Catalytic oxidation plays a crucial role in chemical industry,in which the utilization of abundant and environmental-friendly oxygen(O_(2))as oxidant aligns with sustainable development principles in green chemistry.H...Catalytic oxidation plays a crucial role in chemical industry,in which the utilization of abundant and environmental-friendly oxygen(O_(2))as oxidant aligns with sustainable development principles in green chemistry.However,the intrinsic inertness of ground-state O_(2) 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 Fe_(1) center for O_(2) activation in aerobic oxidation.Combined in/quasi-situ spectroscopic characterizations and control experiments suggest the Fe_(1) site efficiently adsorbs O_(2),and the N_(V) site facilitates electron delocalization to adjacent Fe_(1),providing efficient transformation of O_(2) to reactive oxygen species that boost oxidation reactions mildly.This Fe_(1)--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.展开更多
文摘Catalytic oxidation plays a crucial role in chemical industry,in which the utilization of abundant and environmental-friendly oxygen(O_(2))as oxidant aligns with sustainable development principles in green chemistry.However,the intrinsic inertness of ground-state O_(2) 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 Fe_(1) center for O_(2) activation in aerobic oxidation.Combined in/quasi-situ spectroscopic characterizations and control experiments suggest the Fe_(1) site efficiently adsorbs O_(2),and the N_(V) site facilitates electron delocalization to adjacent Fe_(1),providing efficient transformation of O_(2) to reactive oxygen species that boost oxidation reactions mildly.This Fe_(1)--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.
