Expanding the dimensionality of proton conduction enables ultrahigh anhydrous proton conductivity of phosphoric acid-doped covalent-organic frameworks
Qianqian Yang, Xinyu Li, Changsong Xie, Ning Liu, Jianjian Yang, Zhihui Kong, Zixi Kang, Rongming Wang, Xiyou Li, Daofeng Sun
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.