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Atomically thin micas as proton-conducting membranes

Nature Nanotechnology volume 14, pages 962–966 (2019)Cite this article

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Abstract

Monolayers of graphene and hexagonal boron nitride (hBN) are highly permeable to thermal protons1,2. For thicker two-dimensional (2D) materials, proton conductivity diminishes exponentially, so that, for example, monolayer MoS2 that is just three atoms thick is completely impermeable to protons1. This seemed to suggest that only one-atom-thick crystals could be used as proton-conducting membranes. Here, we show that few-layer micas that are rather thick on the atomic scale become excellent proton conductors if native cations are ion-exchanged for protons. Their areal conductivity exceeds that of graphene and hBN by one to two orders of magnitude. Importantly, ion-exchanged 2D micas exhibit this high conductivity inside the infamous gap for proton-conducting materials3, which extends from ∼100 °C to 500 °C. Areal conductivity of proton-exchanged monolayer micas can reach above 100 S cm−2 at 500 °C, well above the current requirements for the industry roadmap4. We attribute the fast proton permeation to ~5-Å-wide tubular channels that perforate micas’ crystal structure, which, after ion exchange, contain only hydroxyl groups inside. Our work indicates that there could be other 2D crystals5 with similar nanometre-scale channels, which could help close the materials gap in proton-conducting applications.

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Fig. 1: STEM characterization of ion-exchanged micas.
Fig. 2: Proton transport through 2D micas studied using Nafion-coated devices.
Fig. 3: Proton transport through micas measured using Pt-coated devices.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

The work was supported by the Lloyd’s Register Foundation, the Engineering and Physical Sciences Research Council (EPSRC)—EP/N010345/1, EP/M010619/1 and EP/P009050/1, the European Research Council, the Graphene Flagship and the Royal Society. M.L.-H. acknowledges a Leverhulme Early Career Fellowship, G.-P.H. acknowledges a Marie Curie International Incoming Fellowship, and L.M. acknowledges the EPSRC NOWNano programme for funding. Y.Z. acknowledges the assistance of Eric Prestat in TEM specimen preparation. Computational resources were provided by the TUBITAK ULAKBIM High Performance and Grid Computing Center (TR-Grid e-Infrastructure).

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Author notes

  1. These authors contributed equally: L. Mogg, G.-P. Hao, S. Zhang.

Authors and Affiliations

  1. National Graphene Institute, The University of Manchester, Manchester, UK

    L. Mogg, G.-P. Hao, S. Zhang, A. K. Geim & M. Lozada-Hidalgo

  2. School of Physics and Astronomy, The University of Manchester, Manchester, UK

    L. Mogg, A. K. Geim & M. Lozada-Hidalgo

  3. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, China

    G.-P. Hao

  4. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    S. Zhang

  5. Departement Fysica, Universiteit Antwerpen, Antwerp, Belgium

    C. Bacaksiz & F. M. Peeters

  6. School of Materials, The University of Manchester, Manchester, UK

    Y.-C. Zou & S. J. Haigh

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Contributions

M.L.-H. and A.K.G. designed and directed the project. L.M. and G.-P.H. fabricated devices, performed measurements and carried out data analysis with help from S.Z. C.B. and F.M.P. provided theoretical support. Y.Z. and S.J.H. performed electron microscopy imaging and analysis. L.M., A.K.G. and M.L.-H. wrote the manuscript. All authors contributed to discussions.

Corresponding authors

Correspondence to G.-P. Hao, A. K. Geim or M. Lozada-Hidalgo.

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The authors declare no competing interests.

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Peer review information: Nature Nanotechnology thanks Sang Soo Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

supplementary Information

Supplementary Figs. 1–8, methods, discussion and refs. 1–37.

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Mogg, L., Hao, GP., Zhang, S. et al. Atomically thin micas as proton-conducting membranes. Nat. Nanotechnol. 14, 962–966 (2019). https://doi.org/10.1038/s41565-019-0536-5

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