Construction of Dual-Active-Site Copper Catalyst Containing both CuN3 and CuN4 Sites

Abstract

Clear recognition and rational construction of suitable active center for specific reaction is always of great significance in designing highly efficient catalysts. Herein, a dual-active-site copper catalyst (DAS-Cu) containing both CuN₃ and CuN₄ sites is reported. Such catalysts show extremely high catalytic performance (yield: up to 97%) toward oxyphosphorylation of alkenes, while catalysts with single active site (CuN₃ or CuN₄ ) are chemically inert in this reaction. Combined with theoretical and experimental results, the different roles of two different Cu active sites in this reaction are further identified. CuN₃ site captures the oxygen and trigger further oxidizing process, while CuN₄ site provides moderate adsorption sites for the protection of phosphonyl radicals. This work deeply discloses the significant cooperated role with two single-atomic sites in one catalytic active center and brings up a valuable clue for the rational design of better-performing heterogeneous catalyst.

Keywords: dual-active-site catalysts; oxyphosphorylation reaction; single atom catalysts.