State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics Fine Mechanics and Physics, Chinese Academy of Sciences , Changchun 130033, P. R. China.
Key Lab of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University , Changchun 130024, P. R. China.
J Am Chem Soc. 2016 May 11;138(18):5897-903. doi: 10.1021/jacs.5b13490. Epub 2016 Apr 29.
Mimicking proton conduction mechanism of Nafion to construct novel proton-conducting materials with low cost and high proton conductivity is of wide interest. Herein, we have designed and synthesized a cationic covalent organic framework with high thermal and chemical stability by combining a cationic monomer, ethidium bromide (EB) (3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide), with 1,3,5-triformylphloroglucinol (TFP) in Schiff base reactions. This is the first time that the stable cationic crystalline frameworks allowed for the fabrication of a series of charged COFs (EB-COF:X, X = F, Cl, Br, I) through ion exchange processes. Exchange of the extra framework ions can finely modulate the COFs' porosity and pore sizes at nanoscale. More importantly, by introducing PW12O40(3-) into this porous cationic framework, we can greatly enhance the proton conductivity of ionic COF-based material. To the best of our knowledge, EB-COF:PW12 shows the best proton conductivity at room temperature among ever reported porous organic materials.
模仿 Nafion 的质子传导机制，构建具有低成本和高质子传导率的新型质子传导材料引起了广泛关注。在此，我们通过席夫碱反应将阳离子单体溴化乙锭（EB）（3,8-二氨基-5-乙基-6-苯基菲啶溴化物）与 1,3,5-三（三氟甲基）苯三醛（TFP）结合，设计并合成了一种具有高热稳定性和化学稳定性的阳离子共价有机骨架。这是首次通过离子交换过程制备稳定的阳离子结晶骨架，以得到一系列带电荷的 COFs（EB-COF：X，X = F，Cl，Br，I）。通过交换额外的骨架离子，可以在纳米尺度上精细调节 COFs 的孔隙率和孔径。更重要的是，通过将 PW12O40(3-)引入到这个多孔阳离子骨架中，我们可以大大提高离子 COF 基材料的质子传导率。据我们所知，在已报道的多孔有机材料中，EB-COF:PW12 在室温下表现出最佳的质子传导率。
