Membrane-Free Electrosynthesis of Epichlorohydrins Mediated by Bromine Radicals over Nanotips
Ying Gao, Mingming Yan, Chuanqi Cheng, Hao Zhong, Bo‐Hang Zhao, Cuibo Liu, Yongmeng Wu, Bin Zhang
Abstract
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 NiCo 2 O 4 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 g cat –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.