Metal-free catalytic hydrogen production from a polymethylhydrosilane–water mixture

Hydrogen gas is the most promising carbon-free energy carrier although its on-demand generation remains a formidable challenge. One of the potential pathways for generating hydrogen is through hydrolytic oxidation of organosilanes. Here, we demonstrate that the hydroxide ion OH− serves as a potent room-temperature metal-free catalyst in the hydrolytic oxidation of polymethylhydrosilane, PMHS to hydrogen gas and the corresponding silanol with a turnover number and turnover frequency in excess of 200 and 8 min−1 respectively. Kinetic studies suggest the hydrogen generation rate is first order with respect to PMHS and OH− but zero order with respect to water. The first step of the reaction, where the Si center of PMHS is attacked by the OH− ion, is believed to be the rate-determining step.