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

Journal of Computational Chemistry
Riguang ZhangZhong Li

Abstract

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 tha...Continue Reading

References

Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
Jun 28, 2006·The Journal of Physical Chemistry. B·Ian J DrakeAlexis T Bell
Feb 18, 2009·Journal of Molecular Modeling·Zhijun ZuoZhihong Li

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Citations

Mar 21, 2015·Chemical Society Reviews·Shouying HuangXinbin Ma
Jul 5, 2013·Physical Chemistry Chemical Physics : PCCP·Yongli ShenXinbin Ma

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