Single-Crystalline 3D Covalent Organic Frameworks with Exceptionally High Specific Surface Areas and Gas Storage Capacities

Published

October 11, 2024

Author(s)

Baoqiu Yu, Yu Tao, Xuan Yao, Yucheng Jin, Shan Liu, Tongtong Xu, Hailong Wang, Hui Wu, Wei Zhou, Xin Zhou, Xiao Wang, Xu Ding, Xin Xiao, Yue-Biao Zhang, Jianzhuang Jiang

Abstract

Single-crystalline covalent organic frameworks (COFs) are highly desirable towards understanding their pore chemistry and functions. Herein, two 50100 μm single-crystalline three-dimensional (3D) COFs, TAM-TFPB-COF and TAPB-TFS-COF, were fabricated from the condensation of 4,4',4'',4'''-methanetetrayltetraaniline (TAM) with 3,3',5,5'- tetrakis(4-formylphenyl)bimesityl (TFPB) and 3,3',5,5'-tetrakis(4-aminophenyl)bimesityl (TAPB) with 4,4',4'',4'''- silanetetrayltetrabenzaldehyde (TFS), respectively, in 1,4-dioxane under the catalysis of acetic acid. Single-crystal 3D electron diffraction and synchrotron powder X-ray with Le Bail refinements reveal their isostructural doubly interpenetrated dia-b networks. The nitrogen sorption measurements at 77 K disclose the narrow distributed microporosity nature of both activated COFs centered at 1.36 nm for TAM-TFPB-COF and 1.48 nm for TAPB-TFS-COF together with their exceptionally high Brunauer−Emmett−Teller (BET) surface area of 3533 and 4107 m2 g−1, representing the thus far record high specific surface area among imine-bonded COFs. This enables the activated COFs to exhibit also the record high methane uptake capacities up to 28.9 wt.% (570 cm3 g−1) at 25 °C and 200 bar among all COFs reported thus far. This work not only presents the structures of two single-crystalline COFs with exceptional microporosity but also provides an example of atom engineering to adjust permanent microporous structures for methane storage

Citation

Journal of the American Chemical Society

Volume

146

Issue

42

Pub Type

Journals

Download Paper

https://doi.org/10.1021/jacs.4c09680

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Keywords

Porous materials, Gas adsorption

Citation

Yu, B. , Tao, Y. , Yao, X. , Jin, Y. , Liu, S. , Xu, T. , Wang, H. , Wu, H. , Zhou, W. , Zhou, X. , Wang, X. , Ding, X. , Xiao, X. , Zhang, Y. and Jiang, J. (2024), Single-Crystalline 3D Covalent Organic Frameworks with Exceptionally High Specific Surface Areas and Gas Storage Capacities, Journal of the American Chemical Society, [online], https://doi.org/10.1021/jacs.4c09680, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=958470 (Accessed October 9, 2025)