Robust Proton-Exchange Membranes Based on Perfluorosulfonic Acid-Functionalized Poly(phenyl-alkane) and Polyxanthene: Effects of Skeletal Structures on Membrane Properties,Macromolecules

当前位置： X-MOL 学术 › Macromolecules › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Robust Proton-Exchange Membranes Based on Perfluorosulfonic Acid-Functionalized Poly(phenyl-alkane) and Polyxanthene: Effects of Skeletal Structures on Membrane Properties
Macromolecules ( IF 5.1 ) Pub Date : 2024-03-18 , DOI: 10.1021/acs.macromol.4c00117
Boxin Xue ₁ , Zejun Zheng _{1,

2} , Huidong Qian ₃ , Zhen Wang _{1,

2} , Jingling Yan _{1,

2}

Affiliation

Perfluorosulfonic acid-functionalized aromatic polymers are attractive alternatives to commercial Nafion membranes; however, the heteroatoms (O, S, etc.) in traditional poly(arylene ether)s can initiate undesired chemical degradation by radical specie attacks. Herein, two robust proton-exchange membranes (PEMs), PA-BP-PFSA and PX-BP-PFSA, based on perfluorosulfonic acid-functionalized poly(phenyl-alkane) and polyxanthene, respectively, were prepared by copper-catalyzed postfunctionalization of poly(phenyl-alkane) and polyxanthene precursors containing bromine substituents. Molecular simulation results showed that polyxanthene had a higher rigidity than that of poly(phenyl-alkane). Hence, PX-BP-PFSA had higher Brunauer–Emmett–Teller surface area (124 versus 58 m² g^–1) and fractional free volume (0.303 versus 0.228), compared to that of PA-BP-PFSA. The ionic clusters in PA-BP-PFSA were obviously larger than those in PX-BP-PFSA and showed a higher water uptake and swelling ratio. PX-BP-PFSA exhibited higher conductivity than that of PA-BP-PFSA due to its better microporous nanochannels for ion transport. Both PEMs exhibited an excellent oxidative stability, with no noticeable changes in the thermogravimetric analysis and ¹H and ¹⁹F NMR spectra after immersion in Fenton’s reagent for 2 h at 80 °C. This work presents a feasible approach to develop highly robust perfluorosulfonic acid-functionalized PEMs and provides meaningful insights into the structure–property relationship.

中文翻译：

基于全氟磺酸官能化聚苯基烷烃和聚呫吨的鲁棒质子交换膜：骨架结构对膜性能的影响

全氟磺酸官能化芳香族聚合物是商业 Nafion 膜的有吸引力的替代品；然而，传统聚亚芳基醚中的杂原子（O、S等）可能会因自由基攻击而引发不需要的化学降解。在此，两种坚固的质子交换膜（PEM），PA-BP-PFSA和PX-BP-PFSA，分别基于全氟磺酸功能化的聚（苯基烷烃）和聚呫吨，通过铜催化聚氧乙烯的后功能化制备。（苯基烷烃）和含有溴取代基的聚呫吨前体。分子模拟结果表明，聚氧杂蒽比聚苯基烷烃具有更高的刚性。因此，与PA-BP-PFSA相比，PX-BP-PFSA具有更高的 Brunauer-Emmett-Teller 表面积（124 比 58 m ² g ^–1 ）和自由体积分数（0.303 比 0.228）。PA-BP-PFSA中的离子簇明显大于PX-BP-PFSA中的离子簇，并且表现出更高的吸水率和溶胀率。由于具有更好的离子传输微孔纳米通道，PX-BP-PFSA表现出比PA-BP-PFSA更高的电导率。两种PEM均表现出优异的氧化稳定性，在80℃下浸入芬顿试剂2小时后，热重分析以及¹ H和¹⁹ F NMR谱没有明显变化。这项工作提出了一种开发高度稳健的全氟磺酸功能化质子交换膜的可行方法，并为结构-性能关系提供了有意义的见解。

更新日期：2024-03-18

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南