Direct Oxygen Transfer from H₂ O to Cyclooctene over Electron-Rich RuO₂ Nanocrystals for Epoxidation and Hydrogen...

Production of more than 20 million tons of epoxides per year from olefins suffers from low atom economy due to the use of oxidants and complex catalysts with unsatisfactory selectivity, leading to huge environmental and economic costs. We present a proof-of-concept application of electron-rich RuO₂ nanocrystals to boost the highly selective epoxidation of cyclooctene via direct oxygen transfer from water as the sole oxygen source under mild conditions. The enhanced electron enrichment of RuO₂ nanocrystals via the Schottky effect with nitrogen-doped carbons largely promotes the capture and activation of cyclooctene to give a high turnover frequency (260 h^-1 ) of cyclooctene oxide, far surpassing the reported values (<20 h^-1 ) of benchmarked catalysts at room temperature with oxidants. Our electron-rich RuO₂ electrocatalysts enable efficient and durable hydrogen production (Faradaic efficiency >90 %) on the cathode without impacting on the selectivity to epoxide (>99 %) on the anode.