An Isolated Dual Atomic Catalyst with Over‐Boiling Point Associated Strategy to Construct Superb Performance Rechargeable Zinc‐Air Batteries

Abstract Efficient bifunctional oxygen catalysts are essential to construct high‐performance rechargeable zinc‐air batteries (RZABs). The excessive hydrogen bond energy and the slow kinetics of H─O bond reconstruction result in low energy efficiency. Herein, an atomic confinement regulation strategy is proposed to prepare a novel catalyst CoFe _DA /HC ₃ N ₄ by combining CoFe DACs (dual atomic catalysts) confined on hollow carbon nitride with overboiling point hydrogen‐bonding dissociation. This new combination strategy can rationally regulate the reaction pathways and kinetics of water molecule dissociation to achieve optimized performance. The CoFe _DA /HC ₃ N ₄ catalyst exhibits excellent ORR and OER catalytic activity with a half‐wave potential of 0.90 V and an overpotential of 251 mV at 10 mA cm ⁻² , fully demonstrating a stable synergistic effect of the dual coordinated Co─N ₂ and Fe─N ₂ sites. Furthermore, the assembled RZAB equipped with CoFe _DA /HC ₃ N ₄ achieves a super‐high‐energy efficiency (EE = 88.1%) and superb cycling stability (a decay rate of 0.0203%@20 mA cm ⁻² ) at 120 °C, revealing that over‐boiling point environment significantly enhances the dissociation rate of water and oxygen molecules during charge and discharge processes. This work provides a new design direction for the rational control of isolated DACs and a widen operating temperature window for secondary batteries.