Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO₂ and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO₂ and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO₂, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.