A “Pre‐Constrained Metal Twins” Strategy to Prepare Efficient Dual‐Metal‐Atom Catalysts for Cooperative Oxygen Electrocatalysis

Abstract Dual‐metal‐atom‐center catalysts (DACs) are a novel frontier in oxygen electrocatalysis, boasting functional and electronic synergies between contiguous metal centers and higher catalytic activities than single‐atom‐center catalysts. However, the definition and catalytic mechanism of DACs configurations remain unclear. Here, a “pre‐constrained metal twins” strategy is proposed to prepare contiguous FeN 4 and CoN 4 DACs with homogeneous conformations embedded in a N‐doped graphitic carbon (FeCo‐DACs/NC). A programmable phthalocyanines dimer is used as a structural moiety to anchor the bimetallic sites (containing Co and Fe) in a metal–organic framework (MOF) to achieve delocalized dispersion before pyrolysis. The resultant FeCo‐DACs/NC exhibits excellent electrochemical performance in oxygen electrocatalysis and rechargeable Zn–air batteries. Theoretical calculations demonstrate that the synergetic interaction of adjacent metals optimizes the d‐band center position of metal centers and balances the free energy of the *O intermediate, thereby improving the oxygen electrocatalytic activity. This work opens up an avenue for the rational design of DACs with tailored electronic structures and uniform geometric configurations.