Insight into the role of weak interaction played in the fixation of CO2 catalyzed by the amino-functionalized imidazolium-based ionic liquids
Insight into the role of weak interaction played in the fixation of CO2 catalyzed by the amino-functionalized imidazolium-based ionic liquids
复制标题
深入探讨弱相互作用在氨基官能化咪唑基离子液体催化固定CO2中的作用
DOI：
10.1016/j.jcou.2017.01.026
复制
发表时间：
2017-03-01
影响因子：
7.7
通讯作者：
Zhang, Suojiang
中科院分区：
文献类型：
--
作者：
Chen, Ci;Ma, Yuan;Zhang, Suojiang
采用密度泛函理论（DFT）研究了氨基功能化咪唑类离子液体催化CO2与环氧丙烷（PO）偶联反应的机理。虽然在以往的文献中已经从理论上阐述了各种室温离子液体或功能化离子液体催化固定CO2的机理，但并不完全适用于氨基功能化离子液体。首先，1-（3-氨基丙基）-3-甲基咪唑鎓氯化物（[APmim] Cl）将与CO2反应以产生1-（3-氨基甲酸丙基）-3-甲基咪唑鎓氯化物（[CAPmim] Cl）。然后，[APmim] Cl，[CAPmim] Cl，和它们的组合将被用作催化剂，导致九种可能的路线。与以往的工作不同，本工作通过考虑两个相同或不同组分的协同效应的新模型，使人们对该机理有了更好的理解。同时考虑了催化剂与反应物之间的相互作用以及不同催化组分之间的影响。除了Cl阴离子的亲核进攻外，[CAPmim]（+）阳离子作为主要组分活化PO上的O原子，直接导致开环。[APmim]（+）阳离子用于稳定[CAPmim]（+），这是最有利的途径。采用非共价相互作用（NCI）图分析了前三条有利路线催化效率较高的原因。氢键和分散吸引相互作用被证实在催化活性中起决定作用。(C)2017爱思唯尔有限公司版权所有
The mechanism of coupling reaction of CO2 with propylene oxide (PO) catalyzed by the aminofunctionalized imidazolium-based ionic liquid is theoretically investigated by the density functional theory (DFT). Although the mechanisms of the fixation of CO2 catalyzed by various room-temperature ionic liquids or functionalized ionic liquids have been theoretically elucidated in previous literatures, it is not totally suitable for the amino-functionalized ionic liquid. First, the 1-(3-aminopropyl)-3methylimidazolium chloride ([APmim] Cl) would react with CO2 to produce the 1-(3-carbamic acid propyl)-3-methylimidazolium chloride ([CAPmim] Cl). Then, [APmim] Cl, [CAPmim] Cl, and combination of them would be employed as the catalyst leading to nine possible routes. Different from the previous work, this work allows a better comprehension of the mechanism by means of a new model that the cooperative effect of two same or different components is considered. Both the interaction between catalyst and reactant and the influence between different catalytic components are considered. Besides the nucleophilic attack of the Cl anion, the [CAPmim](+) cation is taken as the main component to activate the O atom of PO directly leading to the ring-opening. The [APmim](+) cation is utilized to stabilize the [CAPmim](+), which is the most favorable route. The noncovalent interactions (NCI) plot is employed as a tool to analyze the reason of the higher catalytic efficiency of top three favorable routes. The hydrogen bond and dispersive attractive interaction is confirmed to play a determining role in the catalytic activity. (C) 2017 Elsevier Ltd. All rights reserved.