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Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange

Published

Author(s)

Riho Mikita, Tomoko Aharen, Takafumi Yamamoto, Fumitaka Takeiri, Tang Ya, Wataru Yoshimune, Koji Fujita, Suguru Yoshida, Katsuhisa Tanaka, Dmitry Batuk, Artem M. Abakumov, Craig Brown, Yoji Kobayashi, Hiroshi Kageyama

Abstract

We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x0.18). At 400 °C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3_/H-exchanged product EuTiu4+^O2.82N0.12square}0.06. When the ammonolysis temperature is increased up to 800 °C, we observed a further nitridation involving N3-/O2- exchange, yielding a fully oxidized Eu3+Ti4+O2N with GdFeO3-type distortion(Pnma) as a metastable phase, instead of pyrochlore structure structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N3- with O2- only above 600 °C and resulted in incomplete nitridation to EuTiO2.25Nd0.75^, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N3-/Ou2-) exchange at high temperatures. Hence, by using hydride-induced anion-deficient prefursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.
Citation
Journal of the American Chemical Society
Volume
138
Issue
9

Keywords

Oxynitride, perovskite, structure, diffraction

Citation

Mikita, R. , Aharen, T. , Yamamoto, T. , Takeiri, F. , Ya, T. , Yoshimune, W. , Fujita, K. , Yoshida, S. , Tanaka, K. , Batuk, D. , Abakumov, A. , Brown, C. , Kobayashi, Y. and Kageyama, H. (2016), Topochemical Nitridation with Anion Vacancy-Assisted N<sup>3-</sup>/O<sup>2-</sup> Exchange, Journal of the American Chemical Society, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=920131 (Accessed April 14, 2024)
Created March 8, 2016, Updated October 12, 2021