Mn-doped CeO2 derived from Ce-MOF porous nanoribbons as highly active catalysts for the synthesis of dimethyl carbonate from CO2 and methanol.

It is desirable but challenging to develop highly-efficient catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2. The vacancy-mediated incorporation of heteroatom into surface reconstruction is an efficient method of defect engineering for enhancing the catalytic properties. In this work, manganese-doped cerium oxide porous nanoribbons (Mn/CeO2-BTC) were prepared derived from a Ce-BTC by a sacrificial template approach. It is found that the catalytic activity of Mn/CeO2-BTC catalysts can be readily controlled by varying the amount of Mn dopants and the as-synthesized 0.1-Mn/CeO2-BTC exhibited an outstanding activity for the synthesis of DMC from CO2 and methanol, which reached a high DMC yield (6.53 mmolDMC/gcat.) without any dehydrating agents. Based on characterization results, the enhanced performance may be attributed to the defective structures caused by Mn doping and the porous nanoribbons of the CeO2 crystals, which provide more surface oxygen vacancies and acidic-basic sites, favoring adsorption and activation of CO2 and methanol.