Atomically Dispersed Binary Co‐Ni Sites in Nitrogen‐Doped Hollow Carbon Nanocubes for Reversible Oxygen Reduction and Evolution

With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single‐atom catalysts. However, the identification and mechanism functions of polynary single‐atom structures remain elusive. Atomically dispersed binary Co‐Ni sites embedded in N‐doped hollow carbon nanocubes (denoted as CoNi‐SAs/NC) are synthesized via proposed pyrolysis of dopamine‐coated metal‐organic frameworks. The atomically isolated bimetallic configuration in CoNi‐SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi‐SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc–air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state‐of‐the‐art precious‐metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co‐Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure–performance relationships of nanocatalysts with multiple active sites for various catalytic applications. Atomically dispersed Co‐Ni sites embedded in N‐doped hollow carbon nanocubes are synthesized, promoting oxygen reduction/evolution and zinc–air batteries with reduced overpotentials, increased energy efficiency, and enhanced reversibility. The single atomic sites and synergistic effect of the dual metal centers can decrease the energetic barrier and accelerate the reaction kinetics, contributing to superior electrochemical properties of resultant hybrid catalysts.