Nitrogen and Phosphorus Dual-Coordinated Single-Atom Mn: MnNP Active Sites for Catalytic Transfer Hydrogenation of Nitroarenes.

The coordination environment of atomically metal sites can modulate the electronic states and geometric structure of single-atom catalysts, which determine their catalytic performance. In this work, the porous carbon-supported N, P dual-coordinated Mn single-atom catalyst was successfully prepared via the phosphatization of zeolitic imidazolate frameworks and followed by pyrolysis at 900 °C. The optimal Mn-N/P-C catalyst with atomic MnNP structure has displayed better catalytic activity than the related catalyst with Mn-N structure in catalytic transfer hydrogenation of nitroarenes using formic acid as the hydrogen donor. We find that the doping of P source plays a crucial role in improving the catalytic performance, which affects the morphology and electronic properties of catalyst. This is the first Mn heterogeneous catalyst example for the reduction of nitroarenes, and it also revealed that the MnNP configuration is a more promising alternative in heterogeneous catalysis.