OH‐Induced Surface Reconstitution in Single Atoms and Clusters Integrated Electrocatalysts for Self‐Adaptive Oxygen Electrocatalysis

Abstract The integration of atom clusters and single atoms into a unified system represents a desirable approach for attaining enhanced catalytic performance. Nonetheless, the controllable synthesis of a single‐atom and nanocluster integrated system (SA‐NC) faces considerable challenges, and the mechanisms underlying the catalytic activity remain poorly understood. In this research, a cobalt‐based catalyst containing both coordinatively unsaturated single‐atom (CoN₃) and small nanoclusters (Co@SA‐NC) is synthesized. The Co@SA‐NC not only facilitates charge and mass transfer due to the interconnected long‐range micromorphology, thus endowing efficient oxygen electrocatalytic reaction (ORR/OER), but also undergoes surface reconfiguration upon OH adsorption at high potentials in alkaline ORR/OER conditions. More appealingly, this OH‐involved reconfigured adaptive structure promotes optimization of energy barriers owing to the dynamic regulation from the bridged OH between Co single‐atom and cluster in the whole reaction process. Specific to the application metrics, a zinc–air battery assembled using the Co@SA‐NC catalyst exhibit targeted power density enhancement with 270 mW cm⁻² in an alkaline medium. This work offers an effective insight into the study of SA‐NC catalytic reaction pathways for efficient ORR/OER catalysis.