中国化学工程学报(英文版)2024，Vol.66Issue(2) ：180-188.DOI:10.1016/j.cjche.2023.10.007

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Zijiang Dou Weiqiang Tang Peng Xie Shuangliang Zhao
中国化学工程学报(英文版)2024，Vol.66Issue(2) ：180-188.DOI:10.1016/j.cjche.2023.10.007
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Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Zijiang Dou 1Weiqiang Tang 2Peng Xie 1Shuangliang Zhao1
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作者信息

  • 1. Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology and School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China
  • 2. State Key Laboratory of Chemical Engineering and School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China
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Abstract

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the mul-tiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF6])solventon the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this in-dicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Key words

Solvent effect/Ionic liquids/Diels-Alder reaction/Reaction density functional theory

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基金项目

National Natural Science Foundation of China(22168002)

National Natural Science Foundation of China(22108070)

National Natural Science Foundation of China(21878078)

Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)

Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)

Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)

Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)

出版年

2024
中国化学工程学报(英文版)
中国化工学会

中国化学工程学报(英文版)

CSTPCDEI
影响因子：0.818
ISSN：1004-9541
参考文献量72
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