Wang Zhennan, Lu Dingze, Kondamareddy Kiran Kumar, He Yang, Gu Wenju, Li Jing, Fan Huiqing, Wang Hongmei, Ho Wingkei
School of Science, Xi'an Polytechnic University, No.19 of Jinhua South Road, Beilin District, Xi'an 710048, P. R. China.
Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, New Territories, Hong Kong 999077, P. R. China.
ACS Appl Mater Interfaces. 2024 Sep 18;16(37):48895-48926. doi: 10.1021/acsami.4c09599. Epub 2024 Sep 5.
Combining the hydrogen (H) 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 H 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, ZnCdS 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 ZnCdS 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 ZnCdS, 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 ZnCdS are described. Second, the morphology, structure, modification, synthesis, and vacancy engineering of ZnCdS are surveyed, summarized, and discussed. Then, the research progress in ZnCdS-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 ZnCdS-based photocatalysts are addressed for further research development along this line.
在半导体介导的光氧化还原反应中，将氢（H）提取过程与有机氧化合成相结合是一种理想的策略，因为在光照条件下，少量条件下会产生丰富的化学物质作为副产物与氢一起生成，这是唯一的成果。双功能光催化策略有助于从大量含有X-H（X = C，O）键的化合物中可行地形成C═O/C─C键；因此，无需化学物质等第三试剂的支持就能轻松实现H的产生，从而提供一种生态友好且有吸引力的有机合成策略。在广泛研究的半导体纳米材料中，多年来研究人员一直在不断研究和探索ZnCdS，由于其具有诸如可调节的带边位置、丰富的元素组成、优异的光电性能以及对可见光的响应能力等独特优势，它备受关注。因此，基于ZnCdS的纳米结构作为一种有效制备氢能并将其选择性氧化为高价值精细化学品的可行方法得到了广泛研究。在本综述中，首先描述了ZnCdS的晶体和能带结构、孪晶纳米晶体模型、具有交叉能带的ZB-WZ-ZB同质结的光生电荷分离机制以及ZnCdS的伏默-韦伯生长机制。其次，对ZnCdS的形貌、结构、改性、合成和空位工程进行了调查、总结和讨论。然后，描述了基于ZnCdS的光催化在光催化氢提取（PHE）技术、PHE机制、有机物质（苯甲醇、甲醇等）脱氢、影响有机衍生物光催化辨别氧化效率的因素以及光催化剂协同高效脱氢的选择性C-H活化和C-C偶联方面的研究进展。最后，针对基于ZnCdS的光催化剂适用性方面的挑战进行了阐述，以供该领域的进一步研究发展参考。
