Computationally Led High Pressure Synthesis and Experimental Thermodynamics of Rock Salt Yttrium Monoxide
Computationally Led High Pressure Synthesis and Experimental Thermodynamics of Rock Salt Yttrium Monoxide
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岩盐一氧化钇的计算主导高压合成及实验热力学
DOI：
10.1021/acs.chemmater.3c02166
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发表时间：
2024
影响因子：
8.6
通讯作者：
Navrotsky, Alexandra
中科院分区：
文献类型：
--
作者：
Brugman, Benjamin L.;Han, Yifeng;Leinbach, Logan J.;Leinenweber, Kurt;van de Walle, Axel;Ushakov, Sergey V.;Hong, Qi-Jun;Navrotsky, Alexandra
一氧化钇 (YO) 可能是具有岩盐结构的稀土一氧化物大家族的一员。预计它可以在 10 GPa 以上稳定，并在较低压力下具有较高临界温度的超导性。然而，尚未报道块状 YO 的合成。利用第一性原理计算，我们预测了一氧化钇在高于 8.6 GPa 的压力和高温下的稳定性。在这些预测的指导下，我们在 15 GPa 和 1600 °C 下成功合成了岩盐结构 (Fm3̅m) 中的块状 YO2。 YO 在环境条件下非常亚稳定（热力学和动力学），并在加热时迅速分解。因此，这项工作仅侧重于理论预测、高压合成和实验热力学测量。详细的结构分析和物理性能测量将在未来的工作中发表。我们的实验和计算相结合的方法使我们能够获得块状 YO 的形成焓和晶格常数的一致结果。反应 Y + Y2O3= 3YO 的预测生成焓为 32.7 kJ/mol，实验得出的值为 35.7 kJ/mol，估计不确定度为 ±5%。岩盐结构中的 YO 具有 4.878 ± 0.010 Å 的精细晶格常数和 17.47 ± 0.11 cm3mol–1 的摩尔体积。由此，我们计算了反应的熵和 P-T 斜率。通过这项全面的研究，我们探索了具有挑战性的亚稳态相的合成和分解，该相在高压条件下稳定。此外，我们对 YO 的热力学和物理性质获得了宝贵的见解。这些发现强调了利用压力作为材料合成中的附加维度的重要性，并强调了使用第一原理计算来指导涉及高度亚稳态材料的实验的潜力。
Yttrium monoxide (YO) is a possible member of a large family of rare earth monoxides having the rock salt structure. It was predicted to be stable above 10 GPa and superconducting with higher critical temperatures at lower pressures. However, no syntheses of bulk YO have been reported. Using first-principles calculations, we predicted the stability of yttrium monoxide at pressures above 8.6 GPa and at high temperature. Guided by these predictions, we successfully synthesized bulk YO in the rock salt structure (Fm3̅m) at 15 GPa and 1600 °C. YO is very metastable (both thermodynamically and kinetically) under ambient conditions and decomposes rapidly on heating. Accordingly, this work focuses solely on theoretical prediction, high-pressure synthesis, and experimental thermodynamic measurements. Detailed structural analysis and physical property measurements will be published in future work. Our combined experimental and computational approach enabled us to obtain consistent results for the formation enthalpy and lattice constant of bulk YO. The predicted enthalpy of formation for the reaction Y + Y2O3= 3YO is 32.7 kJ/mol, and experiments yield a value of 35.7 kJ/mol, with an estimated uncertainty of ±5%. YO in the rock salt structure has a refined lattice constant of 4.878 ± 0.010 Å and a molar volume of 17.47 ± 0.11 cm3mol–1. From these, we calculated the entropy andP–Tslope of the reaction. Through this comprehensive investigation, we explored the synthesis and decomposition of a challenging metastable phase, which is stabilized under high pressure conditions. Moreover, we have gained valuable insights into the thermodynamics and physical properties of YO. These findings highlight the importance of leveraging pressure as an additional dimension in materials synthesis and underscore the potential of using first-principles calculations to guide experiments involving highly metastable materials.
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影响因子：
4
作者：
Taku Yamamoto;K. Kaminaga;Daichi Saito;D. Oka;T. Fukumura
通讯作者：
Taku Yamamoto;K. Kaminaga;Daichi Saito;D. Oka;T. Fukumura
具有高铁磁居里温度的岩盐结构 GdO 外延薄膜
影响因子：
4
作者：
Yamamoto Taku;Kaminaga Kenichi;Saito Daichi;Oka Daichi;Fukumura Tomoteru
通讯作者：
Fukumura Tomoteru
钐-氮-氧三元体系及钐低氧化物问题
影响因子：
4.6
作者：
T. Felmlee;L. Eyring
通讯作者：
L. Eyring
Dy2(1−x)Tm2xO3 稀土氧化物陶瓷的相结构和振动光谱
影响因子：
4.5
作者：
Xiaojian Fu;Yuanda Xu;Ji Zhou
通讯作者：
Ji Zhou
DOI：
10.1002/chin.198044028
发表时间：
1980-08
期刊：
ChemInform
影响因子：
--
作者：
J. Leger;N. Yacoubi;J. Loriers
通讯作者：
J. Leger;N. Yacoubi;J. Loriers