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

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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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 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 S 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 long-life reusability can be achieved.

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 × 10−6 S cm−1指数级提 高到了1.3 × 10−3 S 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 × 10−3 S cm−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

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Acknowledgements

This work was supported by “Qilu Young Talent Scholar” program (11190088963032) of Shandong University and the Carbon Neutrality Research Institute Funds (CNIF20230101 and CNIF20230202). Luan T thanks the Wynca Group for its “Chem is Try” Innovation Fund (11190047102082) under “Xin’An Cup” program. We thank the Analytical Center for Structural Constituent and Physical Property of Core Facilities Sharing Platform, Shandong University for the structure analyses.

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Authors and Affiliations

  1. 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

    Tian-Xiang Luan  (栾天翔), Qiurong Wang  (王秋荣), Shuo Kong  (孔硕), Yijing Feng  (冯祎静), Shiling Yuan  (苑世领) & Pei-Zhou Li  (李培洲)

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

    Pengtu Zhang  (张鹏图) & Shiling Yuan  (苑世领)

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

    Wanchao Li  (李万超)

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  1. Tian-Xiang Luan  (栾天翔)
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Contributions

Author contributions Luan TX performed the major part of the experiments. Wang Q, Kong S and Feng Y participated in the experiments and discussion. Luan TX, Zhang P, Yuan S and Li PZ designed the project, discussed and analyzed the data, interpreted the results and jointly wrote the paper.

Corresponding author

Correspondence to Pei-Zhou Li  (李培洲).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Experimental details and supporting data are available in the online version of the paper.

Tianxiang Luan is now a postdoctor at 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, School of Chemistry and Chemical Engineering, Shandong University. He received his PhD degree from the School of Chemistry and Chemical Engineering, Shandong University in 2023. His current research interest focuses on the syntheses and applications of advanced functional porous materials.

Peizhou Li is now a professor at the School of Chemistry and Chemical Engineering, Shandong University, China. He obtained his PhD degree in applied chemistry at Kobe University (AIST, Kansai center) in 2012. After that, he worked as a research fellow at Nanyang Technological University, Singapore. In November 2017, he joined Shandong University as a full professor. His current research interests mainly focus on the construction and application of framework porous materials.

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Luan, TX., Wang, Q., Zhang, P. et al. Remarkably enhancing proton conductivity by intrinsic surface sulfonation of a pyrazine-linked covalent organic framework. Sci. China Mater. 67, 125–133 (2024). https://doi.org/10.1007/s40843-023-2685-5

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