Selective Reduction of CO2 with Silanes over Platinum Nanoparticles Immobilised on a Polymeric Monolithic Support under Ambient Conditions

Here, we demonstrate the use of Pt⁰ nanoparticles immobilised on a polymeric monolithic support as a ligand‐free heterogeneous catalytic system for the reduction of ¹³CO₂ at room temperature and atmospheric pressure. The described system effectively reduces ¹³CO₂ with dihydrosilanes as the hydrogen source to yield a mixture of silylformates, silylacetals and methoxysilanes, which upon further hydrolysis with D₂O, produces their respective C1‐type products, that is H¹³COOD, ¹³CH₂(OD)₂ and ¹³CH₃OD. If a monohydrosilane was used as the hydrogen source, a selective reduction of ¹³CO₂ to a product mixture of only silylformates was observed. Addition of diethylamine to this reaction mixture results in the formation of H¹³COOH and Et₂N¹³CHO. This robust catalytic system is not only maintenance‐free and simple to handle, as compared with organometallic and organocatalyst systems, but also shows 3‐ to 11‐fold better catalytic activity and exhibits higher turnover numbers (TONs) up to 21 900 (activity=6.22 kg g_Pt^?1 bar^?1).