立方萤石结构CeO<sub>2</sub>Cl<sub>0.07</sub>的高压复分解反应合成与物性表征

寇行健; 刘静仪; 王扬斌; 雷力

doi:10.11858/gywlxb.20251286

立方萤石结构CeO₂Cl_0.07的高压复分解反应合成与物性表征

doi: 10.11858/gywlxb.20251286

四川大学原子与分子物理研究所, 四川成都　610065

基金项目: 国家自然科学基金（12374013）；中央高校基本科研业务费（2020SCUNL107）

详细信息

作者简介:
寇行健（2000－），男，硕士研究生，主要从事高压新材料合成与表征研究. E-mail：1245402119@qq.com

通讯作者:
雷　力（1980－），男，博士，研究员，主要从事高压物理与化学研究. E-mail：lei@scu.edu.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2025-12-29
- 修回日期: 2026-02-03
- 网络出版日期: 2026-02-05

High-Pressure Metathesis Synthesis and Physical Property Characterization of Cubic Fluorite-Structured CeO₂Cl_0.07

Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan, China

摘要

摘要: Ce的4f电子长久以来就因其独特的离域机制，以及对原子结构、相变行为、磁性结构的影响而受到广泛的关注。通过改变前驱体（CeCl₃、MgO粉末）化学配比，在大腔体压机提供的高温高压（1873 K、5 GPa）环境下，通过调控高压固相复分解反应（high-pressure solid-state metathesis, HSM），合成了立方萤石结构的CeO₂Cl_0.07。利用金刚石对顶砧（diamond anvil cell，DAC），结合高压原位同步辐射X射线衍射、扫描电子显微镜、能谱仪、高压拉曼光谱等表征手段，获得了样品的压力-比容曲线，并与CeO₂进行比较，发现CeO₂Cl_0.07更易被压缩，获得了高压拉曼声子谱（F_2g），结果显示，非静水压下在0～2 GPa区间以及15 GPa附近CeO₂Cl_0.07的拉曼峰随压力的变化存在异常。分析认为，Cl元素的掺入带来氧空位，使得Ce³⁺浓度升高，进而引起4f电子离域。研究结果揭示了CeO₂Cl_0.07在高压条件下的行为，提供了一种新型铈基化合物的高压合成途径。
- 高压固相复分解反应 /
- CeO₂ /
- 同步辐射 /
- 拉曼散射 /
- 高温高压 /
- 4f电子
Abstract: The 4f electron of Ce has long attracted extensive attention due to their unique delocalization mechanism and their influence on atomic structure, phase transformation behavior, and magnetic structure. In this paper, CeO₂Cl_0.07 was synthesized with a cubic fluorite structure by changing the stoichiometry of the precursors (CeCl₃, MgO powder) and regulating the high-pressure solid-state metathesis (HSM) reaction under high temperature and high pressure conditions (1873 K, 5 GPa) provided by a large volume press. Then pressure was provided by a diamond anvil cell (DAC), and the sample was characterized by high-pressure in-situ synchrotron X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), and high-pressure Raman spectroscopy. By comparing the obtained pressure-volume (p-V) curve with CeO₂, it is found that CeO₂Cl_0.07 is more compressible. The high-pressure Raman phonon spectrum (F_2g) is obtained, indicating that the pressure-dependent behavior of CeO₂Cl_0.07 exhibits anomalous changes at 0–2 GPa and near 15 GPa under non-hydrostatic pressure. We believe that the doping of Cl elements introduces oxygen vacancies, which increases the concentration of Ce³⁺, thereby causing the delocalization of 4f electron and resulting in the observed phenomenon. This study developed a new high-pressure synthesis pathway for cerium-based compounds and revealed their behavior under high-pressure conditions.
- high-pressure solid-state metathesis reaction /
- CeO₂ /
- synchrotron radiation /
- Raman scattering /
- high-temperature and high-pressure /
- 4f electron

HTML全文

图 1 0 GPa 下同步辐射实验测得的合成样品的XRD 谱（左侧插图为样品晶体结构示意图，右侧插图为样品的SEM 图像）

Figure 1. XRD pattern of samples obtained from synchrotron radiation experiments at 0 GPa (The left inset is the schematic diagram of the crystal structure, and the right inset shows a SEM image of the sample.)

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图 2 0 GPa 下 CeO₂Cl_0.07与CeO₂的拉曼峰

Figure 2. Raman peaks of CeO₂Cl_0.07 and CeO₂ at 0 GPa

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图 3 CeO₂Cl_0.07的非静水压升压拉曼谱(a)、静水压升压拉曼谱(b)、非静水压和静水压升压拉曼峰的峰位散点图(c)和半峰宽散点图(d)

Figure 3. Non-hydrostatic pressure boost Raman spectra (a), hydrostatic pressure boost Raman spectra (b), scatter plot of Raman peak positions for non-hydrostatic pressure boost and hydrostatic pressure boost (c), and scatter plot of full width at half maximum (FWHM) (d) of CeO₂Cl_0.07

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图 4 (a) CeO₂Cl_0.07样品的非静水压升压 XRD 谱瀑布图，(b) CeO₂Cl_0.07样品和 CeO₂^[20]的 p-V 曲线

Figure 4. (a) Waterfall plot of XRD patterns of CeO₂Cl_0.07 sample under non-hydrostatic pressure; (b) p-V curves of CeO₂Cl_0.07 sample and CeO₂^[20]

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图 5 CeO₂Cl_0.07（非静水压升压）与 CeO₂（静水压^[26–28]、非静水压升压）的拉曼峰对比

Figure 5. Comparison of Raman shift between CeO₂Cl_0.07 (non-hydrostatic pressure) and CeO₂ (hydrostatic^[26–28] and non-hydrostatic pressure)

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