Li Shuai, Liu Yanze, Li Li, Liu Caixia, Li Jiani, Ashraf Shumaila, Li Pengfei, Wang Bo
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic, Advanced Research Institute of Multidisciplinary Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
ACS Appl Mater Interfaces. 2020 May 20;12(20):22910-22916. doi: 10.1021/acsami.0c04002. Epub 2020 May 8.
Anhydrous proton-conductive materials have attracted great attention in recent years. Doping imidazole as a proton carrier in porous materials, especially pure organic crystalline covalent organic frameworks (COFs), is a promising solution. However, the influence of the hydrogen donor ability of imine functional groups in COFs on the proton conduction has largely been unexplored. Herein, a series of iso-reticular thiophene-based COFs has been synthesized with a similar pore structure and surface area. Different amounts of imidazole were infiltrated to the COFs by vapor diffusion in a highly controlled manner. The introduction of thiophene rings increases the hydrogen bonding donation ability of the imine linker, which resulted in an enhanced proton conductivity of the imidazole-doped COFs by one order of magnitude. The formation of hydrogen bonding between the imine group and imidazole was demonstrated by Fourier transform infrared spectroscopy and density functional theory calculations.
近年来，无水质子传导材料备受关注。在多孔材料，特别是纯有机晶体共价有机骨架（COF）中掺杂咪唑作为质子载体，是一种很有前景的解决方案。然而，COF中亚胺官能团的给氢能力对质子传导的影响在很大程度上尚未得到探索。在此，合成了一系列具有相似孔结构和表面积的同网状噻吩基COF。通过高度可控的气相扩散法，将不同量的咪唑渗透到COF中。噻吩环的引入提高了亚胺连接体的氢键给体能力，这使得咪唑掺杂的COF的质子传导率提高了一个数量级。通过傅里叶变换红外光谱和密度泛函理论计算证明了亚胺基团与咪唑之间氢键的形成。
