Professor Wang Ye of the School of Chemistry and Chemical Engineering teamed with Professor Deng Dehui's research group and Professor Cheng Jun's group (College of Chemistry and Chemical Engineering) to achieve an important breakthrough in the research of methanol-C-C coupled direct glycol production. Related results 'Visible light -driven C−H activation and C−C coupling of methanol into ethylene glycol' was published in Nature Communications (Nat. Commun. 2018, DOI: 10.1038/s41467-018-03543-y). This achievement also applied for Chinese invention patents. (CN201611249732.X) and International Patent PCT (PCT/CN2017/117719).
Compounds of methanol with controlled CC coupling reactions to produce C2 or more carbon atoms are attractive and challenging reactions in the chemical field. Currently the methanol C-C coupling reaction is mainly limited to carbonylation and dehydration coupling to olefins or Aromatic hydrocarbons, ie MTO or MTA processes, are characterized by the difficulty to obtain specific products with high selectivity. Retention of the C-OH bonds of methanol molecules and their selective activation of their C-H bonds to produce ethylene glycol is recognized as the most chemical field One of the challenging reactions.
As an important basic chemical, ethylene glycol is the main raw material of PET, and its use is extensive. At present, more than 90% of ethylene glycol in the industry is produced through the petroleum route, namely the ethylene epoxy hydration route, and the process efficiency is not high. Large. Coal-based synthesis gas synthesis of ethylene glycol by dimethyl oxalate route long process, high cost. And methanol can be from coal, natural gas, biomass and even carbon dioxide synthesis gas or directly prepared, cheap and easy to obtain, is important C1 platform molecules. It is of great significance to produce ethylene glycol directly from methanol.
Wang Ye's research group developed a photocatalytic method to realize the first time reaction of dehydrogenation of methanol to ethylene glycol and hydrogen under visible light irradiation on a CdS catalyst. In terms of catalytic material design, he successfully constructed porous MoS2-foam in cooperation with Deng Dehui's research group. The modified CdS nanorods catalyst greatly enhances the selectivity and activity of ethylene glycol under visible light irradiation. By designing the reaction separation reactor, the selectivity of ethylene glycol can reach 90%, the yield is 16%, and the quantum efficiency is 5 % (450nm). Further collaborated with Cheng Jun group engaged in theoretical calculation research, conducted in-depth research on the reaction mechanism, and proposed that photogenerated holes on CdS can pass protons and electrons without affecting the O—H bond of methanol. The co-transfer (CPET) process selectively activates the methanol C-H bond to generate hydroxyl radicals (•CH 2OH), •CH 2The desorption of OH from the surface of CdS couples to ethylene glycol. This visible light-driven methanol conversion process not only provides a highly efficient method for the preparation of ethylene glycol under mild conditions, but also is inert to small molecules with functional groups such as hydroxyl groups. The activation of the −H key has opened up a new way.
Wang Ye's research group has been working on basic research in the field of C1 chemistry. In syngas, methane and CO 2Catalytic or photocatalytic conversion of small molecules, especially controlled C-C couplings, has led to a series of important breakthroughs (Angew. Chem. Int. Ed. 2011, 50, 5200; Angew. Chem. Int. Ed. 2012, 51, 2438; Angew. Chem. Int. Ed. 2013, 52, 5776; Angew. Chem. Int. Ed. 2015, 54, 4553; Angew. Chem. Int. Ed. 2016, 55, 4725; Chem 2017 , 3, 334).
This work is the result of the close collaboration between Xie Shunji, a research fellow of the Energy Materials Chemistry Collaborative Innovation Center (2011-iChEM), Dr. Shen Zebin, a doctoral student of the 2014 grade, and the 2015-iChEM Fellow, and Master Guo, a 2015 graduate student. Support was provided for high-resolution electron microscopy (SEM) characterization and synchrotron radiation characterization, respectively. This study was supported by the Ministry of Science and Technology's key research and development program (Grant No. 2017YFB0602201, 2016YFA0204100, 2016YFA0200200) and the National Natural Science Foundation of China (Grant No. 21690082, 91545203, 21373166, 21503176 ) Funding for other projects.
