Integrating Dual-Single-Atom Moieties with N, S Co-Coordination Configurations for Oxidative Cascaded Catalysis

Oxidation reaction is of critical importance in chemical industry, in which the primary O₂ activation step still calls for high-performance catalysts. Here, a newly developed precise locating carbonization strategy for the fabrication of 21 kinds of dual-metal single-atom catalysts with N, S co-coordinated configurations is reported. As is exemplified by CoN₃ S₁ /CuN₄ @NC, systematical characterizations and in situ observations imply the atomic CoN₃ S₁ and CuN₄ sites immobilized on N-doped carbon, over which the remarkable electron redistribution originating from their unsymmetrical coordination configurations. Impressively, the obtained CoN₃ S₁ /CuN₄ @NC exhibits unprecedented capability in O₂ activation and enables a spontaneous process through its dynamic configuration, significantly outperforming the CoN₄ /CuN₄ @NC and CoN₃ S₁ @NC counterparts. Hence, the CoN₃ S₁ /CuN₄ @NC shows attractive performance in domino synthesis of natural flavone and 19 kinds of derivatives from benzyl alcohol, 2'-hydroxyacetophenone, and corresponding substituted substrates via aerobic oxidative coupling-dehydrogenation. Detailed reaction mechanisms and molecule behaviors over CoN₃ S₁ /CuN₄ @NC are also investigated through in situ experiments and simulations.