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Preferential Adsorption of Ethylene Oxide on Fe and Chlorine on Ni Enabled Scalable Electrosynthesis of Ethylene Chlorohydrin

Shuyan Han, Chuanqi Cheng, Meng He, Rui Li, Ying Gao, Yifu Yu, Bin Zhang, Cuibo Liu

2023Angewandte Chemie International Edition26 citationsDOI

Abstract

Abstract 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 2 O 4 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 −2 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.

Topics & Concepts

ElectrosynthesisEthylene oxideEthyleneAdsorptionChlorineChemistryOxideInorganic chemistryNickelMaterials scienceOrganic chemistryCatalysisCopolymerPhysical chemistryElectrochemistryPolymerElectrodeElectrocatalysts for Energy ConversionElectrochemical Analysis and ApplicationsCO2 Reduction Techniques and Catalysts