Molecular‐level Modulation of N, S‐Co‐Doped Mesoporous Carbon Nanospheres for Selective Aqueous Catalytic Oxidation of Ethylbenzene

Abstract Selective oxidation of aromatic alkanes into high value‐added products through benzylic C−H bond activation is one of the main reactions in chemical industry. On account of the constantly increasing demand for mass production, efficient, eco‐friendly and sustainable catalysts are urgently needed. Herein, we describe a facile and versatile emulsion‐assisted interface self‐assembly strategy towards molecular‐level fabrication of co‐doped mesoporous carbon nanospheres with controllable active N and S species. The method enables a high degree of control over nanoparticle sizes, mesoporous nanostructures, contents of heteroatoms and the chemical composition. The optimized catalyst exhibits high catalytic performance of 97 % ethylbenzene conversion and 98 % selectivity to acetophenone. Density functional theory simulations reveal that N, S‐co‐doping leads to the redistribution of charge and spin densities, introducing more active carbon atoms and realizing aerobic oxidation of ethylbenzene efficiently. This work presents a general strategy for molecular‐level design of carbon‐based catalysts, and also provides new insight into the influence of heteroatom‐doping on catalytic properties.