An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity

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Abstract

In oxides, the substitution of non-oxide anions (F,S2−,N3− and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements1,2,3,4,5 or as layered cobalt oxides with unusually low oxidation states6,7. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO3, as an O2−/H solid solution with hydride concentrations up to 20% of the anion sites. BaTiO3−xHx is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

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Figure 1: BaTiO3 and its oxyhydride.
Figure 2: Characterization using diffraction (X-ray, neutron and electron) and 1H NMR.
Figure 3: Mass spectrometry of gaseous species during deuteride exchange.
Figure 4: Excerpts from neutron diffraction patterns of BaTiO2.4H0.6 before and after deuteration.

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Acknowledgements

We thank S. Mitsuoka, H. Ohkubo, F. Takeiri, K. Ohoyama, W. Paulus, M. Takata and T. Nishiyama for assistance with various aspects. This work was supported by the Japan Society for the Promotion of Science (JSPS) through its ‘Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) Program’; Grant-in-Aid for Science Research in the Priority Areas (No. 19052004); and Grant-in-Aid for Scientific Research (A) (No. 22245009) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. Y.T. and A.K. were supported by JSPS Research Fellowships for Young Scientists.

Author information

H.K. designed the study, with advice from M.T. The initial synthesis was performed by Y.T., M.M. and A.K., with T.S., T.Y. and M.O. optimizing conditions. T.S., T.Y., A.K. and Y.T. obtained the X-ray and neutron diffraction data with assistance from J.e.K. and N.T., and electron diffraction patterns were obtained by Y. Kusano. The presence of hydride was proposed by O.J.H. and T.R. and confirmed by O.J.H., Z.L. and Y.T. Rietveld refinements were initially performed by Y.T. and then finalized by O.J.H. NMR spectra were measured by Y.N. and Y. Mogami. with advice from K.T. Magnetic susceptibility was measured by Y.T. and M.M. The deuterium exchange reactions were conceived by S.H. and Y. Kobayashi, and performed by T.S.; the acid digestion analysis was performed by Y. Kobayashi. A.F., Y. Matsushita, M.I. and K.Y. also provided assistance with various aspects. All authors discussed the results; Y. Kobayashi wrote the manuscript, with discussions mainly with H.K., O.J.H. and M.T.

Correspondence to Hiroshi Kageyama.

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Kobayashi, Y., Hernandez, O., Sakaguchi, T. et al. An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity. Nature Mater 11, 507–511 (2012) doi:10.1038/nmat3302

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