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

Abstract 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 CoN₃S₁/CuN₄@NC, systematical characterizations and in situ observations imply the atomic CoN₃S₁ and CuN₄ sites immobilized on N‐doped carbon, over which the remarkable electron redistribution originating from their unsymmetrical coordination configurations. Impressively, the obtained CoN₃S₁/CuN₄@NC exhibits unprecedented capability in O₂ activation and enables a spontaneous process through its dynamic configuration, significantly outperforming the CoN₄/CuN₄@NC and CoN₃S₁@NC counterparts. Hence, the CoN₃S₁/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 CoN₃S₁/CuN₄@NC are also investigated through in situ experiments and simulations.