CeO₂ Frustrated Lewis Pairs Improving CO₂ and CH₃OH Conversion to Monomethylcarbonate

Frustrated Lewis pairs (FLPs), discovered in the last few decades for homogeneous catalysts and in the last few years also for heterogeneous catalysts, are stimulating the scientific community's interest for their potential in small-molecule activation. Nevertheless, how an FLP activates stable molecules such as CO₂ is still undefined. Through a careful spectroscopic study, we here report the formation of FLPs over a highly defective CeO₂ sample prepared by microwave-assisted synthesis. Carbon dioxide activation over FLP is shown to occur through a bidentate carbonate bridging the FLP and implying a Ce³⁺-to-CO₂ charge transfer, thus enhancing its activation. Carbon dioxide reaction with methanol to form monomethylcarbonate is here employed to demonstrate active roles of FLP and, eventually, to propose a reaction mechanism clarifying the role of Ce³⁺ and oxygen vacancies.