Liu Qian, Zhang Shouhai, Wang Zhaoqi, Han Jianhua, Song Ce, Xu Peiqi, Wang Xu, Fu Shaokui, Jian Xigao
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Liaoning High-Performance Polymer Engineering Research Center, Dalian Key Laboratory of Membrane Materials and Membrane Processes, Dalian, 116024, China.
Phys Chem Chem Phys. 2022 Jan 19;24(3):1760-1769. doi: 10.1039/d1cp04531h.
Sulfonated N-heterocyclic poly(aryl ether) proton-exchange membranes have potential applications in the fuel-cell field due to their favorable proton conduction capacity and stability. This paper investigates the changes in mass and performance decay, such as proton conduction and mechanical strength, of sulfonated poly(ether ether ketone)s (SPEEKs) and three sulfonated N-heterocyclic poly(aryl ether ketone) (SPPEK, SPBPEK-P-8, and SPPEKK-P) membranes in Fenton's oxidative experiment. The SPEEK membrane exhibited the worst oxidative stability. The oxidative stability of the SPPEK membrane is enhanced due to the introduction of phthalazinone units in the chains. The SPPEKK-P and SPBPEK-P-8 membranes exhibit better radical tolerance than the SPPEK membrane, with proton conductivity retention rates of 66% and 73% for 1 h oxidative treatment, respectively. In addition, the molecular chains of SPPEKK-P and SPBPEK-P-8 exhibit relatively little disruption. The pendant benzenesulfonic groups enhance the steric effects for reducing radical attacks on the ether bonds and reduce the hydration of molecular chains. The introduction of phthalazinone units decreases the rupture points in the main chain. Therefore, the radical tolerance of the membranes is improved. These results provide a reference for the design of highly stable sulfonated heterocyclic poly(aryl ether) membranes.
磺化N-杂环聚芳醚质子交换膜因其良好的质子传导能力和稳定性在燃料电池领域具有潜在应用。本文研究了磺化聚醚醚酮（SPEEKs）以及三种磺化N-杂环聚芳醚酮（SPPEK、SPBPEK-P-8和SPPEKK-P）膜在芬顿氧化实验中质量和性能衰减的变化，如质子传导和机械强度。SPEEK膜表现出最差的氧化稳定性。由于链中引入了酞嗪酮单元，SPPEK膜的氧化稳定性得到增强。SPPEKK-P和SPBPEK-P-8膜比SPPEK膜表现出更好的自由基耐受性，在1小时氧化处理后质子传导率保留率分别为66%和73%。此外，SPPEKK-P和SPBPEK-P-8的分子链受到的破坏相对较小。侧基苯磺酸基团增强了空间效应，减少了自由基对醚键的攻击，并降低了分子链的水合作用。酞嗪酮单元的引入减少了主链中的断裂点。因此，膜的自由基耐受性得到提高。这些结果为设计高度稳定的磺化杂环聚芳醚膜提供了参考。
