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ZIF-62 glass foam self-supported membranes to address CH4/N2 separations

Nature Materials volume 22, pages 888–894 (2023)Cite this article

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Abstract

Membranes with ultrahigh permeance and practical selectivity could greatly decrease the cost of difficult industrial gas separations, such as CH4/N2 separation. Advanced membranes made from porous materials, such as metal–organic frameworks, can achieve a good gas separation performance, although they are typically formed on support layers or mixed with polymeric matrices, placing limitations on gas permeance. Here an amorphous glass foam, agfZIF-62, wherein a, g and f denote amorphous, glass and foam, respectively, was synthesized by a polymer-thermal-decomposition-assisted melting strategy, starting from a crystalline zeolitic imidazolate framework, ZIF-62. The thermal decomposition of incorporated low-molecular-weight polyethyleneimine evolves CO2, NH3 and H2O gases, creating a large number and variety of pores. This greatly increases pore interconnectivity but maintains the crystalline ZIF-62 ultramicropores, allowing ultrahigh gas permeance and good selectivity. A self-supported circular agfZIF-62 with a thickness of 200–330 µm and area of 8.55 cm2 was used for membrane separation. The membranes perform well, showing a CH4 permeance of 30,000–50,000 gas permeance units, approximately two orders of magnitude higher than that of other reported membranes, with good CH4/N2 selectivity (4–6).

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Fig. 1: Preparation and characterization of agfZIF-62.
Fig. 2: Formation route and mechanism of agfZIF-62.
Fig. 3: Characterization of agfZIF-62 membranes with different thicknesses.
Fig. 4: CH4/N2 separation performance of agfZIF-62 membranes.

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Data availability

The authors declare that all data supporting this study are available within the paper and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This research was supported by the National Key R&D Program of China (no. 2021YFB3802200) and the National Natural Science Foundation of China (grant nos. 21875161, 22038010, 22141001 and 22122810). M.D.G. is grateful for the financial support of the State Key Laboratory of Engines, Tianjin University.

Author information

Author notes

  1. These authors contributed equally: Zibo Yang, Youssef Belmabkhout, Lauren N. McHugh.

Authors and Affiliations

  1. State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, China

    Zibo Yang, De Ao, Yuxiu Sun, Zhihua Qiao & Chongli Zhong

  2. Applied Chemistry and Engineering Research Centre of Excellence (ACER CoE) and Technology Development Cell (TechCell), Mohammed VI Polytechnic University, Ben Guerir, Morocco

    Youssef Belmabkhout

  3. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Lauren N. McHugh & Thomas D. Bennett

  4. Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, China

    Shichun Li

  5. State Key Laboratory of Engines, School of Mechanical Engineering, Tianjin University, Tianjin, China

    Michael D. Guiver

  6. National Industry-Education Platform of Energy Storage, Tianjin University, Tianjin, China

    Michael D. Guiver

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Contributions

Z.Y., Z.Q. and S.L. fabricated the membranes and conducted the characterization. C.Z., Z.Q., M.D.G., T.D.B., Y.B., L.N.M., S.L., D.A. and Y.S. helped with experimental design, the membrane formation mechanism and data analyses. Z.Q., Z.Y., C.Z., M.D.G., T.D.B., Y.B. and L.N.M. wrote the paper.

Corresponding authors

Correspondence to Zhihua Qiao, Michael D. Guiver or Chongli Zhong.

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Nature Materials thanks Weishen Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–43, Tables 1–10, Materials and refs. 1–22.

Source data

Source Data Fig. 1

Source data for X-ray scattering factors plotted in Fig. 1b, pair distribution functions plotted in Fig. 1c, pore size distributions plotted in Fig. 1d,e, XANES spectra plotted in Fig. 1f and EXAFS spectra plotted in Fig. 1g.

Source Data Fig. 2

Source data for DSC data plotted in Fig. 2b, TGA-MS data plotted in Fig. 2c–e, pore size distributions plotted in Fig. 2f and kinetic CO2 gas adsorption plotted in Fig. 2g.

Source Data Fig. 4

Source data for pure gas permeance and selectivity data plotted in Fig. 4a and literature survey data plotted in Fig. 4b.

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Yang, Z., Belmabkhout, Y., McHugh, L.N. et al. ZIF-62 glass foam self-supported membranes to address CH4/N2 separations. Nat. Mater. 22, 888–894 (2023). https://doi.org/10.1038/s41563-023-01545-w

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