Yang Zongfan, Chen Pei, Hao Wenjing, Xie Zhen, Feng Yu, Xing Guolong, Chen Long
Department of Chemistry, Institute of Molecular Plus, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin, 300072, China.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institution of Chemistry, Chinese Academy of Sciences (CAS), Beijing, 100190, China.
Chemistry. 2021 Feb 19;27(11):3817-3822. doi: 10.1002/chem.202004727. Epub 2021 Jan 12.
Open 1D channels found in covalent organic frameworks are unique and promising to serve as pathways for proton conduction; how to develop high-rate yet stable transporting systems remains a substantial challenge. Herein, this work reports a strategy for exploring proton-conducting frameworks by engineering pore walls and installing proton-containing polymers into the pores. Amide-linked and sulfonated frameworks were synthesized from imine-linked precursors via sequentially engineering to oxidize into amide linkages and to further anchor sulfonic acid groups onto the pore walls, enabling the creation of sulfonated frameworks with high crystallinity and channel ordering. Integrating sulfonated polyether ether ketone chains into the open channels enables proton hopping to across the channels, greatly increases proton conductivity and enables a stable continuous run. These results suggest a way to explore proton-conducting COFs via systematic engineering of the wall and space of the open nanochannels.
在共价有机框架中发现的开放一维通道具有独特性，有望作为质子传导的途径；如何开发高速率且稳定的传输系统仍然是一项重大挑战。在此，这项工作报告了一种通过设计孔壁并将含质子聚合物安装到孔中来探索质子传导框架的策略。酰胺连接和磺化框架是由亚胺连接的前体通过依次工程化合成的，先氧化形成酰胺键，再进一步将磺酸基团锚定在孔壁上，从而创建出具有高结晶度和通道有序性的磺化框架。将磺化聚醚醚酮链整合到开放通道中可使质子跳跃穿过通道，大大提高质子传导率并实现稳定的连续运行。这些结果表明了一种通过对开放纳米通道的壁和空间进行系统工程来探索质子传导共价有机框架的方法。
