Direct Oxygen Transfer from H2O to Cyclooctene over Electron‐Rich RuO2 Nanocrystals for Epoxidation and Hydrogen Evolution. Issue 35 (14th July 2022)

• Record Type: Journal Article
• Authors: Lin, Xiu; Zhou, Zhaoyu; Li, Qi‐Yuan; Xu, Dong; Xia, Si‐Yuan; Leng, Bing‐Liang; Zhai, Guang‐Yao; Zhang, Shi‐Nan; Sun, Lu‐Han; Zhao, Guohua; Chen, Jie‐Sheng; Li, Xin‐Hao
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 35(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-14
• Subjects: Electron Enrichment -- Epoxidation -- Heterogeneous Electrocatalysis -- Oxygen Transfer -- Schottky Catalyst; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202207108
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Electron enrichment of metallic RuO2 nanocrystals can boost the highly selective epoxidation of cyclooctene via direct oxygen transfer from sustainable water, which is the sole oxygen source under ambient conditions. An efficient hydrogen evolution reaction is also enabled on the counter cathode without sacrificing the high selectivity to epoxide on the working electrode.