State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Nat Commun. 2018 Mar 21;9(1):1181. doi: 10.1038/s41467-018-03543-y.
The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon-carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an important chemical currently produced from petroleum. Ethylene glycol is formed with 90% selectivity and high efficiency, together with hydrogen over a molybdenum disulfide nanofoam-modified cadmium sulfide nanorod catalyst. Mechanistic studies reveal a preferential activation of C-H bond instead of O-H bond in methanol by photoexcited holes on CdS via a concerted proton-electron transfer mechanism, forming a hydroxymethyl radical (⋅CHOH) that can readily desorb from catalyst surfaces for subsequent coupling. This work not only offers an alternative nonpetroleum route for the synthesis of EG but also presents a unique visible-light-driven catalytic C-H activation with the hydroxyl group in the same molecule keeping intact.
将甲醇直接转化为两个或多个碳原子化合物的新方法的发展是一个极具吸引力但极具挑战性的目标。在这里，我们报告了首例可见光驱动的甲醇脱氢偶联反应，将甲醇转化为乙二醇，乙二醇是目前从石油中提取的一种重要化学品。在二硫化钼纳米泡沫修饰的硫化镉纳米棒催化剂的作用下，以 90%的选择性和高效率与氢气一起生成乙二醇。通过协同质子-电子转移机制，机理研究表明，光激发空穴优先活化甲醇中的 C-H 键，而不是 O-H 键，形成羟甲基自由基（⋅CHOH），可以很容易地从催化剂表面解吸，从而进行后续偶联。这项工作不仅为 EG 的合成提供了一种非石油的替代路线，而且还展示了一种独特的可见光驱动的催化 C-H 活化，其中同一分子中的羟基保持完整。
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