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Research Article

Expanding the dimensionality of proton conduction enables ultrahigh anhydrous proton conductivity of phosphoric acid-doped covalent-organic frameworks

Qianqian Yang2, Xinyu Li1, Changsong Xie1, Ning Liu2, Jianjian Yang1, Zhihui Kong1, Zixi Kang1, Rongming Wang1,2( ), Xiyou Li1,2( ), Daofeng Sun1( )
School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China
State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
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Graphical Abstract

In this work, we prove that the increase of hydrophilic groups in the channels of two-dimensional covalent organic frameworks (2D COFs) can make phosphoric acid (PA) insert into its interlayer to expand the proton conduction pathways, and thus significantly enhance the proton conductivity of COF-3@PA-30 to 1.4 S·cm−1, which is a record of anhydrous proton conductivity reported to date.

Abstract

It is of great significance to develop high-temperature anhydrous proton conducting materials. Herein, we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks (COFs) through expanding the dimensionality of proton conduction. Three COF-based composites, COF-1@PA, COF-2@PA, and COF-3@PA (PA: phosphoric acid), are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups. With the increase of hydrophilic groups, COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks. powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) analyses show that PA can not only enter the channels of COF-3, but also insert into its 2D interlayers. This expands the proton conduction pathways from one-dimensional (1D) to three-dimensional (3D), which greatly improves the proton conductivity of COF-3. Meanwhile, the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30 (30 μL of PA loaded on COF-3). At 150 °C, COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1, which is a record of anhydrous proton conductivity reported to date. This work develops a new strategy for increasing the proton conductivity of 2D COF materials.

Keywords

dopingcovalent organic frameworkproton conductorsanhydrous proton conductionphosphoric acid (PA)

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Nano Research
Volume 16 Issue 8,
August 2023
Pages 10946-10955
DOI: 10.1007/s12274-023-5812-x
Cite this article:
Yang Q, Li X, Xie C, et al. Expanding the dimensionality of proton conduction enables ultrahigh anhydrous proton conductivity of phosphoric acid-doped covalent-organic frameworks. Nano Research, 2023, 16(8): 10946-10955. https://doi.org/10.1007/s12274-023-5812-x
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Received: 04 January 2023
Revised: 27 April 2023
Accepted: 07 May 2023
Published: 05 July 2023
© Tsinghua University Press 2023
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