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

作　　者：Zijiang Dou Weiqiang Tang Peng Xie Shuangliang Zhao 

机构地区：[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

出　　处：《Chinese Journal of Chemical Engineering》2024年第2期180-188,共9页中国化学工程学报（英文版）

基　　金：supported by the National Natural Science Foundation of China(22168002,22108070,21878078);the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119);the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012);the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106);the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。

摘　　要：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 multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on 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 indicates 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.

关 键 词：Solvent effect Ionic liquids Diels-Alder reaction Reaction density functional theory 

分 类 号：O645.1[理学—物理化学]