Selective Reduction of CO<sub>2</sub> to Methanol via Hydrosilylation Boosted by a Porphyrinic Metal–Organic Framework
Chunying Chen, Qijie Mo, Yongsheng Huang, Li Zhang
Abstract
Methanol has been widely used in organic synthesis and fuel fields. The capture and selective reduction of CO 2 to methanol can not only decrease CO 2 concentrations but also produce methanol as a value-added chemical and fuel. Herein, the selective reduction of CO 2 to methanol via hydrosilylation was reported to be accelerated by a porphyrinic metal–organic framework (Ir-PCN-222). Catalytic results showed that Ir-PCN-222 was efficient for CO 2 reduction. Under atmospheric CO 2 pressure, the turnover frequency was up to 157 h –1 and the turnover number could reach up to 1875 with a decrease in catalyst. The catalytic reactions could also be accomplished under a low CO 2 concentration (15% CO 2 and 85% N 2 ) with more than 99% conversion and 99% selectivity. The reaction mechanism was studied by density functional theory calculations and molecular dynamics simulations, revealing that the concentration balance between CO 2 and hydrosilanes around the catalytically active iridium porphyrin units in the confined catalytic spaces of Ir-PCN-222 played an important role in the product selectivity.