P‐Bridging Asymmetry Diatomic Catalysts Sites Drive Efficient Bifunctional Oxygen Electrocatalysis for Zinc‐Air Batteries

Rechargeable zinc-air batteries (ZABs) rely on the development of high-performance bifunctional oxygen electrocatalysts to facilitate efficient oxygen reduction/evolution reactions (ORR/OER). Single-atom catalysts (SACs), characterized by their precisely defined active sites, have great potential for applications in ZABs. However, the design and architecture of atomic site electrocatalysts with both high activity and durability present significant challenges, owing to their spatial confinement and electronic states. In this study, a strategy is proposed to fabricate structurally uniform dual single-atom electrocatalyst (denoted as P-FeCo/NC) consisting of P-bridging Fe and Co bimetal atom (i.e., Fe-P-Co) decorated on N, P-co-doped carbon framework as an efficient and durable bifunctional electrocatalyst for ZABs. Experimental investigations and theoretical calculations reveal that the Fe-P-Co bridge-coupling structure enables a facile adsorption/desorption of oxygen intermediates and low activation barrier. The resultant P-FeCo/NC exhibits ultralow overpotential of 340 mV at 10 mA cm^-2 for OER and high half-wave potential of 0.95 V for ORR. In addition, the application of P-FeCo/NC in rechargeable ZABs demonstrates enhanced performance with maximum power density of 115 mW cm^-2 and long cyclic stability, which surpass Pt/C and RuO₂ catalysts. This study provides valuable insights into the design and mechanism of atomically dispersed catalysts for energy conversion applications.