The synthesis of dimethyl carbonate (DMC) by oxidative carbonylation of methanol on atomic Cu supported on N-doped graphene (Cu₁/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 Cu₁/NG, DMC can be formed via 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 −63.4 kJ/mol, respectively. The activity of the Cu₁/NG catalysts increases in the order Cu/PNG < Cu/GNG < Cu/MG < Cu/ANG. To summarize, the presence of pyridinic- and graphitic-N in Cu₁/NG catalysts is beneficial to the oxidative carbonylation of methanol, while amino-N has a negative effect on DMC formation.

利用密度泛函理论研究了甲醇在氮掺杂石墨烯（Cu ₁ / NG）上负载的Cu上的羰基氧化反应合成碳酸二甲酯（DMC）的方法。已经系统地研究了将Cu原子锚定于吡啶-（Cu / PNG），石墨-（Cu / GNG）和氨基N（Cu / ANG）掺杂石墨烯的构型，并将其与掺杂Cu的单空位石墨烯（Cu / MG）和原始石墨烯（Cu / PG）。发现Cu原子的结合能以Cu / GNG> Cu / ANG> Cu / MG> Cu / PNG> Cu / PG的顺序降低。对Cu ₁ / NG，DMC可以经由CO插入形成为CH ₃ O操作形成CH ₃OCO，然后与其他甲醇反应。已发现在Cu / PNG，Cu / GNG，Cu / MG和Cu / ANG表面上CO插入甲醇中的限速反应的势垒能分别为31.0、52.1、73.5和92.0 kJ / mol。 。并且相应的反应能分别为-38.2，-51.3，-44.6和-63.4kJ / mol。Cu ₁ / NG催化剂的活性按Cu / PNG <Cu / GNG <Cu / MG <Cu / ANG的顺序增加。总而言之，Cu ₁ / NG催化剂中吡啶-和石墨-N的存在有利于甲醇的氧化羰基化，而氨基-N对DMC的形成具有负面影响。