Atomic Engineering Modulates Oxygen Reduction of Hollow Carbon Matrix Confined Single Metal‐Nitrogen Sites for Zinc‐Air Batteries

The systematical understanding of metal-dependent activity in electrocatalyzing oxygen reduction reaction (ORR), a vital reaction with sluggish kinetics for zinc-air batteries, remains quite unclear. An atomic and spatial engineering modulating ORR activity over hollow carbon quasi-sphere (HCS) confined in a series of single M-N (M = Cu, Mn, Ni) sites is reported here. Based on the theoretical prediction and experimental validation, Cu-N₄ site with the lowest overpotential shows a better ORR kinetics than Mn-N₄ and Ni-N₄ . The ORR activity of single-atom Cu center can be further improved by decreasing the coordination number of N to two, namely Cu-N₂ , due to the enhancement of electrons with lower coordination structure. Benefitting from the unique spatial confinement effect of the HCS structure in modulating electronic feature of active sites, the Cu-N₂ site confined in HCS also delivers highly improved ORR kinetics and activity relative to that on planner graphene. Additionally, the best catalyst holds excellent promise in the application of zinc-air batteries. The findings will pave a new way to atomically and electronically tune active sites with high efficiency for other single-atom catalysts.