in dual‐atom catalysts (Fe,Ni/N‐C@NG) is developed. Experiments and theoretical analysis reveal that Fe sites exhibit favorable bonding behaviors (Fe–O: d xz ‐p, d yz ‐p, and d z 2 ‐p) and spin configurations, which can enable rapid desorption of *OH and thus enhance the intrinsic activity of oxygen reduction. In situ monitoring techniques and Gibbs free energy diagram further demonstrate that the adjacent Ni could serve as second active center to participate in oxygen reduction. The Fe,Ni/N‐C@NG exhibits enhanced oxygen reduction reaction activity and excellent stability. Meanwhile, the assembled Zn–air battery maintains stability for over 300 h with a small voltage gap. This study provides multiple insights into the orbital scale laws of oxygen reduction.