In Situ IR Studies on the Mechanism of Dimethyl Carbonate Synthesis from Methanol and Carbon Dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and Carbon dioxide (CO2) has been investigated over 5% Rh/Al2O3 catalyst. Diffuse Reflectance Infrared Fourier Transfer Spectroscopy (DRIFTS) was used to probe the reaction adsorbates which showed that activation of methanol and CO2 involves generation of intermediate methoxy species and formate ingredients, participating in elementary steps of DMC formation. Formation of DMC involves parallel routes comprising interaction of the OH group of Al2O3 through an acid/base mechanism and formate pathway with participation of metal sites. DMC in acid/base pathway is formed via methoxy species to form methoxy carbonate (CH3O)CO2 (active adsorbate), which then reacts with the methyl species to form DMC. The pathway involving metal Rh sites generates an additional elementary step for the involvement of CO2 in the reaction through active formate species. The synergy of parallel pathways determines the performance of the 5% Rh/Al2O3 catalyst. Further improvement of catalyst performance should be based on such a feature of the reaction mechanism.