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Interfacial self-organization of large-area mixed-dimensional polyamide membranes for rapid aqueous nanofiltration

Nature Water volume 2, pages 1238–1248 (2024)Cite this article

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Abstract

Mixed-dimensional membranes are promising candidates for efficient water purification. Integrating a conventional flat two-dimensional (2D) membrane with structures of different dimensionalities is expected to create additional water transport sites. However, organizing the membrane building blocks into a mixed-dimensional hierarchy capable of facilitating rapid water transfer, while also enabling large-scale, cost-effective manufacturing, remains a significant challenge. Here we report the discovery of rapid self-organization of large-area mixed-dimensional polyamide membranes with an intriguing hierarchical structure consisting of one-dimensional nanotubes on a 2D nanofilm under room temperature using only two types of small molecules at an oil–water interface. The resulting architecture with one-dimensional nanotubes on a 2D nanofilm offers a substantially increased available area for water transport per projected area, enabling energy-efficient nanofiltration membranes with outstanding water–salt separation performance that well surpasses most state of the art membranes. Control experiments, coupled with molecular dynamic simulations, reveal that the two types of molecular monomers self-organize into a 2D nanopore network during the incipient reaction stage and then capillarity within these nanopores drives the upwards polymerization of these nanotubes. Our findings provide valuable insights into how the interplay of interfacial physical and chemical interactions organizes molecular seeds into large-scale, complex hierarchical nanostructures under ambient conditions. This opens new opportunities for developing scalable, mixed-dimensional water purification membranes.

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Fig. 1: Schematic illustration of the mixed-dimensional polyamide membrane with NoN structure, juxtaposed with the flat 2D polyamide membrane for comparison.
Fig. 2: External and internal structure characterization of the resulting mixed-dimensional polyamide membrane.
Fig. 3: Simulation of the NoN formation process and structural manipulation.
Fig. 4: Surface morphology evolution with reaction time and free volume analysis by PALS.
Fig. 5: Separation performance comparison and structure–property relationship diagram.

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The data supporting the findings of this study are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank H. Jia, W. Li, X. F. Li, J. D. Li, L. R. Liang, Y. N. Li, Y. Li and J. F. Xu for technical assistance. This work was supported by the National Natural Science Foundation of China (grant nos. 51978466 (to C.W.) and 52170047 (to C.W.)), National Key R&D Programme of China (2021YFC330010003-2 to C.W.) and the research funding provided by Cangzhou Institute of Tiangong University (grant no. TGCYY-F-0102 to C.W.). C.W., S.-H.L., B.X., J.S., L.S. and X.L. are inventors on patent application 201910669603.3 submitted by Tiangong University, which covers polyamide membranes with nanotube surface. We thank the Analytical and Testing Centre of Tiangong University for membrane structure analysis (for example, XPS, FESEM and TEM) work. We also thank Z. Jiang from Queen Mary University of London for a productive suggestion.

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Authors and Affiliations

  1. State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Separation Membranes, School of Material Science and Engineering, Tiangong University, Tianjin, P. R. China

    Si-Hua Liu, Le Shi, Bai Xue, Jingguo She, Ziping Song, Xiaolong Lu & Chunrui Wu

  2. School of Chemical Engineering and Technology, Tiangong University, Tianjin, P. R. China

    Si-Hua Liu & Chunrui Wu

  3. Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, P. R. China

    Wenxiong Shi

  4. Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan

    Wei-Song Hung

  5. Institute for Sustainable Industries and Liveable Cities, Victoria University, Melbourne, Victoria, Australia

    Stephen Gray

  6. R&D Center for Membrane Technology, Department of Chemical Engineering, Chung Yuan University, Taoyuan, Taiwan

    Kueir-Rarn Lee

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  1. Si-Hua Liu
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Contributions

S.-H.L., C.W. and X.L. designed the experiments and analysed the data. S.-H.L. performed the experiments. W.S. conducted the simulation analysis. W.-S.H. and K.-R.L. performed the PAS analysis. S.-H.L., L.S., B.X., J.S. and Z.S. performed the SEM tests. S.G. contributed to data analysis. All authors discussed the results and wrote the paper.

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Correspondence to Chunrui Wu.

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Nature Water thanks Jiangnan Shen, Lin Zhang and Yatao Zhang for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–24, Discussion and Tables 1–2.

Supplementary Video 1

Top view of simulation of nanopore network formation during the initial reaction stage of interfacial polycondensation.

Supplementary Video 2

Side view of simulation of nanopore network formation during the initial reaction stage of interfacial polycondensation.

Supplementary Video 3

Capillary flow process in PPA nanopore with a diameter of 9 nm and nanopore height of 9 nm.

Supplementary Video 4

Capillary flow process in PPA nanopore with a diameter of 9 nm and nanopore height of 18 nm.

Supplementary Video 5

Capillary flow process in PPA nanopore with a diameter of 18 nm and nanopore height of 9 nm.

Supplementary Video 6

Capillary flow process in PPA nanopore with a diameter of 30 nm and nanopore height of 9 nm.

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Liu, SH., Shi, W., Hung, WS. et al. Interfacial self-organization of large-area mixed-dimensional polyamide membranes for rapid aqueous nanofiltration. Nat Water 2, 1238–1248 (2024). https://doi.org/10.1038/s44221-024-00348-w

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