Peripheral N_V-induced electron transfer to Fe₁ single atoms for highly efficient O₂ activation

Catalytic oxidation plays a crucial role in chemical industry, in which the utilization of abundant and environmental-friendly oxygen (O₂) as oxidant aligns with sustainable development principles in green chemistry. However, the intrinsic inertness of ground-state O₂ molecule poses a long-standing challenge in developing an efficient non-noble metal-based catalyst. Herein, inspired by the electron transfer process in respiratory chain, we engineered long-range N_V to mediate Fe₁ center for O₂ activation in aerobic oxidation. Combined in/quasi-situ spectroscopic characterizations and control experiments suggest the Fe₁ site efficiently adsorbs O₂, and the N_V site facilitates electron delocalization to adjacent Fe₁, providing efficient transformation of O₂ to reactive oxygen species that boost oxidation reactions mildly. This Fe₁–N_V single-atom catalyst demonstrates outstanding catalytic performance in aerobic oxidations of alkanes, N-heterocycles, alcohols, and amines under relatively mild conditions. Our findings offer a new perspective for designing high-efficiency heterogeneous catalysts in aerobic oxidations, promising various potential applications.