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Metal-induced ordered microporous polymers for fabricating large-area gas separation membranes

Nature Materials volume 18, pages 163–168 (2019)Cite this article

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Abstract

Metal-induced ordered microporous polymers (MMPs), a class of porous polymer, are synthesized from amine-bearing polymers, small organic linkers and divalent metal ions using a polymer-directed chemical synthesis process. Specifically, small organic linkers first coordinate to metal ions, with the resulting unit cells then self-assembling along the extension of polymer chains to construct three-dimensional frameworks. The MMPs demonstrate good controllability of crystal and framework size, as well as hydrolytic stability. MMP dispersions were coated on a modified polysulfone substrate to fabricate MMP/mPSf membranes with an ultrathin selective layer (below 50 nm) and surface areas of >100 cm2. The MMPs are readily fabricated into defect-free thin selective-layered membranes with high CO2 permeance (3,000 GPU) and stable CO2/N2 selectivity (78) under both humid and dry gas feed conditions, demonstrating promising CO2 membrane separation performance. This synthetic methodology could be extended to other polymers, potentially enabling facile synthesis of membrane materials.

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Fig. 1: Construction of MMP frameworks using the PDCS process.
Fig. 2: Representation of the crystal structures and morphological images of MMPs.
Fig. 3: Pore diameter distribution, thermogravimetry curves, dried gas sorption capacities and humidified gas sorption capacities of the MMPs.
Fig. 4: Membrane optical images, surface SEM images, cross-sectional SEM images and mixed-gas CO2/N2 separation performance of the MMP/mPSf membranes.

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All the data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This research is supported by the National Key R&D Program of China (no. 2017YFB0603400) and the Natural Science Foundation of China (no. 21436009).

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Author notes

  1. These authors contributed equally: Zhihua Qiao and Song Zhao

Authors and Affiliations

  1. Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Zhihua Qiao, Song Zhao, Menglong Sheng, Jixiao Wang, Shichang Wang & Zhi Wang

  2. State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin, China

    Zhihua Qiao & Chongli Zhong

  3. Tianjin Key Laboratory of Membrane Science and Desalination Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin, China

    Zhihua Qiao, Song Zhao, Menglong Sheng, Jixiao Wang, Shichang Wang & Zhi Wang

  4. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China

    Menglong Sheng, Jixiao Wang, Zhi Wang & Michael D. Guiver

  5. State Key Laboratory of Engines, Tianjin University, Tianjin, China

    Michael D. Guiver

Authors
  1. Zhihua Qiao
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  6. Zhi Wang
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Contributions

Z.Q., S.Z. and M.S. fabricated the materials and conducted the characterization. Z.W., C.Z. and M.D.G. carried out experimental design. J.W. and S.W. performed data analysis. Z.Q., S.Z., Z.W., C.Z. and M.D.G. wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Zhi Wang, Chongli Zhong or Michael D. Guiver.

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Supplementary Information

Supplementary Sections 1–8, Supplementary Figures 1–19, Supplementary Tables 1–2, Supplementary References 1–13

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Qiao, Z., Zhao, S., Sheng, M. et al. Metal-induced ordered microporous polymers for fabricating large-area gas separation membranes. Nature Mater 18, 163–168 (2019). https://doi.org/10.1038/s41563-018-0221-3

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