Three-Dimensional Covalent Organic Framework for Efficient Hydrogen Storage through Polarization-Wall Engineering.

Chen, Jia; Tang, Zhuozhuo; Zhu, Da; Sheng, Li; Li, Zonglong; Yang, Yang; Wang, Jianlong; Tang, Yaping et al. · Nano Lett · 2025

basic_science · Level V

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Abstract

Covalent organic frameworks (COFs), characterized by high surface areas and tunable pore structures/environments, are regarded as a promising alternative to physisorption H<sub>2</sub> storage materials. However, their interaction with hydrogen is often too weak, necessitating the exploration of strategies to enhance sorption heat. Herein, we strengthened the adsorption induction of COF on H<sub>2</sub> through a polarized wall engineering. The fluorine groups on the pore wall of three-dimensional COFs polarize their surrounding regions, resulting in high sorption heat sites. Due to the enhanced H<sub>2</sub> sorption heat, the total H<sub>2</sub> uptake of 3D-F-COF is up to to 5.96 wt % at 77 K and 90 bar. Moreover, the H<sub>2</sub> adsorption enhancement effect of the polar group does not involve chemisorption, and the material exhibits excellent cycling stability. These results reveal that modulating the H<sub>2</sub> sorption heat by incorporating polar groups is a promising strategy for achieving efficient H<sub>2</sub> storage in porous materials.