Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

Abstract

Graphene oxide membranes—partially oxidized, stacked sheets of graphene1—can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution2,3,4,5,6. These materials have shown potential in a variety of applications, including water desalination and purification7,8,9, gas and ion separation10,11,12,13, biosensors14, proton conductors15, lithium-based batteries16 and super-capacitors17. Unlike the pores of carbon nanotube membranes, which have fixed sizes18,19,20, the pores of graphene oxide membranes—that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)—are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution21,22,23,24,25. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation–π interaction with the graphene sheet than Na+ has26, suggesting that other ions could be used to produce a wider range of interlayer spacings.

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Figure 1: Interlayer spacings in freestanding cation-controlled GOMs.
Figure 2: Solution adsorption of freestanding GOMs with different ions.
Figure 3: Single-ion permeation tests of GOMs supported by ceramic substrates.
Figure 4: Theoretical computations for cations between two graphene oxide sheets.

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Acknowledgements

We thank P. Ball, L. Kong, J. Liu, Z. Hou, G. Lei and H. Yang for constructive suggestions. We acknowledge support from the National Natural Science Foundation of China (grant numbers 11290164, 41430644, 21490585, 11574339, 11404361 and 21476107), the National Science Fund for Outstanding Young Scholars (number 11722548), the Key Research Program of the Chinese Academy of Sciences (grant number KJZD-EW-M03), the Deepcomp7000 and ScGrid of the Supercomputing Center, the Computer Network Information Center of the Chinese Academy of Sciences, the Special Program for Applied Research on SuperComputation of the NSFC-Guangdong Joint Fund (second phase), the Shanghai Supercomputer Center of China, and the BL16B1 and BL14W1 beamlines at the Shanghai Synchrotron Radiation Facility.

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Contributions

H.F. had the idea of controlling the interlayer spacing using ions based on cation–π interactions. H.F., M.W., W.J., J.L. and G.S. designed the experiments and simulations. L.C., G.S., J.S., B.P., G.X., B.Z., Y.W., F.B., J.W., D.L., Z.Q., G.L., J.Z. and L.Z. performed the experiments. G.S., Y.Y. and L.C. performed the simulations. G.S., L.C., H.F., J.L., W.J., M.W., G.X. and G.Z. analysed the data, G.S., L.C., H.F., W.J. and M.W. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Minghong Wu or Wanqin Jin or Jingye Li or Haiping Fang.

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The authors declare no competing financial interests.

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Reviewer Information Nature thanks R. Karnik and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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This file contains Supplementary Information sections PS1-PS12. See Contents page for more details. (PDF 2152 kb)

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Chen, L., Shi, G., Shen, J. et al. Ion sieving in graphene oxide membranes via cationic control of interlayer spacing. Nature 550, 380–383 (2017). https://doi.org/10.1038/nature24044

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