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Reaction Mechanism for Direct Cyclization of Linear C 5 , C 6 , and C 7 Alkenes over H‐ITQ‐13 Zeolite Investigated Using Density Functional Theory
Author(s) -
Ma Hong,
Chen Yanyan,
Wei Zhihong,
Wang Sen,
Qin Zhangfeng,
Dong Mei,
Li Junfen,
Wang Jianguo,
Fan Weibin
Publication year - 2018
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201701020
Subject(s) - chemistry , alkene , density functional theory , aromatization , computational chemistry , methanol , diene , reaction mechanism , carbocation , medicinal chemistry , photochemistry , catalysis , organic chemistry , natural rubber
Although dienes or trienes have been shown to be possible precursors for cyclization, direct cyclization of alkenes or alkoxides has not been systematically studied yet. Thus, the reaction mechanism of cyclization of linear alkenes over H‐ITQ‐13 was investigated here by density functional theory considering dispersive interactions (DFT‐D). The similar free energy of different linear alkoxides of the same carbon number suggests that they can co‐exist in the H‐ITQ‐13 intersection at 673.15 K during the methanol to olefins (MTO) process. The formation of linear alkenes by olefins methylation with methoxyl groups (ZOCH 3 ), trimethyloxonium ions (TMO + ), and methanol are kinetically more favorable than by dimerization of olefins. Linear alkoxides or alkenes prefer direct cyclization to cycloalkanes rather than hydride transfer to diene. This study provides new insight into the alkene cyclization and aromatization mechanisms in MTO process.