Membrane-Free Electrosynthesis of Epichlorohydrins Mediated by Bromine Radicals over Nanotips,Journal of the American Chemical Society

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Membrane-Free Electrosynthesis of Epichlorohydrins Mediated by Bromine Radicals over Nanotips
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-29 , DOI: 10.1021/jacs.3c10585
Ying Gao ₁ , Mingming Yan ₁ , Chuanqi Cheng ₂ , Hao Zhong ₁ , Bo-Hang Zhao ₁ , Cuibo Liu ₁ , Yongmeng Wu ₁ , Bin Zhang ₁

Affiliation

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 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.

中文翻译：

纳米尖端上溴自由基介导的环氧氯丙烷的无膜电合成

环氧氯丙烷 (ECH) 的工业生产经常面临过量的腐蚀性氯和多步骤的过程。在这里，我们报道了一种一锅式无膜 Br 自由基介导的 ECH 电合成。 Br ^-离子电氧化溴自由基引发反应，然后从溴醇中消除 HBr，得到 ECH 并释放 Br ^-离子以供重复使用。 *OH 氧化的高能垒和孤立的 Br 吸附位点使 NiCo ₂ O ₄能够抑制竞争性的氧气和溴析出反应。高曲率纳米尖端具有增强的电场，可集中 Br^和^OH离子，以加速 ECH 电合成。该策略使 ECH 在 100 mA cm ^–2的高电流密度下具有 47% 的法拉第效率和 1.4 mol h ^–1 g _cat ^–1的反应速率，超出了技术经济分析的盈利目标。经济有利可图的电合成、方法的通用性以及环氧化物药物嵌段的扩展合成凸显了它们的巨大潜力。

更新日期：2023-12-29

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