Spirocyclic quaternary ammonium cations for alkaline anion exchange membrane applications: an experimental and theoretical study

被引：52
作者：
Gu, Liang [1 ]
Dong, Huilong [2 ]
Sun, Zhe [1 ]
Li, Youyong [2 ]
Yan, Feng [1 ]
机构：
[1] Soochow Univ, Jiangsu Key Lab Adv Funct Polymer Design & Applic, Dept Polymer Sci & Engn, Coll Chem Chem Engn & Mat Sci, Suzhou 215123, Peoples R China
[2] Soochow Univ, Collaborat Innovat Ctr Suzhou Nano Sci & Technol, Inst Funct Nano & Soft Mat FUNSOM, Jiangsu Key Lab Carbon Based Funct Mat & Devices, Suzhou 215123, Peoples R China
来源：
RSC ADVANCES | 2016年 / 6卷 / 97期
关键词：
FUEL-CELL MEMBRANES; POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE); POLYATOMIC-MOLECULES; IMIDAZOLIUM CATIONS; IONIC LIQUIDS; STABILITY; POLYMER; CONDUCTIVITY; POLYETHYLENE; COPOLYMERS;
D O I：
10.1039/c6ra22313c
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Spirocyclic quaternary ammonium (QA) cation based anion exchange membranes (AEMs) were prepared and studied by both experimental measurements and theoretical calculations. Spirocyclic QA cations, including 5-azoniaspiro[4.4]nonane ([ASN](+)), 5-azoniaspiro[4.5]decane ([ASD](+)), and 5-azoniaspiro[4.6] undecane ([ASU](+)) were synthesized as small molecule model compounds and investigated in terms of their chemical stability in alkaline media at elevated temperatures. Compared with nonspirocyclic QA cations, spirocyclic QAs possessed higher alkaline stability, which correlates with their higher energy barrier value associated with a transition state. Furthermore, analogous spirocyclic QA cation based AEMs with promising alkaline stability in alkaline medium were synthesized via photo-cross-linking. The results indicated that alkaline stability studies on small molecule cations may provide a basis for evaluating that in corresponding polymer membranes, and also inspired a feasible way for the preparation of alkaline stable AEMs.
引用
收藏
页码：94387 / 94398
页数：12
相关论文
共 62 条
[1]   A MULTICENTER NUMERICAL-INTEGRATION SCHEME FOR POLYATOMIC-MOLECULES [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1988, 88 (04) :2547-2553
[2]   A mini-review on anion exchange membranes for fuel cell applications: Stability issue and addressing strategies [J].
Cheng, Jie ;
He, Gaohong ;
Zhang, Fengxiang .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2015, 40 (23) :7348-7360
[3]   RING-OPENING REACTIONS .3. MECHANISTIC PATH VS RING STRAIN CONTROL IN ELIMINATION AND SUBSTITUTION-REACTIONS OF 1,1-DIMETHYL CYCLIC AMMONIUM-IONS AND THEIR ALPHA,ALPHA'-DIMETHYL-SUBSTITUTED DERIVATIVES [J].
COSPITO, G ;
ILLUMINATI, G ;
LILLOCCI, C ;
PETRIDE, H .
JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (14) :2944-2947
[4]   Exploring Different Cationic Alkyl Side Chain Designs for Enhanced Alkaline Stability and Hydroxide Ion Conductivity of Anion-Exchange Membranes [J].
Dang, Hai-Son ;
Jannasch, Patric .
MACROMOLECULES, 2015, 48 (16) :5742-5751
[5]   Poly(phenylene oxide) functionalized with quaternary ammonium groups via flexible alkyl spacers for high-performance anion exchange membranes [J].
Dang, Hai-Son ;
Weiber, Eva Annika ;
Jannasch, Patric .
JOURNAL OF MATERIALS CHEMISTRY A, 2015, 3 (10) :5280-5284
[6]   AN ALL-ELECTRON NUMERICAL-METHOD FOR SOLVING THE LOCAL DENSITY FUNCTIONAL FOR POLYATOMIC-MOLECULES [J].
DELLEY, B .
JOURNAL OF CHEMICAL PHYSICS, 1990, 92 (01) :508-517
[7]   From molecules to solids with the DMol3 approach [J].
Delley, B .
JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (18) :7756-7764
[8]   Improving the Alkaline Stability of Imidazolium Cations by Substitution [J].
Dong, Huilong ;
Gu, Fenglou ;
Li, Min ;
Lin, Bencai ;
Si, Zhihong ;
Hou, Tingjun ;
Yan, Feng ;
Lee, Shuit-Tong ;
Li, Youyong .
CHEMPHYSCHEM, 2014, 15 (14) :3006-3014
[9]   Alkaline Anion-Exchange Membranes Containing Mobile Ion Shuttles [J].
Ge, Xiaolin ;
He, Yubin ;
Guiver, Michael D. ;
Wu, Liang ;
Ran, Jin ;
Yang, Zhengjin ;
Xu, Tongwen .
ADVANCED MATERIALS, 2016, 28 (18) :3467-+
[10]   Preparation and characterization of quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) as anion exchange membrane for alkaline polymer electrolyte fuel cells [J].
Gopi, K. Hari ;
Peera, S. Gouse ;
Bhat, S. D. ;
Sridhar, P. ;
Pitchumani, S. .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2014, 39 (06) :2659-2668
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