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

Nature Energy volume 2, pages 786–794 (2017)Cite this article

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Abstract

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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Fig. 1: Electron microscopy images showing nanocrystalline, dense TiN x membranes formed over the porous alumina support.
Fig. 2: Hydrogen permeability of TiN x membranes at temperatures between ambient and 500 °C.
Fig. 3: Enhanced hydrogen permeability of nanocrystalline TiN x membranes with reducing grain sizes.
Fig. 4: Hydrogen solubility in TiN x films.
Fig. 5: Identification of mobile hydrogen species in TiN0.7 membranes.
Fig. 6: DFT calculations for hydrogen adsorption on the TiN surface.

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Acknowledgements

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’).

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Authors and Affiliations

  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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Contributions

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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Correspondence to Yoshitaka Aoki.

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Kura, C., Kunisada, Y., Tsuji, E. et al. Hydrogen separation by nanocrystalline titanium nitride membranes with high hydride ion conductivity. Nat Energy 2, 786–794 (2017). https://doi.org/10.1038/s41560-017-0002-2

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