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

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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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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