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Chemically stable polyarylether-based covalent organic frameworks

Nature Chemistry volume 11, pages 587–594 (2019)Cite this article

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Abstract

The development of crystalline porous materials with high chemical stability is of paramount importance for their practical application. Here, we report the synthesis of polyarylether-based covalent organic frameworks (PAE-COFs) with high crystallinity, porosity and chemical stability, including towards water, owing to the inert nature of their polyarylether-based building blocks. The PAE-COFs are synthesized through nucleophilic aromatic substitution reactions between ortho-difluoro benzene and catechol building units, which form ether linkages. The resulting materials are shown to be stable against harsh chemical environments including boiling water, strong acids and bases, and oxidation and reduction conditions. Their stability surpasses the performance of other known crystalline porous materials such as zeolites, metal–organic frameworks and covalent organic frameworks. We also demonstrate the post-synthetic functionalization of these materials with carboxyl or amino functional groups. The functionalized PAE-COFs combine porosity, high stability and recyclability. A preliminary application of these materials is demonstrated with the removal of antibiotics from water over a wide pH range.

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Fig. 1: Strategy for preparing stable porous crystalline PAE-COFs.
Fig. 2: Crystallinity and stability.
Fig. 3: Gas adsorption and separation.
Fig. 4: Study of antibiotic uptake.

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The authors declare that the data supporting the findings of this study are available within the Article and its Supplementary Information or from the corresponding author upon reasonable request.

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Acknowledgements

Q.F., V.V., S.Q. and M.X. acknowledge support from the National Natural Science Foundation of China (21571079, 21621001, 21390394, 21571076 and 21571078), the ‘111’ project (B07016 and B17020), Guangdong and Zhuhai Science and Technology Department Project (2012D0501990028), the programme for JLU Science and Technology Innovative Research Team and Sino-French joint laboratory. Q.F. and V.V. acknowledge support from the Thousand Talents programme (China).

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Authors and Affiliations

  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, China

    Xinyu Guan, Hui Li, Yunchao Ma, Ming Xue, Qianrong Fang, Valentin Valtchev & Shilun Qiu

  2. Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, DE, USA

    Yushan Yan

  3. Normandie Université, ENSICAEN, UNICAEN, CNRS, Caen, France

    Valentin Valtchev

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Contributions

Q.F., V.V., Y.Y. and S.Q. were responsible for the overall design, direction and supervision of the project. X.G. performed the experimental work. H.L. and Y.M. took SEM images and helped with the TGA and PXRD tests. M.X. was in charge of other physical measurements. All authors discussed the results and contributed to the writing of the manuscript.

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Correspondence to Qianrong Fang, Yushan Yan or Valentin Valtchev.

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Guan, X., Li, H., Ma, Y. et al. Chemically stable polyarylether-based covalent organic frameworks. Nat. Chem. 11, 587–594 (2019). https://doi.org/10.1038/s41557-019-0238-5

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