Takeiri Fumitaka, Aidzu Kohei, Yajima Takeshi, Matsui Toshiaki, Yamamoto Takafumi, Kobayashi Yoji, Hester James, Kageyama Hiroshi
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University , Nishikyo-ku, Kyoto 615-8510, Japan.
Institute for Solid State Physics, The University of Tokyo , Kashiwa, Chiba 277-8581, Japan.
Inorg Chem. 2017 Nov 6;56(21):13035-13040. doi: 10.1021/acs.inorgchem.7b01845.
We investigated topochemical anion exchange reactions for a Sc-substituted SrTiO perovskite, Sr(TiSc)O□ (y ≤ 0.1), using CaH. It was found that the initial introduction of a small amount of anion vacancies (y/2) is crucial to enhance the anion (H/O) exchangeability. For example, hydride reduction of Sr(TiSc)O yielded the oxyhydride SrTiScOH in which the hydride concentration is increased by 33% with respect to pristine SrTiO (leading to SrTiOH). This observation highlights the importance of anion vacancies to improve anion (H/O) diffusion, which is a well-known strategy for improving oxide anion conductivity, and suggests that such a vacancy-assisted reaction could be applied to other anion exchange reactions (e.g., F/O and N/O) to extend the solubility range.
我们使用氢化钙研究了Sc取代的钙钛矿SrTiO（Sr(TiSc)O□，y≤0.1）的拓扑化学阴离子交换反应。结果发现，最初引入少量的阴离子空位（y/2）对于增强阴离子（H/O）交换能力至关重要。例如，Sr(TiSc)O的氢化物还原产生了氢氧化物SrTiScOH，其中氢化物浓度相对于原始SrTiO增加了33%（导致SrTiOH）。这一观察结果突出了阴离子空位对于改善阴离子（H/O）扩散的重要性，这是提高氧化物阴离子导电性的一种众所周知的策略，并表明这种空位辅助反应可应用于其他阴离子交换反应（例如，F/O和N/O）以扩展溶解度范围。
