吡嗪基共价有机框架的内表面磺化作用显著增强质子传导性

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中文摘要：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Py-HATP-1.研究发现,在353 K和98％相对湿度条件下,磺化样品Py-HATP-1-SO3H的质子电导率从PyHATP-1的7.2 × 10-6 S cm-1指数级提高到了 1.3 × 10-3Scm-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 × 10-3 Scm-1)具有显著提高的质子传导性(0.88 × 10-1 S 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.

外文标题：Remarkably enhancing proton conductivity by intrinsic surface sulfonation of a pyrazine-linked covalent organic framework

外文摘要：Enhancing the proton conductivity and long-life reusability of the electrolytes by surface modification is a feasible way to fabricate effective proton-conductive electro-lytes for the practical application of proton exchange mem-brane.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 post-sulfonation,the proton conductivity of the sulfonated sample,PyHATP-1-SO3H,exponentially increases to 1.3 × 10-3 from 7.2 × 10-6 S cm-1 of 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 × 10-1 S cm-1)compared with the unsulfonated H3PO4@PyHATP-1(2.0 × 10-3 Son-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-con-ductive electrolytes with high proton conductivity and long-life reusability can be achieved.

外文关键词：

covalent organic frameworkelectrolytesurface modificationproton conductionpyrazine linkage

作者：

栾天翔、王秋荣、张鹏图、李万超、孔硕、冯祎静、苑世领、李培洲

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作者单位：

School of Chemistry and Chemical Engineering,Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion,Science Centre for Material Creation and Energy Conversion,Institute of Frontier and Interdisciplinary Science,Shandong University,Jinan 250100,China

School of Chemical Engineering,Shandong Institute of Pertroleum and Chemical Technology,Dongying 257061,China

No.1 Institute of Geology and Mineral Resources of Shandong Province,Jinan 250100,China

关键词：

covalent organic framework electrolyte surface modification proton conduction pyrazine linkage

基金：

"Qilu Young Talent Scholar"program of Shandong UniversityCarbon Neutrality Research Institute FundsCarbon Neutrality Research Institute FundsWynca Group for its"Chem is Try"Innovation Fund under"Xin'An Cup"program

项目编号：

11190088963032CNIF20230101CNIF2023020211190047102082

出版年：

2024

DOI：

10.1007/s40843-023-2685-5

中国科学:材料科学(英文)

CSTPCD

ISSN：

年,卷(期)：2024.67(1)

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