Customized Heteronuclear Dual Single‐Atom and Cluster Assemblies via D‐Band Orchestration for Oxygen Reduction Reaction

Abstract Advanced oxygen reduction reaction (ORR) catalysts, integrating with well‐dispersed single atom (SA) and atomic cluster (AC) sites, showcase potential in bolstering catalytic activity. However, the precise structural modulation and in‐depth investigation of their catalytic mechanisms pose ongoing challenges. Herein, a proactive cluster lockdown strategy is introduced, relying on the confinement of trinuclear clusters with metal atom exchange in the covalent organic polymers, enabling the targeted synthesis of a series of multicomponent ensembles featuring FeCo (Fe or Co) dual‐single‐atom ( D SA) and atomic cluster (AC) configurations (FeCo‐ D SA/AC) via thermal pyrolysis. The designed FeCo‐ D SA/AC surpasses Fe‐ and Co‐derived counterparts by 18 mV and 49 mV in ORR half‐wave potential, whilst exhibiting exemplary performance in Zn‐air batteries. Comprehensive analysis and theoretical simulation elucidate the enhanced activity stems from adeptly orchestrating d z 2 ‐ d xz and O 2p orbital hybridization proximate to the Fermi level, fine‐tuning the antibonding states to expedite OH* desorption and OOH* formation, thereby augmenting catalytic activity. This work elucidates the synergistic potentiation of active sites in hybrid electrocatalysts, pioneering innovative targeted design strategies for single‐atom‐cluster electrocatalysts.