Tailoring Coordination and Pore Structure of MOF‐Derived Co Single‐Atom Catalysts Anchored on Graphene for Rechargeable Zinc–Air Batteries

ABSTRACT Achieving high‐performance single‐atom catalysts (SACs) for rechargeable Zn–air batteries (ZABs) requires simultaneous optimization of pore structure and coordination environment. However, MOF‐derived SACs typically feature micropore‐dominated carbon frameworks and planar coordination symmetry, restricting oxygen diffusion and intrinsic activity. Here, we introduce a dual‐engineering strategy that combines polymer encapsulation with wavy graphene oxide (GO) substrates. Bimetallic Co/Zn zeolitic imidazole framework (Co‐ZIF‐8) precursors were coated with polyvinylpyrrolidone (PVP) and assembled on GO, followed by pyrolysis to yield CoSA@P‐NC/rGO. The PVP layer induced mesopores via controlled shrinkage of the ZIF structure, while the wavy GO substrate modulated the coordination environment of atomically dispersed Co─N x sites, extending bond lengths and introducing symmetry distortion. Benefiting from these structural and electronic features, CoSA@P‐NC/rGO exhibited outstanding bifunctional activity, with a half‐wave potential of 0.90 V for oxygen reduction reaction and a low overpotential of 397 mV at 10 mA cm −2 for oxygen evolution reaction. When employed as a ZAB cathode, it achieved a high power density of 190 mW cm −2 , a specific capacity of 832 mA h g −1 , and durable cycling over 600 cycles. This synergistic strategy of pore and coordination engineering provides a promising platform for developing efficient, long‐lived SACs for energy storage applications.