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 O-2 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 O-2 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.

Automated summary

A newly developed precise locating carbonization strategy is reported for the fabrication of 21 kinds of dual-metal single-atom catalysts with N, S co-coordinated configurations. The CoN3S1/CuN4@NC catalyst shows remarkable performance in O-2 activation and enables a spontaneous process through its dynamic configuration, significantly outperforming the CoN4/CuN4@NC and CoN3S1@NC counterparts. Hence, CoN3S1/CuN4@NC exhibits attractive performance in the domino synthesis of natural flavone and 19 kinds of derivatives.