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Microporous membranes comprising conjugated polymers with rigid backbones enable ultrafast organic-solvent nanofiltration

Abstract

Conventional technology for the purification of organic solvents requires massive energy consumption, and to reduce such expending calls for efficient filtration membranes capable of high retention of large molecular solutes and high permeance for solvents. Herein, we report a surface-initiated polymerization strategy through C–C coupling reactions for preparing conjugated microporous polymer (CMP) membranes. The backbone of the membranes consists of all-rigid conjugated systems and shows high resistance to organic solvents. We show that 42-nm-thick CMP membranes supported on polyacrylonitrile substrates provide excellent retention of solutes and broad-spectrum nanofiltration in both non-polar hexane and polar methanol, the permeance for which reaches 32 and 22 l m−2 h−1 bar−1, respectively. Both experiments and simulations suggest that the performance of CMP membranes originates from substantially open and interconnected voids formed in the highly rigid networks.

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Fig. 1: Preparation and characterization of all-conjugated CMP membranes with various dibromobenzene monomers, and investigation of their mechanical properties.
Fig. 2: Nanofiltration performances of p-CMP, m-CMP and o-CMP membranes.
Fig. 3: Structural analysis of amorphous polymer models.

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Acknowledgements

This work was supported by the National Key Basic Research Program of China (2014CB931801 and 2016YFA0200700 to Z.T.), National Natural Science Foundation of China (51472054 to L.L.; 21475029, 91427302 and 21721002 to Z.T.; and 11422215 and 11672079 to X.S.), Frontier Science Key Project of the Chinese Academy of Sciences (QYZDJ-SSW-SLH038 to Z.T.), Instrument Developing Project of the Chinese Academy of Sciences (YZ201311 to Z.T.), CAS-CSIRO Cooperative Research Program (GJHZ1503 to Z.T.) and Strategic Priority Research Program of the Chinese Academy of Sciences (XDA09040100 to Z.T.), K. C. Wong Education Foundation (to Z.T.), and Youth Innovation Promotion Association CAS (to L.L.). We thank H. Sun for discussion on PFQNM.

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Contributions

B.L., L.L. and Z.T. conceived the project, analysed the data and wrote the paper. H.W. and X.S. contributed to preparation of the manuscript. B.L. prepared the samples and performed the nanofiltration evaluation. X.H., Z.A.G., N.A.K., H.S. and A.M.K. characterized the samples. X.S., H.W. and B.S. performed the density functional theory calculations and simulations. All authors discussed the results and commented on the manuscript.

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Correspondence to Lianshan Li or Zhiyong Tang.

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Supplementary characterization and simulation details, Supplementary Figures 1–31, Supplementary Tables 1–7

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Liang, B., Wang, H., Shi, X. et al. Microporous membranes comprising conjugated polymers with rigid backbones enable ultrafast organic-solvent nanofiltration. Nature Chem 10, 961–967 (2018). https://doi.org/10.1038/s41557-018-0093-9

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