【摘要】 通过表面改性方法以提高电解质的质子传导性和长寿命使用性是制造高效质子传导电解质的可行方法.本文以吡嗪基共价有机框架（CS-COF）作为模板,构建了其叔丁基缺失的COF结构,命名为PyHATP-1.研究发现,在353 K和98%相对湿度条件下,磺化样品PyHATP-1-SO₃H的质子电导率从PyHATP-1的7.2×10^-6S cm^-1指数级提高到了1.3×10^-3S cm^-1.此外,在骨架中加入磷酸分子后,磺化的H₃PO₄@PyHATP-1-SO₃H不仅比未磺化的H₃PO₄@PyHATP-1 (2.0×10^-3S cm^-1)具有显著提高的质子传导性(0.88×10^-1S cm^-1),而且表现出更佳的重复使用性.接触角测试和密度泛函理论计算表明,其质子传导性的显著增强和长寿命重复使用性应归功于孔隙表面的后磺化修饰,这大大提高了对质子载体（水和磷酸分子）的亲和力.这项研究表明,通过改变多孔材料的固有表面性质,可以获得具有高质子电导率和长寿命重复使用性的质子传导电解质.更多还原

【Abstract】 Enhancing the proton conductivity and long-life reusability of the electrolytes by surface modification is a feasible way to fabricate effective proton-conductive electrolytes for the practical application of proton exchange membrane. Herein, on account of its framework robustness and the proton-accepting nitrogen atoms uniformly located in its skeleton, a pyrazine-based covalent organic framework（COF）was selected as a masterplate, and its tert-butyl-absent COF structure, PyHATP-1, was constructed. Experimental results reveal that after its intrinsic pore surface is treated by postsulfonation, the proton conductivity of the sulfonated sample,Py HATP-1-SO₃H, exponentially increases to 1.3 × 10^-3from7.2 × 10^-6S cm^-1of PyHATP-1 at 353 K and 98% relative humidity. Moreover, while loading H₃PO₄ molecules into the skeletons, the sulfonated H₃PO₄@PyHATP-1-SO₃H not only displays a remarkable increase in the proton conductivity(0.88 × 10^-1S cm^-1) compared with the unsulfonated H₃PO₄@PyHATP-1(2.0 × 10^-3S cm^-1), but also exhibits a longer reusability. Contact angle tests and density functional theory calculations reveal that its remarkable enhancement in the proton conductivity and long-life reusability are attributed to the post-sulfonation of the pore surface, which significantly improves the affinity towards proton carriers（H₂O and H₃PO₄ molecules）. This work demonstrates that by modifying the intrinsic surface of porous materials, effective proton-conductive electrolytes with high proton conductivity and longlife reusability can be achieved.更多还原