Elucidating the Role of Surface Ce4+ and Oxygen Vacancies of CeO2 in the Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol

Cerium dioxide (CeO₂) was pretreated with reduction and reoxidation under different conditions in order to elucidate the role of surface Ce⁴⁺ and oxygen vacancies in the catalytic activity for direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol. The corresponding catalysts were comprehensively characterized using N₂ physisorption, XRD, TEM, XPS, TPD, and CO₂-FTIR. The results indicated that reduction treatment promotes the conversion of Ce⁴⁺ to Ce³⁺ and improves the concentration of surface oxygen vacancies, while reoxidation treatment facilitates the conversion of Ce³⁺ to Ce⁴⁺ and decreases the concentration of surface oxygen vacancies. The catalytic activity was linear with the number of moderate acidic/basic sites. The surface Ce⁴⁺ rather than oxygen vacancies, as Lewis acid sites, promoted the adsorption of CO₂ and the formation of active bidentate carbonates. The number of moderate basic sites and the catalytic activity were positively correlated with the surface concentration of Ce⁴⁺ but negatively correlated with the surface concentration of oxygen vacancies. The surface Ce⁴⁺ and lattice oxygen were active Lewis acid and base sites respectively for CeO₂ catalyst, while surface oxygen vacancy and lattice oxygen were active Lewis acid and base sites, respectively, for metal-doped CeO₂ catalysts. This may result from the different natures of oxygen vacancies in CeO₂ and metal-doped CeO₂ catalysts.