Han Shuyan, Cheng Chuanqi, He Meng, Li Rui, Gao Ying, Yu Yifu, Zhang Bin, Liu Cuibo
Institute of Molecular Plus, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, China.
Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China.
Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202216581. doi: 10.1002/anie.202216581. Epub 2023 Feb 16.
Industrial manufacturing of ethylene chlorohydrin (ECH) critically requires excess corrosive hydrochloric acid or hypochlorous acid with dealing with massive by-products and wastes. Here we report a green and efficient electrosynthesis of ECH from ethylene oxide (EO) with NaCl over a NiFe O nanosheet anode. Theoretical results suggest that EO and Cl preferentially adsorb on Fe and Ni sites, respectively, collaboratively promoting the ECH synthesis. A Cl radical-mediated ring-opening process is proposed and confirmed, and the key Cl and carbon radical species are identified by high-resolution mass spectrometry. This strategy can enable scalable electrosynthesis of 185.1 mmol of ECH in 1 h with 92.5 % yield at a 55 mA cm current density. Furthermore, a series of other chloro- and bromoethanols with good to high yields and paired synthesis of ECH and 4-amino-3,6-dichloropyridine-2-carboxylicacid via respectively loading and unloading Cl are achieved, showing the promising potential of this strategy.
环氧乙烷（ECH）的工业制造严重依赖过量的腐蚀性盐酸或次氯酸，同时会产生大量副产物和废物。在此，我们报道了一种在NiFe O纳米片阳极上，以环氧乙烷（EO）和氯化钠为原料，绿色高效地电合成ECH的方法。理论结果表明，EO和Cl分别优先吸附在Fe和Ni位点上，协同促进ECH的合成。提出并证实了一种由Cl自由基介导的开环过程，通过高分辨率质谱鉴定了关键的Cl和碳自由基物种。该策略能够在55 mA cm的电流密度下，以92.5%的产率在1小时内可扩展地电合成185.1 mmol的ECH。此外，通过分别负载和卸载Cl，还实现了一系列其他氯代和溴代乙醇的高产率合成，以及ECH与4-氨基-3,6-二氯吡啶-2-羧酸的成对合成，显示了该策略的广阔前景。
