Photoelectrocatalytic Cl-mediated C(sp<sup>3</sup>)-H aminomethylation of hydrocarbons by BiVO<sub>4</sub> photoanodes.

Shi, Anzai; Xie, Pengfei; Wang, Yanwei; Qiu, Youai · Nat Commun · 2025

basic_science · Level V

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Abstract

Interfacial photoelectrochemistry at photoanodes has been extensively researched for solar energy conversion, but its application for the production of high-value-added chemical compounds in organic chemistry still presents challenges. Herein, we report photoelectrocatalytic Cl-mediated C(sp<sup>3</sup>)-H aminomethylation of alkanes with self-developed and reusable BiVO<sub>4</sub> photoanodes. The swift condensation of aniline with aldehydes, along with the decrease of the electricity input of aniline by photogenerated holes in the BiVO<sub>4</sub> photoanodes, work together to prevent excessive oxidation of aniline, leading to high yields of the desired product. Mechanistic experiments demonstrate that Cl<sup>-</sup> ions, as the key mediators, could be attracted to holes in the photoanodes and oxidized to form the Cl<sub>2</sub>. This is followed by light-promoted homolytic cleavage of Cl<sub>2</sub>, generating Cl radicals that efficiently abstract hydrogen atoms from hydrocarbons. This work opens an avenue for interfacial photoelectrochemical organic synthesis and demonstrates a potential method for optimizing solar energy conversion into fuels.