Ajana Dutta, Diptikanta Swain*, Digamber G. Porob, Janaky Sunil, Chandrabhas Narayana and Tayur N. Guru Row*,
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The room temperature crystal structure is refined from powder X-ray diffraction (PXRD) data, and it belongs to a monoclinic system, space group <i>P</i>2<sub>1</sub>/<i>c</i>, with <i>Z</i> = 2. Differential scanning calorimetry analysis suggests the possibility of multiple structural phase transitions between 338 and 400 °C. These phase transitions are substantiated by <i>in situ</i> powder X-ray diffraction and Raman spectroscopy. PXRD data with temperature reveal structural phase transitions with a change in crystal symmetry accompanied by the appearance/disappearance of diffraction peaks. Further, the dynamics of the SO<sub>4</sub> tetrahedra units are probed using variable temperature Raman spectroscopy to understand the mechanism of structural phase transitions. These phase transitions are driven by the anomalies of the molecular vibration of sulfate tetrahedra at higher temperatures as revealed from Raman data. 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引用次数: 0
摘要
研究矿物或类似矿物结构的合成化合物的相变是不同科学学科的基本兴趣,其应用范围从了解地球地质历史到推进材料科学和技术。他们为开发具有所需性能的新功能材料提供了有价值的数据和见解。在此背景下,我们研究了Na6Zn(SO4)4的结构相变。Na6Zn(SO4)4是一种类似于钒辉石矿物Na6Mg(SO4)4的合成化合物,在自然界中大量存在于海盐矿床中。根据粉末x射线衍射(PXRD)数据对其室温晶体结构进行了细化,属于单斜晶系,空间群P21/c, Z = 2。差示扫描量热分析表明,在338 ~ 400℃之间可能发生多种结构相变。这些相变是由原位粉末x射线衍射和拉曼光谱证实的。随温度变化的PXRD数据显示结构相变,晶体对称性改变,并伴有衍射峰的出现/消失。此外,利用变温拉曼光谱对SO4四面体单元的动力学进行了探测,以了解结构相变的机制。这些相变是由拉曼数据显示的硫酸盐四面体在高温下的分子振动异常驱动的。此外,离子电导率测量也描述了这些结构相变随温度升高斜率的变化。
Phase Transitions in a Vanthoffite-Type Compound, Na6Zn(SO4)4: Insights from In Situ PXRD and Raman Spectroscopy
The study of phase transitions in minerals or synthetic compounds analogous to mineral structures is of fundamental interest in different scientific disciplines, with applications ranging from understanding the Earth’s geological history to advancing materials science and technology. They provide valuable data and insight into developing new functional materials with desired properties. In this context, we have investigated the structural phase transitions of Na6Zn(SO4)4, a synthetic compound analogous to the Vanthoffite mineral Na6Mg(SO4)4, which occurs abundantly in nature as oceanic salt deposits. The room temperature crystal structure is refined from powder X-ray diffraction (PXRD) data, and it belongs to a monoclinic system, space group P21/c, with Z = 2. Differential scanning calorimetry analysis suggests the possibility of multiple structural phase transitions between 338 and 400 °C. These phase transitions are substantiated by in situ powder X-ray diffraction and Raman spectroscopy. PXRD data with temperature reveal structural phase transitions with a change in crystal symmetry accompanied by the appearance/disappearance of diffraction peaks. Further, the dynamics of the SO4 tetrahedra units are probed using variable temperature Raman spectroscopy to understand the mechanism of structural phase transitions. These phase transitions are driven by the anomalies of the molecular vibration of sulfate tetrahedra at higher temperatures as revealed from Raman data. Additionally, ionic conductivity measurements also depict these structural phase transitions with a change in slope with an increase in temperature.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.