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Methanol to hydrocarbons reaction over H beta zeolites studied by high resolution solid-state NMR spectroscopy: Carbenium ions formation and reaction mechanism
Zhang, Mozhi1,5; Xu, Shutao1; Li, Jinzhe1; Wei, Yingxu1; Gong, Yanjun2; Chu, Yueying3; Zheng, Anmin3; Wang, Jinbang1,5; Zhang, Wenna1,5; Wu, Xinqiang1,5; Deng, Feng3; Liu, Zhongmin1,4
KeywordMethanol-to-hydrocarbons C-13 Mas Nmr Carbenium Ions Methylcyclopentenyl Cations Heptamethylbenzenium Cation
Source PublicationJOURNAL OF CATALYSIS
2016-03-01
ISSN0021-9517
DOI10.1016/j.jcat.2015.12.007
Volume335Pages:47-57
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences ; Technology
WOS SubjectChemistry, Physical ; Engineering, Chemical
WOS Research AreaChemistry ; Engineering
WOS KeywordSURFACE METHOXY GROUPS ; TO-OLEFINS CONVERSION ; IN-SITU NMR ; STABLE CARBOCATIONS ; MAS NMR ; HEPTAMETHYLBENZENIUM CATION ; CYCLOPENTENYL CATIONS ; CATALYTIC CYCLE ; ACIDIC ZEOLITES ; POOL MECHANISM
AbstractCarbenium ions as active intermediates play very important roles in methanol conversion to hydrocarbons (MTH) reactions, while their observation and structure confirmation is of great difficulty. In this contribution, solid-state magic-angle-spinning (MAS) NMR spectroscopy has been applied in the investigation of methanol conversions over H beta zeolite. By attempting the batch-like and continuous-flow reactions over the catalysts with varied acid site densities and under the condition of different reaction temperatures and atmosphere pressures, an optimized way for direct observation of carbenium ions has been developed. For the first time, two types of carbenium ions, including methylcyclopentenyl (MCP+) cations and heptamethylbenzenium (heptaMB(+)) cation, have been successfully captured by C-13 MAS NMR during methanol conversion over H beta zeolite. For the batch-like reactions, methanol conversion and carbenium ions observation have been promoted by using the Hp catalysts with more Bronsted acid sites and performing the reaction under relatively high atmosphere pressure. The competitive adsorption from reactants and products on the catalyst surface may cause the deprotonation of the carbenium ions. In the continuous-flow reactions, both the heptaMB(+) and MCP+ cations are formed and more easily observed compared with batch-like reactions due to the improved methanol conversion and the reduced competitive adsorption on the Bronsted acid sites. Based on the carbenium ions identification, a catalytic cycle is proposed to explain the generation of isobutene, a predominantly generated product on Hp zeolite, during methanol conversion. (C) 2015 Elsevier Inc. All rights reserved.
Language英语
WOS IDWOS:000371098200005
PublisherACADEMIC PRESS INC ELSEVIER SCIENCE
Citation statistics
Cited Times:25[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/171273
Collection中国科学院大连化学物理研究所
Corresponding AuthorWei, Yingxu; Liu, Zhongmin
Affiliation1.Chinese Acad Sci, Dalian Inst Chem Phys, iChEM Collaborat Innovat Ctr Chem Energy Mat, Natl Engn Lab Methanol Olefins,Dalian Natl Lab Cl, Dalian 116023, Peoples R China
2.China Univ Petr, CNPC Key Lab Catalysis, State Key Lab Heavy Oil Proc, Beijing 102249, Peoples R China
3.Chinese Acad Sci, Wuhan Inst Phys & Math, State Key Lab Magnet Resonance & Atom & Mol Phys, Natl Ctr Magnet Resonance Wuhan, Wuhan 430071, Peoples R China
4.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
5.Univ Chinese Acad Sci, Beijing 100039, Peoples R China
Recommended Citation
GB/T 7714
Zhang, Mozhi,Xu, Shutao,Li, Jinzhe,et al. Methanol to hydrocarbons reaction over H beta zeolites studied by high resolution solid-state NMR spectroscopy: Carbenium ions formation and reaction mechanism[J]. JOURNAL OF CATALYSIS,2016,335:47-57.
APA Zhang, Mozhi.,Xu, Shutao.,Li, Jinzhe.,Wei, Yingxu.,Gong, Yanjun.,...&Liu, Zhongmin.(2016).Methanol to hydrocarbons reaction over H beta zeolites studied by high resolution solid-state NMR spectroscopy: Carbenium ions formation and reaction mechanism.JOURNAL OF CATALYSIS,335,47-57.
MLA Zhang, Mozhi,et al."Methanol to hydrocarbons reaction over H beta zeolites studied by high resolution solid-state NMR spectroscopy: Carbenium ions formation and reaction mechanism".JOURNAL OF CATALYSIS 335(2016):47-57.
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