{"title":"还原氨基工程双功能网络增强了聚乙烯吡咯烷酮AEMs的碱性稳定性和氢氧化物电导率","authors":"Shiyu Dong, Yutong Fan, Fuhai Wang, Chunhui Shen, Shanjun Gao","doi":"10.1007/s11581-025-06554-0","DOIUrl":null,"url":null,"abstract":"<div><p>While ether-free anion exchange membranes (AEMs) have demonstrated enhanced alkaline stability, the simultaneous enhancement of hydroxide conductivity and dimensional stability remains a challenging aspect to address. This study proposes a reductive amination strategy for synthesizing cross-linked polyvinylpyrrolidone (PVP)-based AEMs. The strategy involves controlled molecular weight variation (K16, K30, and K60) and alkylamine functionalization. The employment of n-propylamine, 3-(Dimethylamino)propylamine (DMAPA), and hexadecylamine in conjunction with a 1,6-dibromohexane cross-linker has enabled the systematic tailoring of membrane architectures. The K16-PVP grafted with DMAPA demonstrated the highest grafting degree, as confirmed by FT-IR and <sup>1</sup>H NMR analyses, and exhibited enhanced cross-linking density. This synergy resulted in a significant improvement in ion transportation and mechanical stability. The optimized membrane performed exceptionally, with 94.15 mS·cm<sup>−1</sup> of hydroxide conductivity at 80 °C, surpassing PVP-based AEM reports, while still maintaining 85.3% conductivity after 240 h in 2 M NaOH at 80 °C. These results establish molecular weight-controlled reductive amination as an effective approach to resolve the critical conductivity-stability trade-off in anion exchange membranes.</p><h3>Graphical Abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":599,"journal":{"name":"Ionics","volume":"31 9","pages":"9147 - 9161"},"PeriodicalIF":2.6000,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reductive amination–engineered dual-function networks enhance alkaline stability and hydroxide conductivity in polyvinylpyrrolidone AEMs\",\"authors\":\"Shiyu Dong, Yutong Fan, Fuhai Wang, Chunhui Shen, Shanjun Gao\",\"doi\":\"10.1007/s11581-025-06554-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>While ether-free anion exchange membranes (AEMs) have demonstrated enhanced alkaline stability, the simultaneous enhancement of hydroxide conductivity and dimensional stability remains a challenging aspect to address. This study proposes a reductive amination strategy for synthesizing cross-linked polyvinylpyrrolidone (PVP)-based AEMs. The strategy involves controlled molecular weight variation (K16, K30, and K60) and alkylamine functionalization. The employment of n-propylamine, 3-(Dimethylamino)propylamine (DMAPA), and hexadecylamine in conjunction with a 1,6-dibromohexane cross-linker has enabled the systematic tailoring of membrane architectures. The K16-PVP grafted with DMAPA demonstrated the highest grafting degree, as confirmed by FT-IR and <sup>1</sup>H NMR analyses, and exhibited enhanced cross-linking density. This synergy resulted in a significant improvement in ion transportation and mechanical stability. The optimized membrane performed exceptionally, with 94.15 mS·cm<sup>−1</sup> of hydroxide conductivity at 80 °C, surpassing PVP-based AEM reports, while still maintaining 85.3% conductivity after 240 h in 2 M NaOH at 80 °C. These results establish molecular weight-controlled reductive amination as an effective approach to resolve the critical conductivity-stability trade-off in anion exchange membranes.</p><h3>Graphical Abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":599,\"journal\":{\"name\":\"Ionics\",\"volume\":\"31 9\",\"pages\":\"9147 - 9161\"},\"PeriodicalIF\":2.6000,\"publicationDate\":\"2025-07-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Ionics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11581-025-06554-0\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Ionics","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11581-025-06554-0","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
虽然无醚阴离子交换膜(AEMs)已经证明了增强的碱性稳定性,但同时增强氢氧化物电导率和尺寸稳定性仍然是一个具有挑战性的方面。本研究提出了一种合成交联聚乙烯吡咯烷酮(PVP)基AEMs的还原性胺化策略。该策略包括控制分子量变化(K16, K30和K60)和烷基胺功能化。正丙胺、3-(二甲胺)丙胺(DMAPA)和十六胺与1,6-二溴己烷交联剂结合使用,使膜结构的系统定制成为可能。FT-IR和1H NMR分析证实,DMAPA接枝的K16-PVP接枝度最高,交联密度增强。这种协同作用导致离子传输和机械稳定性的显著改善。优化后的膜表现优异,在80°C下氢氧化物电导率为94.15 mS·cm−1,超过了基于pvp的AEM报告,在80°C下2 M NaOH中240 h后仍保持85.3%的电导率。这些结果建立了分子量控制的还原性胺化反应是解决阴离子交换膜中关键的电导率-稳定性权衡的有效方法。图形抽象
Reductive amination–engineered dual-function networks enhance alkaline stability and hydroxide conductivity in polyvinylpyrrolidone AEMs
While ether-free anion exchange membranes (AEMs) have demonstrated enhanced alkaline stability, the simultaneous enhancement of hydroxide conductivity and dimensional stability remains a challenging aspect to address. This study proposes a reductive amination strategy for synthesizing cross-linked polyvinylpyrrolidone (PVP)-based AEMs. The strategy involves controlled molecular weight variation (K16, K30, and K60) and alkylamine functionalization. The employment of n-propylamine, 3-(Dimethylamino)propylamine (DMAPA), and hexadecylamine in conjunction with a 1,6-dibromohexane cross-linker has enabled the systematic tailoring of membrane architectures. The K16-PVP grafted with DMAPA demonstrated the highest grafting degree, as confirmed by FT-IR and 1H NMR analyses, and exhibited enhanced cross-linking density. This synergy resulted in a significant improvement in ion transportation and mechanical stability. The optimized membrane performed exceptionally, with 94.15 mS·cm−1 of hydroxide conductivity at 80 °C, surpassing PVP-based AEM reports, while still maintaining 85.3% conductivity after 240 h in 2 M NaOH at 80 °C. These results establish molecular weight-controlled reductive amination as an effective approach to resolve the critical conductivity-stability trade-off in anion exchange membranes.
期刊介绍:
Ionics is publishing original results in the fields of science and technology of ionic motion. This includes theoretical, experimental and practical work on electrolytes, electrode, ionic/electronic interfaces, ionic transport aspects of corrosion, galvanic cells, e.g. for thermodynamic and kinetic studies, batteries, fuel cells, sensors and electrochromics. Fast solid ionic conductors are presently providing new opportunities in view of several advantages, in addition to conventional liquid electrolytes.