Hydrogen separation by nanocrystalline titanium nitride membranes with high hydride ion conductivity

  • Nature Energyvolume 2pages786794 (2017)
  • doi:10.1038/s41560-017-0002-2
  • Download Citation


The production of pure hydrogen for use in energy applications and related industries often relies on the permeation of hydrogen through palladium-based membranes. However, the scarcity of Pd reserves necessitates the development of affordable alternatives with high hydrogen permeability. Here we report room-temperature hydrogen permeability of titanium nitrides (widely used as tough and inert coating materials) enabled by mixed hydride ion–electron conductivity. Combined spectroscopic, permeability and microgravimetric measurements reveal that nanocrystalline TiN x membranes feature enhanced grain-boundary diffusion of hydride anions associated with interfacial Ti cations on nanograins. Since the corresponding activation energies are very low (<10 kJ mol–1), these membranes yield a considerably higher room-temperature hydrogen flux than Pd membranes of equivalent thickness. Overall, the current study establishes general guidelines for developing hydride ion transport membranes based on a simple transition metal nitride for hydrogen purification, membrane reactors and other applications.

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This work was supported by the PRESTO `Creation of Innovative Core Technology for Manufacture and Use of Energy Carriers from Renewable Energy’ project, funded by Japan Science and Technology Agency, Japan and the `Nanotechnology Platform’ programme of the MEXT Japan. C.K. was supported by the MEXT Japan through the programme for Leading Graduate Schools (Hokkaido University `Ambitious Leader’s Program’).

Author information


  1. Graduate School of Chemical Sciences and Engineering, Hokkaido University, N13W8 Kita-ku, Sapporo, 060-8628, Japan

    • Chiharu Kura
  2. Faculty of Engineering, Hokkaido University, N13W8 Kita-ku, Sapporo, 060-8628, Japan

    • Yuji Kunisada
    • , Chunyu Zhu
    • , Hiroki Habazaki
    •  & Yoshitaka Aoki
  3. Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Tottori, 680-8552, Japan

    • Etsushi Tsuji
  4. Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Sendai, 980-8577, Japan

    • Shinji Nagata
  5. Institute of Physical Chemistry, RWTH Aachen University and JARA-FIT, 52056, Aachen, Germany

    • Michael P. Müller
    •  & Roger A. De Souza
  6. JST-PRESTO, 4-1-8 Honcho, Kawaguchi, 332-0012, Japan

    • Yoshitaka Aoki


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Y.A. designed the present work; Y.A. and C.K. prepared the manuscript; C.K. performed the membrane fabrications, electron microscopy, FT-IR, QCM and NMR measurements and hydrogen permeation tests with supervision from Y.A., and discussed the data with Y.A., E.T., C.Z. and H.H.; SIMS measurements were performed by C.K., R.S. and M.M.; C.K. and Y.K. conducted the density functional theory calculations; Y.A. and S.N. performed Rutherford back scattering measurements.

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The authors declare no competing financial interests.

Corresponding author

Correspondence to Yoshitaka Aoki.

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  1. Supplementary Information

    Supplementary Figures 1–10, Supplementary Tables 1–4 and Supplementary References