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Ultrastable ceramic-based metal–organic framework membranes with missing linkers for robust desalination

Nature Water (2024)Cite this article

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Abstract

The rational design of high-performance desalination membranes is critical to enable sustainable water treatment applications. However, conventional polymeric membranes suffer from insufficient stability especially under harsh chemical conditions. Here we show a novel robust ceramic-based UiO-66 metal–organic framework nanoporous membrane molecularly engineered with missing linkers, enabling more challenging chemically harsh desalination applications. The membranes show competitive desalination performance, which is higher than most state-of-the-art asymmetric and thin-film composite polymeric osmotic membranes. Experimental and molecular simulation results indicate that introducing missing-linker defects substantially increases water flux, allowing faster transport of water clusters with a lower energy barrier via enlarging the pore size of metal–organic framework nanochannels. Notably, the UiO-66 membranes exhibit exceptional stability compared with polymeric membranes under high oxidizing (chlorine) and alkaline conditions and promising application potential in industrial wastewater treatment. Our work provides a new rational design of robust high-performance desalination membranes for expanded water treatment applications that are not feasible by conventional polymeric membranes.

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Fig. 1: Synthesis route and morphological and chemical structural characterization of ultrathin UiO-66 membranes without and with missing linkers.
Fig. 2: The intra-crystalline defect-enhanced water permeation and desalination performance of the UiO-66 and ML-UiO-66 membranes.
Fig. 3: Thermally enhanced desalination performance and operation stability for ML-UiO-66 and commercial CTA membranes.
Fig. 4: Atomic level mechanism of defect- and heat-enhanced desalination performance for ML-UiO-66 membranes.
Fig. 5: Performance and operating stability of ML-UiO-66 and commercial CTA membranes under harsh chemical conditions.
Fig. 6: Operation performance and stability of ML-UiO-66 membrane in treatment of real alkaline industrial petrochemical wastewater via an osmotically driven process.

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All data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

Code availability

All simulation codes are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (NSFC)-Research Grants Council (RGC) Joint Program (number 52261160381, Y.D.) and NSFC General Program (number 52070033, Y.D.). The work is also partially supported by the NSFC-RGC Joint Research Scheme (project number N_HKU721/22, C.T.) from the Research Grants Council of the Hong Kong Special Administration Region, China. We also would like to express our sincere appreciations to USTC, DUT and CUHK for support.

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Authors and Affiliations

  1. School of Science and Engineering, The Chinese University of Hong Kong, Hong Kong, China

    Yingchao Dong

  2. School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao, China

    Qiang Lyu

  3. Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan

    Li-Chiang Lin

  4. Department of Chemical and Environmental Engineering, Yale University, New Haven, CT, USA

    Camille Violet & Menachem Elimelech

  5. School of Mechanical and Electrical Engineering, University of Electronic Science and Technology of China, Chengdu, China

    Bin Lin

  6. Center for Electron Microscopy, South China University of Technology, Guangzhou, China

    Yu Han

  7. Department of Civil Engineering, The University of Hong Kong, Hong Kong, China

    Chuyang Tang

  8. Department of Environmental Science and Engineering, University of Science and Technology of China, Hefei, China

    Han-Qing Yu

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Contributions

H.-Q.Y., M.E. and Y.D. supervised this project. Y.D. made the idea and contributions. Q.L. and L.-C.L. performed the computational simulations. Y.H. performed the low-dose TEM experiments. Y.D. wrote the manuscript. M.E., H.-Q.Y. and Y.D. revised the manuscript. Q.L., C.V., C.T. and B.L. made some important contributions to this work. All authors approved the manuscript.

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Correspondence to Yingchao Dong, Han-Qing Yu or Menachem Elimelech.

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Dong, Y., Lyu, Q., Lin, LC. et al. Ultrastable ceramic-based metal–organic framework membranes with missing linkers for robust desalination. Nat Water (2024). https://doi.org/10.1038/s44221-024-00218-5

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