Recent advances and insights in designing Zn_xCd_1-xS-based photocatalysts for hydrogen production and synergistic selective oxidation to value-added chemical production

Combining the hydrogen (H₂) extraction process and organic oxidation synthesis in photooxidation-reduction reactions mediated by semiconductors is a desirable strategy because rich chemicals are evolved as byproducts along with hydrogen in trifling conditions upon irradiation, which is the only effort. The bifunctional photocatalytic strategy facilitates the feasible formation of a C═O/C─C bond from a large number of compounds containing a X-H (X = C, O) bond; therefore, the production of H₂ can be easily realized without support from third agents like chemical substances, thus providing an eco-friendly and appealing organic synthesis strategy. Among the widely studied semiconductor nanomaterials, Zn_xCd_1-xS has been continuously studied and explored by researchers over the years, and it has attracted much consideration owing to its unique advantages such as adjustable band edge position, rich elemental composition, excellent photoelectric properties, and ability to respond to visible light. Therefore, nanostructures based on Zn_xCd_1-xS have been widely studied as a feasible way to efficiently prepare hydrogen energy and selectively oxidize it into high-value fine chemicals. In this Review, first, the crystal and energy band structures of Zn_xCd_1-xS, the model of twin nanocrystals, the photogenerated charge separation mechanism of the ZB-WZ-ZB homojunction with crisscross bands, and the Volmer-Weber growth mechanism of Zn_xCd_1-xS are described. Second, the morphology, structure, modification, synthesis, and vacancy engineering of Zn_xCd_1-xS are surveyed, summarized, and discussed. Then, the research progress in Zn_xCd_1-xS-based photocatalysis in photocatalytic hydrogen extraction (PHE) technology, the mechanism of PHE, organic substance (benzyl alcohol, methanol, etc.) dehydrogenation, the factors affecting the efficiency of photocatalytic discerning oxidation of organic derivatives, and selective C-H activation and C-C coupling for synergistic efficient dehydrogenation of photocatalysts are described. Conclusively, the challenges in the applicability of Zn_xCd_1-xS-based photocatalysts are addressed for further research development along this line. Copyright © 2024 American Chemical Society.