MIL-53(Al) 在超宽压力范围内的重入负线性压缩率,Chemistry of Materials

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MIL-53(Al) 在超宽压力范围内的重入负线性压缩率
Chemistry of Materials ( IF 7.2 ) Pub Date : 2022-02-21 , DOI: 10.1021/acs.chemmater.1c04398
Dequan Jiang ₁ , Ting Wen ₁ , Yanzhen Guo ₂ , Jie Liang ₃ , Zimin Jiang ₁ , Chen Li ₁ , Ke Liu ₁ , Wenge Yang ₁ , Yonggang Wang ₁

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诸如负线性可压缩性 (NLC) 和负面积可压缩性 (NAC) 等异常压缩行为是极端条件下公用事业必不可少的新兴功能。金属有机框架 (MOF) 在公认的“酒架”机制下呈现出一大类 NLC/NAC 材料。然而，MOF 的工作压力通常限制在不超过 3 GPa。在这里，我们报告了 MIL-53(Al) 在高达 41.6 GPa 的超宽压力区域内罕见的再入 NLC 行为的观察结果。具有经典酒架拓扑的 MIL-53(Al) 首先表现出沿c的 NLC 行为轴在 0-2.7 GPa 的压力区域，然后是 2.7 和 12.9 GPa 之间的正常压缩过程。之后，令人惊讶的是，在先前报道的 MOF 中，重入 NLC 特性仍处于创纪录的高压（>40 GPa）。通过结合 X 射线衍射分析、拉曼光谱和 DFT 计算，研究了 MIL-53(Al) 在三个阶段的不同压缩行为的机制。特别是，Cr ³⁺的光致发光可作为一种独特的探针，用于研究 Al ³⁺在压缩下局部配位环境的细微变化。Cr ^{3+的吸收光谱和光致发光}掺杂的 MIL-53(Al) 不仅验证了三级压缩过程，还揭示了 22.0 GPa 左右的隐藏结构/电相变。这些发现提供了对局部结构水平异常压缩行为的结构-性能关系的深入理解。

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Reentrant Negative Linear Compressibility in MIL-53(Al) over an Ultrawide Pressure Range

Anomalous compression behaviors such as negative linear compressibility (NLC) and negative area compressibility (NAC) are emerging functionalities essential for utilities under extreme conditions. Metal–organic frameworks (MOFs) present a large family of NLC/NAC materials under the well-recognized “wine-rack” mechanism. Nevertheless, the working pressure of MOFs is limited to typically no more than 3 GPa. Herein, we report the observation of a rare reentrant NLC behavior of MIL-53(Al) over an ultrawide pressure region up to 41.6 GPa. MIL-53(Al) with the classic wine-rack topology first exhibits an NLC behavior along the c-axis in the pressure region of 0–2.7 GPa, followed by a normal compression process between 2.7 and 12.9 GPa. After that, it is surprising to find that the reentrant NLC property remains at a record-high pressure (>40 GPa) among the previously reported MOFs. The mechanisms of the distinct compression behaviors of MIL-53(Al) in the three stages are studied by combining the X-ray diffraction analyses, Raman spectra, and DFT calculation. Particularly, the photoluminescence of Cr³⁺ is used as a unique probe for the subtle changes of the local coordination environments of Al³⁺ under compression. Both the absorption spectra and photoluminescence of Cr³⁺-doped MIL-53(Al) not only verify the three-stage compression processes but also reveal a hidden structural/electrical phase transition around 22.0 GPa. These findings provide an in-depth understanding of the structure–property relationship of abnormal compression behavior at the local-structure level.

更新日期：2022-02-21

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