Membrane-Free Electrosynthesis of Epichlorohydrins Mediated by Bromine Radicals over Nanotips

被引：25

作者：

Gao, Ying ^{[1
]}

Yan, Mingming ^{[1
]}

Cheng, Chuanqi ^{[2
]}

Zhong, Hao ^{[1
]}

Zhao, Bo-Hang ^{[1
]}

Liu, Cuibo ^{[1
]}

Wu, Yongmeng ^{[1
]}

Zhang, Bin ^{[1
]}

机构：

[1] Tianjin Univ, Inst Mol Plus, Sch Sci, Dept Chem, Tianjin 300072, Peoples R China

[2] Tianjin Univ, Inst New Energy Mat, Sch Mat Sci & Engn, Tianjin 300072, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2023年 / 146卷 / 01期

基金：

中国国家自然科学基金;

关键词：

HIGHLY EFFICIENT; ALLYL CHLORIDE; EPOXIDATION;

D O I：

10.1021/jacs.3c10585

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The industrial manufacture of epichlorohydrin (ECH) often suffers from excessive corrosive chlorine and multistep processes. Here, we report a one-pot membrane-free Br radical-mediated ECH electrosynthesis. Bromine radicals electro-oxidized from Br- ions initiate the reaction and then eliminate HBr from bromohydrin to give ECH and release Br- ions for reuse. A high energy barrier for *OH oxidation and isolated Br adsorption sites enables NiCo2O4 to suppress the competitive oxygen and bromine evolution reactions. The high-curvature nanotips with an increased electric field concentrate Br- and OH- ions to accelerate ECH electrosynthesis. This strategy delivers ECH with a Faradaic efficiency of 47% and a reaction rate of 1.4 mol h(-1) gcat( -1) at a high current density of 100 mA cm(-2), exceeding the profitable target from the techno-economic analysis. Economically profitable electrosynthesis, methodological universality, and the extended synthesis of epoxide-drug blocks highlight their promising potential.

引用

页码：714 / 722

页数：9

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