期刊
ACS CATALYSIS
卷 9, 期 8, 页码 7373-7379出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b02487
关键词
methanol-to-olefins; H-SAPO-34; indirect mechanism; methylcyclopentadiene; cyclopentadienes-based cycle
资金
- National Natural Science Foundation of China [91745109, 21703239, 91545104, 21473182]
- Youth Innovation Promotion Association of the Chinese Academy of Sciences [2014165]
- LiaoNing Revitalization Talents Program [XLYC1807227]
- Key Research Program of Frontier Sciences, CAS [QYZDY-SSW-JSC024]
Starting from C1 raw material, methanol conversion to hydrocarbons has been realized via a rather complicated pathway. In this contribution, we proposed an alternative methanol reaction route and provided a general understanding of such complex indirect mechanism. The methylcyclopentenyl cations and their deprotonated counterparts (methylcyclopentadienes) were validated to appear on the working H-SAPO-34 catalyst by in situ C-13 MAS NMR spectroscopy and the GC-MS technique, and their catalytic reactivity was revealed by the C-12/C-13-CH3OH isotopic switch experiment. In this context, a cyclopentadienes-based cycle was established, in which light olefins were formed with methylcyclopentadienes as critical intermediates. The feasibility of this alternative route was confirmed by density functional theory calculations. Notably, the cyclopentadienes-based cycle runs in parallel with the traditional alkenes-based and aromatics-based cycles; these three mechanistic cycles are interrelated through interconversion of the involved intermediates, including alkene, cyclopentadiene, and aromatic species. All these three cycles work together for the C-C bond assembly in the methanol-to-olefins reaction system. These findings help to build a more complete methanol conversion network and advance the in-depth understanding of indirect mechanism of methanol conversion.
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