Atomic Cu‐N‐P‐C Active Complex with Integrated Oxidation and Chlorination for Improved Ethylene Oxychlorination

Fine constructing the chemical environment of the central metal is vital in developing efficient single‐atom catalysts (SACs). Herein, the atomically dispersed Cu on the N‐doped carbon is modulated by introducing Cu—P moiety to Cu—N—C SAC. Through fine‐tuning with another heteroatom P, the Cu SAC shows the superior performance of ethylene oxychlorination. The Cu site activity of Cu‐NPC is four times higher than the P‐free Cu‐NC catalyst and 25 times higher than the Ce‐promoted CuCl(2)/Al(2)O(3) catalyst in the long‐term test (>200 h). The selectivity of ethylene dichloride can be splendidly kept at ≈99%. Combined experimental and simulation studies provide a theoretical framework for the coordination of Cu, N, and P in the complex active center and its role in effectively catalyzing ethylene oxychlorination. It integrates the oxidation and chlorination reactions with superior catalytic performance and unrivaled ability of corrosive‐HCl resistance. The concept of fine constructing with another heteroatom is anticipated to provide with inspiration for rational catalyst design and expand the applications of carbon‐based SACs in heterogeneous catalysis.