Photocatalytic Cascade Reaction Driven by Directed Charge Transfer over V_S -Zn_0.5 Cd_0.5 S/GO for Controllable Benzyl...

Photocatalysis is an important technique for synthetic transformations. However, little attention has been paid to light-driven synergistic redox reactions for directed synthesis. Herein, the authors report tunable oxidation of benzyl to phenylcarbinol with the modest yield (47%) in 5 h via singlet oxygen (¹ O₂ ) and proton-coupled electron transfer (PCET) over the photocatalyst Zn_0.5 Cd_0.5 S (ZCS)/graphene oxide (GO) under exceptionally mild conditions. Theoretical calculations indicate that the presence of S vacancies on the surface of ZCS/GO photocatalyst is crucial for the adsorption and activation of O₂ , successively generating the superoxide radical (^• O₂ ^- ) and ¹ O₂ , attributing to the regulation of local electron density on the surface of ZCS/GO and photogenerated holes (h⁺ ). Meanwhile, accelerated transfer of photogenerated electrons (e^- ) to GO caused by the π-π stacking effect is conducive to the subsequent aldehyde hydrogenation to benzyl alcohol rather than non-selective oxidation of aldehyde to carboxylic acid. Anisotropic charge transport driven by the built-in electric field can further promote the separation of e^- and h⁺ for multistep reactions. Promisingly, one-pot photocatalytic conversion of p-xylene to 4-methylbenzyl alcohol is beneficial for reducing the harmful effects of aromatics on human health. Furthermore, this study provides novel insights into the design of photocatalysts for cascade reactions.