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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Dikin, D. A. et al. Preparation and characterization of graphene oxide paper. Nature 448, 457–460 (2007)
Joshi, R. K. et al. Precise and ultrafast molecular sieving through graphene oxide membranes. Science 343, 752–754 (2014)
Elimelech, M. & Phillip, W. A. The future of seawater desalination: energy, technology, and the environment. Science 333, 712–717 (2011)
Gin, D. L. & Noble, R. D. Designing the next generation of chemical separation membranes. Science 332, 674–676 (2011)
Han, Y., Xu, Z. & Gao, C. Ultrathin graphene nanofiltration membrane for water purification. Adv. Funct. Mater. 23, 3693–3700 (2013)
Liu, G. P., Jin, W. Q. & Xu, N. P. Graphene-based membranes. Chem. Soc. Rev. 44, 5016–5030 (2015)
Sun, P. et al. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions. ACS Nano 8, 850–859 (2014)
Surwade, S. P. et al. Water desalination using nanoporous single-layer graphene. Nat. Nanotechnol. 10, 459–464 (2015)
Lin, L. C. & Grossman, J. C. Atomistic understandings of reduced graphene oxide as an ultrathin-film nanoporous membrane for separations. Nat. Commun. 6, 8335 (2015)
Celebi, K. et al. Ultimate permeation across atomically thin porous graphene. Science 344, 289–292 (2014)
Kim, H. W. et al. Selective gas transport through few-layered graphene and graphene oxide membranes. Science 342, 91–95 (2013)
Li, H. et al. Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation. Science 342, 95–98 (2013)
Koenig, S. P., Wang, L., Pellegrino, J. & Bunch, J. S. Selective molecular sieving through porous graphene. Nat. Nanotechnol. 7, 728–732 (2012)
Liu, Y. X., Dong, X. C. & Chen, P. Biological and chemical sensors based on graphene materials. Chem. Soc. Rev. 41, 2283–2307 (2012)
Lozada-Hidalgo, M. et al. Sieving hydrogen isotopes through two-dimensional crystals. Science 351, 68–70 (2016)
Yao, F. et al. Diffusion mechanism of lithium ion through basal plane of layered graphene. J. Am. Chem. Soc. 134, 8646–8654 (2012)
Wang, H. L. et al. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability. Nano Lett. 11, 2644–2647 (2011)
De Volder, M. F. L ., Tawfick, S. H ., Baughman, R. H. & Hart, A. J. Carbon nanotubes: present and future commercial applications. Science 339, 535–539 (2013)
Koga, K., Gao, G. T., Tanaka, H. & Zeng, X. C. Formation of ordered ice nanotubes inside carbon nanotubes. Nature 412, 802–805 (2001)
Liu, J., Shi, G. S., Guo, P., Yang, J. R. & Fang, H. P. Blockage of water flow in carbon nanotubes by ions due to interactions between cations and aromatic rings. Phys. Rev. Lett. 115, 164502 (2015)
Huang, H. B. et al. Ultrafast viscous water flow through nanostrand-channelled graphene oxide membranes. Nat. Commun. 4, 2979 (2013)
Goh, K. et al. All-carbon nanoarchitectures as high-performance separation membranes with superior stability. Adv. Funct. Mater. 25, 7348–7359 (2015)
Hung, W. S. et al. Cross-linking with diamine monomers to prepare composite graphene oxide-framework membranes with varying d-spacing. Chem. Mater. 26, 2983–2990 (2014)
Su, Y. et al. Impermeable barrier films and protective coatings based on reduced graphene oxide. Nat. Commun. 5, 4843 (2014)
Sun, P., Wang, K. & Zhu, H. Recent developments in graphene-based membranes: structure, mass-transport mechanism and potential applications. Adv. Mater. 28, 2287–2310 (2016)
Shi, G. S. et al. Ion enrichment on the hydrophobic carbon-based surface in aqueous salt solutions due to cation-π interactions. Sci. Rep 3, 3436 (2013)
Abraham, J. et al. Tunable sieving of ions using graphene oxide membranes. Nat. Nanotechnol. 12, 546–550 (2017)
Raidongia, K. & Huang, J. Nanofluidic ion transport through reconstructed layered materials. J. Am. Chem. Soc. 134, 16528–16531 (2012)
Shen, J. et al. Membranes with fast and selective gas-transport channels of laminar graphene oxide for efficient CO2 capture. Angew. Chem. Int. Ed. 54, 578–582 (2015)
Huang, K. et al. A graphene oxide membrane with highly selective molecular separation of aqueous organic solution. Angew. Chem. Int. Ed. 53, 6929–6932 (2014)
Mahadevi, A. S. & Sastry, G. N. Cation-π interaction: its role and relevance in chemistry, biology, and material science. Chem. Rev. 113, 2100–2138 (2013)
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.
The authors declare no competing financial interests.
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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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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