Atomically Defined Undercoordinated Copper Active Sites over Nitrogen-Doped Carbon for Aerobic Oxidation of Alcohols.

Abstract

Selective aerobic oxidation of alcohols offers an attractive means to address challenges in the modern chemical industry, but the development of non-noble metal catalysts with superior efficacy for this reaction remains a grand challenge. Here, this study reports on such a catalyst based on atomically defined undercoordinated copper atoms over nitrogen-doped carbon support as an efficient, durable, and scalable heterogeneous catalyst for selective aerobic oxidation of alcohols. This catalyst exhibits extremely high intrinsic catalytic activity (TOF of 7692 h-1 ) in the oxidation of cinnamyl alcohol to afford cinnamaldehyde, along with exceptional recyclability (at least eight cycles), scalability, and broad substrate scope. DFT calculations suggest that the high activity derives from the low oxidation state and the unique coordination environment of the copper sites in the catalyst. These findings pave the way for the design of highly active and stable single atom catalysts to potentially address challenges in synthetic chemistry.