Photoelectrocatalytic C-H halogenation over an oxygen vacancy-rich TiO<sub>2</sub> photoanode.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 34795245.
- Also identified by DOI 10.1038/s41467-021-26997-z and PMC identifier 8602285.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Photoelectrochemical cells are emerging as powerful tools for organic synthesis. However, they have rarely been explored for C-H halogenation to produce organic halides of industrial and medicinal importance. Here we report a photoelectrocatalytic strategy for C-H halogenation using an oxygen-vacancy-rich TiO<sub>2</sub> photoanode with NaX (X=Cl<sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>). Under illumination, the photogenerated holes in TiO<sub>2</sub> oxidize the halide ions to corresponding radicals or X<sub>2</sub>, which then react with the substrates to yield organic halides. The PEC C-H halogenation strategy exhibits broad substrate scope, including arenes, heteroarenes, nonpolar cycloalkanes, and aliphatic hydrocarbons. Experimental and theoretical data reveal that the oxygen vacancy on TiO<sub>2</sub> facilitates the photo-induced carriers separation efficiency and more importantly, promotes halide ions adsorption with intermediary strength and hence increases the activity. Moreover, we designed a self-powered PEC system and directly utilised seawater as both the electrolyte and chloride ions source, attaining chlorocyclohexane productivity of 412 µmol h<sup>-1</sup> coupled with H<sub>2</sub> productivity of 9.2 mL h<sup>-1</sup>, thus achieving a promising way to use solar for upcycling halogen in ocean resource into valuable organic halides.