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Chemically stable polyarylether-based covalent organic frameworks

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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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).

Author information

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.

Competing interests

The authors declare no competing interests.

Correspondence to Qianrong Fang or Yushan Yan or Valentin Valtchev.

Supplementary information

  1. Supplementary Information

    Supplementary methods, supplementary synthetic procedures and supplementary experimental data

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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.