Porous CuBi<sub>2</sub>O<sub>4</sub> Photocathode with Intrinsic Cu<sup>+</sup>/Cu<sup>2+</sup> Redox Improves Solar C(sp<sup>3</sup>)-H Bond Conversion Efficiency by an Order of Magnitude.
basic_science · Level V
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- Record sourced from PubMed, PMID 40159860.
- Also identified by DOI 10.1002/adma.202502321.
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Abstract
Selective C-H activation is the most important step for organic molecule transformation. Photocatalytic radicals driven C-H activation is considered a promising route but suffers from simultaneously utilizing electron/hole pairs which are limited to broad-band gap semiconductors. Herein, a half-photocathodic reaction strategy is demonstrated to activate and oxygenate C(sp<sup>3</sup>)-H bonds of toluene toward selective benzaldehyde production using a narrow-bandgap CuBi<sub>2</sub>O<sub>4</sub> (CBO) porous photocathode. The intrinsic Cu<sup>+</sup>/Cu<sup>2+</sup> redox of porous CBO photocathode catalyzes the photocathodic oxygen reductive H<sub>2</sub>O<sub>2</sub> to generate ·OH capable of oxidation which activates the C(sp<sup>3</sup>)-H bond that is further oxygenated via ·O<sub>2</sub> <sup>-</sup> formed of the photocathodic oxygen reduction. As a result, the benzaldehyde selectivity is up to 90%. Impressively, the narrow-band gap of CBO enables record-high light-driven benzaldehyde yields of 111.93 mmol m<sup>-2</sup> h<sup>-1</sup> with stability of over 20 h. This work opens a green and efficient light-driven C(sp<sup>3</sup>)-H bond oxidation strategy by using a narrow-bandgap photocathode.