Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol

化学化工学院王野教授课题组与邓德会研究员课题组(中科院大连化物所、能源材料化学协同创新中心)、程俊教授课题组（化学化工学院）合作，在甲醇C−C偶联直接制乙二醇的研究上取得重要突破，相关成果发表在Nature Communications（Nat. Commun. 2018, DOI: 10.1038/s41467-018-03543-y）。该成果同时也申请了中国发明专利（CN201611249732.X）和国际专利PCT（PCT/CN2017/117719）。 该工作是能源材料化学协同创新中心(2011-iChEM)研究员谢顺吉、2014级博士生沈泽斌、2011-iChEM Fellow邓浇和2015级硕士生郭璞等紧密合作的成果。湖南大学马超和上海光源姜政分别在高分辨电镜表征和同步辐射表征中提供了支持。【Abstract】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 (⋅CH2OH) 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.This work was supported by the National Key Research and Development Program of the Ministry of Science and Technology of China (nos.2017YFB0602201, 2016YFA0204100, and 2016YFA0200200), and the National Natural Science Foundation of China (nos. 21690082, 91545203, 21373166, and 21503176), the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (no. QYZDB-SSW-JSC020). We thank staffs at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facilities (SSRF) for assistance with the EXAFS measurements. 该研究得到了科技部重点研发计划（批准号：2017YFB0602201、2016YFA0204100、2016YFA0200200）和国家自然科学基金（批准号：21690082、91545203、21373166、21503176）等项目的资助