Suppression of H–/O2–exchange by incorporated nitride anions in the perovskite lattice

Year: 2017 DOI: 10.1016/j.jssc.2017.08.025

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Fumitaka Takeiri, Takeshi Yajima, Takafumi Yamamoto, Yoji Kobayashi, Toshiaki Matsui, James Hester, Hiroshi Kageyama.   Journal of Solid State Chemistry, 2017, 256, 33-37.


We investigate the low temperature anion exchange behavior of hydride and oxide in perovskite oxynitrides. CaH2 reduction of (Sr1–xLax)Ti(O3–xNx) (0<x ≤ 1) resulted in the selective anion exchange of hydride for oxide rather than nitride, yielding the oxyhydride-nitride  (Sr1–xLax)Ti(O3–x–yHyNx). However, the exchange of hydride is drastically suppressed with increasing nitrogen content and is completely impeded when the nitride content reaches 10% of the anionic site. This implies that the N3– anions in the oxide lattice play a crucial role in lowering diffusion of O2–(and H). The present study indicates the necessity to consider kinetic aspects when manipulating anion compositions, in particular in a mixed anion system with a small amount of anion vacancies.