Highly Stable N3-Substituted Imidazolium-Based Alkaline Anion Exchange Membranes: Experimental Studies and Theoretical Calculations
Highly Stable N3-Substituted Imidazolium-Based Alkaline Anion Exchange Membranes: Experimental Studies and Theoretical Calculations
复制标题
高稳定性 N3 取代咪唑基碱性阴离子交换膜：实验研究和理论计算
DOI：
10.1021/ma402334t
复制
发表时间：
2014-01-14
期刊：
影响因子：
5.5
通讯作者：
Yan, Feng
中科院分区：
文献类型：
--
作者：
Gu, Fenglou;Dong, Huilong;Yan, Feng
合成了具有各种 N3 取代基（包括甲基、丁基、庚基、十二烷基、异丙基和二苯基甲基）的咪唑鎓阳离子，并研究了其碱性稳定性。通过定量 1H NMR 谱和密度泛函理论 (GGA-BLYP) 计算研究了 N3-取代基对碱性稳定性的影响。具有最高LUMO能量值的异丙基取代咪唑鎓阳离子([DMIIm]+)在NaOH水溶液中表现出最高的碱性稳定性。在高温下的 CD3OD/D2O NaOH 溶液中，[DMIIm]+ 阳离子还表现出比季铵阳离子苄基三甲基铵 ([BTMA]+) 更高的碱性稳定性。这一观察启发了基于[DMIIm]+的碱性阴离子交换膜（AEM）的制备，该膜在碱性溶液中表现出高碱性稳定性。
Imidazolium cations with various N3-substituents (including methyl, butyl, heptyl, dodecyl, isopropyl, and diphenylmethyl groups) were synthesized and investigated in terms of their alkaline stability. The effect of the N3-substituent on the alkaline stability was studied by quantitative 1H NMR spectra and density functional theory (GGA-BLYP) calculations. The isopropyl substituted imidazolium cation ([DMIIm]+) with the highest LUMO energy value exhibited the highest alkaline stability in aqueous NaOH. The [DMIIm]+ cation also exhibited higher alkaline stability than that of a quaternary ammonium cation, benzyltrimethyl-ammonium ([BTMA]+), in CD3OD/D2O NaOH solution at elevated temperatures. This observation inspired the preparation of [DMIIm]+-based alkaline anion exchange membranes (AEMs) which showed high alkaline stability in alkaline solution.