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Methanol to Olefins Reaction over Cavity-type Zeolite: Cavity Controls the Critical Intermediates and Product Selectivity

文献类型：期刊论文

作者Liu, Zhongmin4; Deng, Feng3; Xiao, Fengshou2; Meng, Xiangju2; Wu, Xinqiang1,4; Zheng, Anmin3; Huang, Jindou4; Zhi, Yuchun4; Wei, Yingxu4; Chu, Yueying3
刊名ACS CATALYSIS
出版日期2018-12-01
卷号8期号:12页码:10950-10963
ISSN号2155-5435
关键词methanol to olefins H-RUB-SO critical intermediates product selectivity host guest interaction cavity-control
DOI10.1021/acscatal.8b02164
英文摘要Methanol to olefins (MTO) reaction over H-RUB 50 zeolite, an eight-membered ring (8-MR) and cavity-type zeolite, presents higher selectivity for ethene. The host-guest interaction was dissected and used to explain the cavity-controlled reaction route and product selectivity. By the aid of the in situ C-13 MAS NMR spectroscopy, GC-MS, C-12/C-13-methanol switch experiments, and theoretical calculations, the methylbenzenium cations, methylcyclopentenyl cations (triMB(+), tetraMB(+), and triMCP(+)), and their deprotonated forms with less methyl groups substitution were captured over LEV zeolite and confirmed as the critical reaction intermediates. The energetic span model was employed to identify the preferred reaction mechanism and provide the theoretical evidence to understand product selectivity. The side-chain methylation mechanism was theoretically predicated to be the energetically favorable route for olefins generation with the participation of these active intermediates. Paring cycle with trimethlycyclopentadienyl cation as the intermediate makes less contribution to ethene formation due to the relatively large energy span. Based on the overall evaluation of the catalytic cycle, the difference of energy span of the whole reaction pathway for ethene and propene formation can give direct theoretical evidence for product selectivity. Additional study to the steps for generating precursors of ethene and propene offers extra support on the understanding of product selectivity and the dominant generation of ethene. This study captured the critical intermediates and established a rational and energetically feasible route of light olefins generation from MTO reaction over H-RUB-50. More importantly, it is exhibited that cavity controls the product selectivity via the important steric constraint for the formation of critical intermediates and the proceeding of critical reaction steps, based on the understanding of the host guest interaction of the cavity-type zeolite catalyzed MTO reaction.
WOS关键词STATE NMR-SPECTROSCOPY ; HYDROCARBON-POOL ; TO-HYDROCARBONS ; REACTION-MECHANISM ; HEPTAMETHYLBENZENIUM CATION ; SHAPE-SELECTIVITY ; REACTION CENTERS ; CATALYTIC CYCLE ; 1ST PRINCIPLES ; CARBENIUM IONS
资助项目National Natural Science Foundation of China[91745109] ; National Natural Science Foundation of China[91545104] ; National Natural Science Foundation of China[21473182] ; National Natural Science Foundation of China[21703239] ; National Natural Science Foundation of China[21522310] ; Youth Innovation Promotion Association of the Chinese Academy of Sciences[2014165] ; Key Research Program of Frontier Sciences, CAS[QYZDY-SSW-JSC024] ; Key Research Program of Frontier Sciences, CAS[QYZDB-SSW-SLH026]
WOS研究方向Chemistry
语种英语
出版者AMER CHEMICAL SOC
WOS记录号WOS:000453491100003
资助机构National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Youth Innovation Promotion Association of the Chinese Academy of Sciences ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS
源URL[http://ir.wipm.ac.cn/handle/112942/13928]  
专题中国科学院武汉物理与数学研究所
通讯作者Liu, Zhongmin; Zheng, Anmin; Wei, Yingxu
作者单位1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
2.Zhejiang Univ, Dept Chem, Hangzhou 310028, Zhejiang, Peoples R China
3.Chinese Acad Sci, State Key Lab Magnet Resonance & Atom Mol Phys, Natl Ctr Magnet Resonance Wuhan, Inst Phys & Math, Wuhan 430071, Hubei, Peoples R China
4.Chinese Acad Sci, Natl Engn Lab Methanol Olefins, IChEM Collaborat Innovat Ctr Chem Energy Mat, Dalian Natl Lab Clean Energy,Dalian Inst Chem Phy, Dalian 116023, Peoples R China
推荐引用方式
GB/T 7714		 Liu, Zhongmin,Deng, Feng,Xiao, Fengshou,et al. Methanol to Olefins Reaction over Cavity-type Zeolite: Cavity Controls the Critical Intermediates and Product Selectivity[J]. ACS CATALYSIS,2018,8(12):10950-10963.
APA Liu, Zhongmin.,Deng, Feng.,Xiao, Fengshou.,Meng, Xiangju.,Wu, Xinqiang.,...&Zhang, Wenna.(2018).Methanol to Olefins Reaction over Cavity-type Zeolite: Cavity Controls the Critical Intermediates and Product Selectivity.ACS CATALYSIS,8(12),10950-10963.
MLA Liu, Zhongmin,et al."Methanol to Olefins Reaction over Cavity-type Zeolite: Cavity Controls the Critical Intermediates and Product Selectivity".ACS CATALYSIS 8.12(2018):10950-10963.

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来源：武汉物理与数学研究所

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