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Efficient metal ion sieving in rectifying subnanochannels enabled by metal–organic frameworks

Abstract

Biological ion channels have remarkable ion selectivity, permeability and rectification properties, but it is challenging to develop artificial analogues. Here, we report a metal–organic framework-based subnanochannel (MOFSNC) with heterogeneous structure and surface chemistry to achieve these properties. The asymmetrically structured MOFSNC can rapidly conduct K+, Na+ and Li+ in the subnanometre-to-nanometre channel direction, with conductivities up to three orders of magnitude higher than those of Ca2+ and Mg2+, equivalent to a mono/divalent ion selectivity of 103. Moreover, by varying the pH from 3 to 8 the ion selectivity can be tuned further by a factor of 102 to 104. Theoretical simulations indicate that ion–carboxyl interactions substantially reduce the energy barrier for monovalent cations to pass through the MOFSNC, and thus lead to ultrahigh ion selectivity. These findings suggest ways to develop ion selective devices for efficient ion separation, energy reservation and power generation.

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Fig. 1: Fabrication of Asy-MOFSNC using a facilitated interfacial growth strategy, MOF = UiO-66-(COOH)2.
Fig. 2: Rectifying, ultraselective monovalent metal ion transport in Asy-UiO-66-(COOH)2-SNC.
Fig. 3: pH-dependent mono/divalent ion conductance and selectivity in the Asy-UiO-66-(COOH)2-SNC.
Fig. 4: Concentration-dependent ion conductance and selectivity, and binary ion selectivity of the Asy-UiO-66-(COOH)2-SNC.
Fig. 5: Ion sieving mechanism in the UiO-66-(COOH)2-SNC.
Fig. 6: Energy barriers, dehydration effects and ion‒framework interactions of K+ and Mg2+ in the UiO-66-(COOH)2-SNC.

Data availability

All relevant source data within the article and the Supplementary Information are available for download through figshare (https://doi.org/10.6084/m9.figshare.11678046). Additional data related to the paper may be requested from the authors.

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Acknowledgements

This project is supported by the Australian Research Council (grant nos. DP180100298, DE170100006, DP170102964 and DP180102890). J.L. thanks the Chinese Scholarship Council for a PhD scholarship. J.Z.L. thanks the start-up fund from The University of Melbourne. G.J. thanks the National Natural Science Foundation of China (grant no. 21905215) for support. B.D.F.’s work is supported by the Center for Materials for Water and Energy Systems (M-WET), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0019272. We acknowledge assistance from B.Qian and X.Chen in the experiments and use of the facilities and assistance from Y.Chen and X.Fang in the Monash Center for Electron Microscopy. We also acknowledge the assistance of resources and services from the National Computational Infrastructure, which is supported by the Australian Government. We acknowledge the assistance of P. Cook in editing the manuscript.

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H.Z. conceived the project concept. H.Z. and H.W. designed the detailed project scope. H.Z. and J.L. designed the experiments. J.L. and H.Z. performed the sample preparation. J.L. conducted sample measurements and characterizations. G.J. conducted the MD simulations under the guidance of J.Z.L. J.H., X.L., X.H. and Y.H. helped conduct the SEM, PXRD and Zeta potential measurements. C.D.E. carried out the XPS analysis. C.S. and Q.L. did the DFT calculations. J.L. and H.Z. analysed the data and wrote the paper. B.D.F., A.J.H., A.W.T., M.R.H., X.Z., L.J. and H.W. discussed the results and commented on the manuscript. H.Z., J.L., G.J., J.Z.L. and H.W. revised the manuscript. H.Z. and H.W. supervised the work.

Corresponding authors

Correspondence to Huacheng Zhang or Gengping Jiang or Huanting Wang.

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H.Z., H.W., X.L., J.L., B.D.F. and A.J.H. are inventors on an international patent application related to this work filed by Monash University (application no. PCT/AU2018/051341). All other authors have no competing interests.

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Supplementary materials and methods, Notes 1 and 2, Figs. 1–16, Tables 1–7 and refs. 1–56.

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Lu, J., Zhang, H., Hou, J. et al. Efficient metal ion sieving in rectifying subnanochannels enabled by metal–organic frameworks. Nat. Mater. 19, 767–774 (2020). https://doi.org/10.1038/s41563-020-0634-7

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