Attaining the Sabatier Sweet Spot via d‐Orbital Occupancy Engineering for High‐Performance Zn–Air Batteries

ABSTRACT Precise control of oxygen‐intermediate binding near the Sabatier optimum is crucial for designing high‐performance oxygen electrocatalysts for zinc–air batteries (ZABs). In CoFe bimetallic alloys, Co nanoclusters predominantly drive the oxygen evolution reaction (OER), while Fe sites promote the oxygen reduction reaction (ORR), albeit with kinetic limitations. Achieving superior oxygen activity thus demands rational modulation of d‐orbital occupancy via engineered heterointerfaces. Herein, we report a dual N‐source‐assisted partial nitridation strategy that in situ forms Co 4 N adjacent to the CoFe alloy (CNFC‐3), resulting in a well‐defined heterointerfacial interface within N‐doped graphitic carbon tubes. Combined experimental and theoretical analyses reveal that orbital coupling between nitride and alloy species optimizes oxygen intermediate adsorption, expediting *OH formation for ORR and *OOH formation for OER. This synergy results in an ultra‐low oxygen overpotential (Δ E ≈ 0.631 V) and nearly 4‐electron selectivity. Notably, CNFC‐3‐based liquid ZABs deliver a high‐power density of ≈201 mW cm −2 and a specific capacity of 812 mAh g Zn −1 . At larger scales, ZABs incorporating the same catalyst also demonstrate promising performance. Furthermore, flexible ZABs employing NTA‐modified P‐P‐N gel exhibit temperature resilience, dendrite suppression, and robust durability under high current densities, indicating their potential for next‐generation alternative batteries.