期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 51, 页码 26847-26854出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202112948
关键词
carbocations; methanol conversion; noncovalent interactions; solid-state NMR spectroscopy; zeolites
资金
- National Natural Science Foundation of China [21733013, 22072165, U1932218, 21991092]
- Royal Society-Newton Advanced Fellowships [NAF\R1\201066]
- National Natural Science Foundation of China-Royal Society [22061130202]
- Youth Innovation Promotion Association of the Chinese Academy of Sciences [2021329]
The study demonstrates that electron-deficient cyclopentenyl cations in ZSM-5 zeolite can capture compounds produced in the MTO reaction through noncovalent interactions, including alkanes, methanol, and olefins. These carbocation-induced noncovalent interactions modulate the product selectivity of the hydrocarbon pool reaction. The research identified intermolecular spatial proximities/interactions through two-dimensional C-13-C-13 correlation solid-state NMR spectroscopy.
Carbocations such as cyclic carbenium ions are important intermediates in the zeolite-catalyzed methanol-to-olefins (MTO) reaction. The MTO reaction propagates through a complex hydrocarbon pool process. Understanding the carbocation-involved hydrocarbon pool reaction on a molecular level still remains challenging. Here we show that electron-deficient cyclopentenyl cations stabilized in ZSM-5 zeolite are able to capture the alkanes, methanol, and olefins produced during MTO reaction via noncovalent interactions. Intermolecular spatial proximities/interactions are identified by using two-dimensional C-13-C-13 correlation solid-state NMR spectroscopy. Combined NMR experiments and theoretical analysis suggests that in addition to the dispersion and CH/pi interactions, the multiple functional groups in the cyclopentenyl cations produce strong attractive force via cation-induced dipole, cation-dipole and cation-pi interactions. These carbocation-induced noncovalent interactions modulate the product selectivity of hydrocarbon pool reaction.
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