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Advanced carbon molecular sieve membranes derived from molecularly engineered cross-linkable copolyimide for gas separations

Nature Materials volume 22, pages 109–116 (2023)Cite this article

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Abstract

Carbon molecular sieve (CMS) membranes with precise molecular discrimination ability and facile scalability are attractive next-generation membranes for large-scale, energy-efficient gas separations. Here, structurally engineered CMS membranes derived from a tailor-made cross-linkable copolyimide with kinked structure are reported. We demonstrate that combining two features, kinked backbones and cross-linkable backbones, to engineer polyimide precursors while controlling pyrolysis conditions allows the creation of CMS membranes with improved gas separation performance. Our results indicate that the CMS membranes provide a versatile platform for a broad spectrum of challenging gas separations. The gas transport properties of the resulting CMS membranes are interpreted in terms of a model reflecting both molecular sieving Langmuir domains and a disordered continuous phase, thereby providing insight into structure evolution from the cross-linkable polyimide precursor to a final CMS membrane. With this understanding of CMS membrane structure and separation performance, these systems are promising for environmentally friendly gas separations.

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Fig. 1: Preparation and characterization of cross-linkable copolyimide precursor with kinked structure for CMS membrane.
Fig. 2: Characterizations of CMS membranes.
Fig. 3: Gas transport properties of CMS membranes.
Fig. 4: Comparison and stability of mixed-gas separation performance.

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Data availability

The data that support the findings in this study are available within the paper and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

W.J.K. acknowledges the support by the Roberto C. Goizueta Chair fund and the US Department of Energy grant (no. DE‐FG02‐04ER15510), and we acknowledge the Specialty Separations Center at Georgia Institute of Technology for assistance in equipment resource funds.

Author information

Authors and Affiliations

  1. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Zhongyun Liu, Wulin Qiu, Wenying Quan & William J. Koros

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  1. Zhongyun Liu
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  4. William J. Koros
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Contributions

Z.L., W. Qiu and W.J.K. conceived and designed the project. Z.L. prepared the CMS membranes and performed the membrane permeation and sorption tests. Z.L. and W. Qiu synthesized the copolyimide precursors. W. Quan carried out the X-ray diffraction measurement and pore size distribution test by CO2 physisorption. Z.L. conducted the gas diffusion analysis using the dual sorption and transport models. Z.L. W. Qiu and W.J.K. discussed the findings in this paper. Z.L. and W.J.K. drafted the paper, and all authors contributed to revising the paper.

Corresponding author

Correspondence to William J. Koros.

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Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–8, Figs. 1–23, Tables 1–24 and References 1–95.

Source data

Source Data Fig. 1

Source Data for NMR data plotted in Fig. 1b, TGA data plotted in Fig. 1c and ATR–FTIR data plotted in Fig. 1d.

Source Data Fig. 2

Source Data for Raman spectra data plotted in Fig. 2d, WAXRD data plotted in Fig. 2e and pore sizes plotted in Fig. 2f.

Source Data Fig. 3

Source Data for pure gas selectivity data plotted in Fig. 3a–c, and solubility/diffusivity data plotted in Fig. 3d–f.

Source Data Fig. 4

Source data for mixed-gas selectivity data plotted in Fig. 4a–d.

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Liu, Z., Qiu, W., Quan, W. et al. Advanced carbon molecular sieve membranes derived from molecularly engineered cross-linkable copolyimide for gas separations. Nat. Mater. 22, 109–116 (2023). https://doi.org/10.1038/s41563-022-01426-8

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