Geometric and Electronic Engineering of Atomically Dispersed Copper‐Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc–Air Batteries

Abstract The development of rechargeable zinc–air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional oxygen reduction/evolution reaction (ORR/OER) activities. However, the design of such electrocatalysts with high activity and durability is challenging. Herein, a strategy is proposed to create an electrocatalyst comprised of copper‐cobalt diatomic sites on a highly porous nitrogen‐doped carbon matrix (Cu‐Co/NC) with abundantly accessible metal sites and optimal geometric and electronic structures. Experimental findings and theoretical calculations demonstrate that the synergistic effect of Cu‐Co dual‐metal sites with metal‐N 4 coordination induce asymmetric charge distributions with moderate adsorption/desorption behavior with oxygen intermediates. This electrocatalyst exhibits extraordinary bifunctional oxygen electrocatalytic activities in alkaline media, with a half‐wave potential of 0.92 V for ORR and a low overpotential of 335 mV at 10 mA cm −2 for OER. In addition, it demonstrates exceptional ORR activity in acidic (0.85 V) and neutral (0.74 V) media. When applied to a zinc–air battery, it achieves extraordinary operational performance and outstanding durability (510 h), ranking it as one of the most efficient bifunctional electrocatalysts reported to date. This work demonstrates the importance of geometric and electronic engineering of isolated dual‐metal sites for boosting bifunctional electrocatalytic activity in electrochemical energy devices.