Indirect methanol synthesis from CO2 through high-efficient dimethyl carbonate hydrogenation as a bridge below 100°C.

Developing an energy-efficient process to convert chemically inert CO2 to methanol is of great significance in sustainable chemistry. Herein, we report an indirect pathway for methanol synthesis below 100 °C, utilizing CO2-derived dimethyl carbonate (DMC) as a bridging molecule. By engineering oxygen vacancies in In2O3, we construct a Lewis acidic combination of In5 sites and In4…In4 ּpairs that efficiently activate H2 and DMC, respectively. The spatial intimacy of In5 and In4…In4 enables efficient transfer of generated *H, achieving a methanol generation rate of 31.6 mmol ּgcat-1 h-1 with >99.99% selectivity at 100 °C. Integrating DMC synthesis from CO2 with subsequent hydrogenation in a single reactor via alternating feedstreams from CO2 to H2, the optimized In2O3 catalysts yield a methanol production rate of 5.2 mmol ּgcat-1 h-1 at 100 °C, outperforming the performance of previous catalysts through direct CO2 hydrogenation even at temperatures over 200 °C.