Regulating electron configuration of single Cu sites via unsaturated N,O-coordination for selective oxidation of benzene.

Developing highly efficient catalyst for selective oxidation of benzene to phenol (SOBP) with low H 2 O 2 consumption is highly desirable for practical application, but challenge remains. Herein, we report unique single-atom Cu 1 -N 1 O 2 coordination-structure on N/C material (Cu-N 1 O 2 SA/CN), prepared by water molecule-mediated pre-assembly-pyrolysis method, can efficiently boost SOBP reaction at a 2:1 of low H 2 O 2 /benzene molar ratio, showing 83.7% of high benzene conversion with 98.1% of phenol selectivity. The Cu 1 -N 1 O 2 sites can provide a preponderant reaction pathway for SOBP reaction with less steps and lower energy barrier. As a result, it shows an unexpectedly higher turnover frequency (435 h -1 ) than that of Cu 1 -N 2 (190 h -1 ), Cu 1 -N 3 (90 h -1 ) and Cu nanoparticle (58 h -1 ) catalysts, respectively. This work provides a facile and efficient method for regulating the electron configuration of single-atom catalyst and generates a highly active and selective non-precious metal catalyst for industrial production of phenol through selective oxidation of benzene.