Direct Mechanism of the First Carbon–Carbon Bond Formation in the Methanol‐to‐Hydrocarbons Process

• Published in: Angewandte Chemie International Edition Vol. 56; no. 31; pp. 9039 - 9043
• Main Authors: Wu, Xinqiang, Xu, Shutao, Zhang, Wenna, Huang, Jindou, Li, Jinzhe, Yu, Bowen, Wei, Yingxu, Liu, Zhongmin
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 24-07-2017
• Edition: International ed. in English
• Subjects: Bonding; Breakage; Catalysts; Dimethyl ether; Hydrocarbons; Hydrogen bonds; Magnetic resonance spectroscopy; Methanol; methanol to hydrocarbons; NMR spectroscopy; reaction mechanisms; surface chemistry; Zeolites; methanol to hydrocarbons; reaction mechanisms; surface chemistry; zeolites; NMR spectroscopy
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201703902

In the past two decades, the reaction mechanism of C−C bond formation from either methanol or dimethyl ether (DME) in the methanol‐to‐hydrocarbons (MTH) process has been a highly controversial issue. Described here is the first observation of a surface methyleneoxy analogue, originating from the surface‐activated DME, by in situ solid‐state NMR spectroscopy, a species crucial to the first C−C bond formation in the MTH process. New insights into the first C−C bond formation were provided, thus suggesting DME/methanol activation and direct C−C bond formation by an interesting synergetic mechanism, involving C−H bond breakage and C−C bond coupling during the initial methanol reaction within the chemical environment of the zeolite catalyst.
In a fine state: A crucial surface methyleneoxy analogue group originating from surface‐activated dimethyl ether (DME) was directly observed by in situ solid‐state NMR spectroscopy. New insights into the first C−C bond formation for the methanol‐to‐hydrocarbons process are provided.