A density functional theory investigation on the mechanism and kinetics of dimethyl carbonate formation on Cu2 O catalyst.

A theoretical analysis about the mechanism and kinetics of dimethyl carbonate (DMC) formation via oxidative carbonylation of methanol on Cu(2)O catalyst is explored using periodic density functional calculations, both in gas phase and in solvent. The effect of solvent is taken into account using the conductor-like screening model. The calculated results show that CO insertion to methoxide species to produce monomethyl carbonate species is the rate-determining step, the corresponding activation barrier is 161.9 kJ mol(-1). Then, monomethyl carbonate species reacts with additional methoxide to form DMC with an activation barrier of 98.8 kJ mol(-1), above reaction pathway mainly contributes to the formation of DMC. CO insertion to dimethoxide species to form DMC is also considered and analyzed, the corresponding activation barrier is 308.5 kJ mol(-1), suggesting that CO insertion to dimethoxide species is not competitive in dynamics in comparison with CO insertion to methoxide species. The solvent effects on CO insertion to methoxide species involving the activation barriers suggest that the rate-determining step can be significantly affected by the solvent, 70.2 kJ mol(-1) in methanol and 63.9 kJ mol(-1) in water, which means that solvent effect can reduce the activation barrier of CO insertion to methoxide species and make the reaction of CO insertion to methoxide in solvents much easier than that in gas phase. Above calculated results can provide good theoretical guidance for the mechanism and kinetics of DMC formation and suggest that solvent effect can well improve the performance of DMC formation on Cu(2)O catalyst in a liquid-phase slurry.