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

Abstract

AbstractOxidation 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.