▎ 摘　　要

The synthesis of dimethyl carbonate (DMC) by oxidative carbonylation of methanol on atomic Cu supported on N-doped graphene (Cu-1/NG) was explored by density-functional theory. The configurations with which the Cu atom is anchored to pyridinic- (Cu/PNG), graphitic-(Cu/GNG) and amino-N (Cu/ANG) doped graphene have been systematically investigated and compared with Cu-doped monovacancy graphene (Cu/MG) and pristine graphene (Cu/PG). The binding energy of the Cu atom was found to decrease in the order Cu/GNG > Cu/ANG > Cu/MG > Cu/PNG > Cu/PG. On Cu-1/NG, DMC can be formed via0 CO insertion into CH3O to form CH3OCO, which then reacts with additional methoxide. The barrier energies of the rate-limiting reaction of CO insertion into methoxide on Cu/PNG, Cu/GNG, Cu/MG, and Cu/ANG surfaces have been found to be 31.0,52.1,73.5, and 92.0 kJ/mol, respectively. And the corresponding reaction energies are -38.2, -51.3, -44.6, and -63.4kJ/mol, respectively. The activity of the Cu-1/NG catalysts increases in the order Cu/PNG < Cu/GNG < Cu/MG < Cu/ANG. To summarize, the presence of pyridinic- and graphitic-N in Cu-1/NG catalysts is beneficial to the oxidative carbonylation of methanol, while amino-N has a negative effect on DMC formation. (c) 2017 Elsevier B.V. All rights reserved.