Oxygen‐Mediated Hydrogen Spillover Promotes Stable Synthesis of Vinyl Chloride on Ru Single‐Atom Catalysts

Ru single‐atom catalysts hold great promise for the robust synthesis of vinyl chloride through acetylene hydrochlorination. However, the easy over‐chlorination of Ru atoms during reaction suppress the catalytic activity and stability. Herein, we have synthesized an oxygen doped Ru single‐atom catalyst by a sequential oxygen etching strategy, which delivers the remarkable yield of vinyl chloride monomer (>99.38%) and stability (>900 h, 180 h‐1), far beyond those reported Ru counterparts. Experimental results and theoretical calculations reveal that the asymmetric structure of single‐atom Ru promotes an unconventional oxygen‐mediated hydrogen spillover after the activation of hydrogen chloride, which enables the reaction to proceed through Eley‐Rideal mechanism with a reduced energy barrier of acetylene hydrochlorination compared to the traditional Langmuir‐Hinshelwood pathway. As a result, the enhanced reaction kinetics further restrict over‐chlorination of single‐atom Ru, thereby ensuring the excellent durability. This work offers a strategy for designing multifunctional catalysts with enhanced performances for acetylene hydrochlorination.