Professor Wang Ye of the School of Chemistry and Chemical Engineering teamed with the research team of Deng Dehui's team of researchers and Professor Cheng Jun's group (School 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 of obtaining 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 the design of catalytic materials, in cooperation with Deng Dehui's research group, the porous MoS2-foam was successfully constructed. The modified CdS nanorod catalysts significantly increase the selectivity and activity of ethylene glycol under visible light irradiation. By designing a reaction-separated reactor, the selectivity of ethylene glycol can reach 90%, the yield is 16%, and the quantum efficiency is 5 % (450nm). Further cooperation with Cheng Jun group engaged in theoretical calculation research, conducted in-depth research on the reaction mechanism, proposed that CdS photogenerated holes can pass protons and electrons without affecting the methanol O-H bond. The co-transfer (CPET) process selectively activates the methanol C-H bond to generate hydroxymethyl radicals (•CH2OH), • the desorption of CH2OH from the CdS surface couples to ethylene glycol. This visible-light-driven methanol conversion process, This not only provides a highly efficient method for the preparation of ethylene glycol under mild conditions, but also opens up a new way for the selective activation of inert C-H bonds in small molecules with functional groups such as hydroxyl groups.
Wang Ye's research group has been working on basic research in the field of C1 chemistry. In syngas, catalytic or photocatalytic conversion of methane and CO2 and other small molecules, especially controlled C-C coupling, has made a series of important breakthroughs.
This work is the result of the close collaboration between Xie Shunji, a researcher of the Energy Material Chemistry Collaborative Innovation Center (2011-iChEM), Dr. Shen Zebin, a doctoral student of the 2014 grade, and Guo Shuo, a master student of the 2015-iChEMFellow. Support was provided in high-resolution electron microscopy characterization and synchrotron radiation characterization. This research 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 such projects.