Oxygen vacancies generated by Sn-doped ZrO2 promoting the synthesis of dimethyl carbonate from methanol and CO2.

Abstract

Oxygen vacancy sites on a catalyst surface have been extensively studied and been proved to promote the adsorption and activation of carbon dioxide. We use Sn-doped ZrO2 to prepare a Zr/Sn catalyst rich in oxygen vacancies (OVs) by co-precipitation. The yield of dimethyl carbonate is 5 times that of ZrO2. Compared with the original ZrO2, Zr/Sn exhibits a higher specific surface area, number of acid–base sites and a lower band gap, which improves the conductivity of electrons and creates more surface. The number of reaction sites greatly enhances the adsorption and activation capacity of CO2 molecules on the catalyst surface. In situ infrared spectroscopy shows that CO2 adsorbs on oxygen vacancies to form monomethyl carbonate, and participates in the reaction as an intermediate species. This work provides new clues for the preparation of ZrO2-based catalysts rich in oxygen vacancies to directly catalyze the synthesis of dimethyl carbonate from methanol and CO2.