HClO-Mediated Photoelectrochemical Epoxidation of Alkenes with Near 100 % Conversion Rate and Selectivity by Regulating Lattice Chlorine Cycle

Angew Chem Int Ed Engl. 2024 Feb 26;63(9):e202314383. doi: 10.1002/anie.202314383. Epub 2024 Jan 26.

Abstract

Directional organic transformation via a green, sustainable catalytic reaction has attracted a lot of attention. Herein, we report a photoelectrochemical approach for highly selective epoxidation of alkenes in a salt solution using Co2 (OH)3 Cl (CoOCl) as a bridge of photo-generated charge, where the lattice Cl- of CoOCl can be oxidized to generate HClO by the photo-generated holes of BiVO4 photoanode and be spontaneously recovered by Cl- of a salt solution, which then oxidizes the alkenes into the corresponding epoxides. As a result, a series of water-soluble alkenes, including 4-vinylbenzenesulfonic acid sodium, 2-methyl-2-propene-1-sulfonic acid sodium, and 3-methyl-3-buten-1-ol can be epoxidized with near 100 % conversion rate and selectivity. Through further inserting a MoOx protection layer between BiVO4 and CoOCl, the stability of CoOCl-MoOx /BiVO4 can be maintained for at least 120 hours. This work opens an avenue for solar-driven organic epoxidation with a possibility of on-site reaction around the abundant ocean.

Keywords: Charge Transfer; Organic Synthesis; Oxidant; Photoelectrochemistry.