Thermal expansion in Prussian Blue analogs M3[Cr(CN)6]2.nH2O (M = Mn, Fe, Co, Ni)

IF 3.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Solid State Sciences Pub Date : 2024-09-26 DOI:10.1016/j.solidstatesciences.2024.107712

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Abstract

Thermal expansion in Prussian Blue Analogs (PBAs) M₃[Cr(CN)₆]₂.nH₂O (M = Mn, Fe, Co, Ni; n = 10–16) was studied using powder X-ray diffraction (XRD) as a function of temperature in the range 123–298 K. Standard chemical precipitation was used to prepare the materials and they were characterized using standard characterization techniques XRD, X-ray fluorescence (XRF), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. All materials were found to crystallize in the cubic structure with space group

F m \overline{3} m

. Strong compositional dependence of thermal expansion is found in this series of PBAs. While Mn₃[Cr(CN)₆]₂.12H₂O and Ni₃[Cr(CN)₆]₂.16H₂O show positive thermal expansion (PTE) behavior the other two PBAs, Fe₃[Cr(CN)₆]₂.10H₂O and Co₃[Cr(CN)₆]₂.14H₂O, show strong negative thermal expansion (NTE) behavior with as large coefficient of thermal expansion (CTE) as −19.7 x 10⁻⁶ K⁻¹ (for M = Fe) in the temperature range 123–223 K. For the PBAs showing NTE, the magnitude of NTE coefficients can be correlated with the trends for M cation size and cell (or lattice) parameter.

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普鲁士蓝类似物 M3[Cr(CN)6]2.nH2O（M = Mn、Fe、Co、Ni）的热膨胀率

使用粉末 X 射线衍射 (XRD) 研究了普鲁士蓝类似物（PBAs）M3[Cr(CN)6]2.nH2O（M = Mn、Fe、Co、Ni；n = 10-16）在 123-298 K 范围内的热膨胀与温度的函数关系。制备材料时使用了标准化学沉淀法，并使用标准表征技术 XRD、X 射线荧光 (XRF)、热重分析 (TGA) 和傅立叶变换红外光谱 (FTIR) 对材料进行了表征。所有材料均为立方结构，空间群为 Fm3-‾m。在这一系列 PBA 中，发现热膨胀与成分有很强的相关性。Mn3[Cr(CN)6]2.12H2O 和 Ni3[Cr(CN)6]2.16H2O 表现出正热膨胀 (PTE) 行为，而另外两种 PBA，Fe3[Cr(CN)6]2.10H2O 和 Co3[Cr(CN)6]2.14H2O 则表现出强烈的负热膨胀 (NTE) 行为，热膨胀系数 (CTE) 大至 -19.对于显示 NTE 的 PBA，NTE 系数的大小与 M 阳离子尺寸和晶胞（或晶格）参数的变化趋势相关。

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来源期刊

Solid State Sciences 化学-无机化学与核化学

CiteScore

6.60

自引率

2.90%

发文量

214

审稿时长

27 days

期刊介绍： Solid State Sciences is the journal for researchers from the broad solid state chemistry and physics community. It publishes key articles on all aspects of solid state synthesis, structure-property relationships, theory and functionalities, in relation with experiments. Key topics for stand-alone papers and special issues: -Novel ways of synthesis, inorganic functional materials, including porous and glassy materials, hybrid organic-inorganic compounds and nanomaterials -Physical properties, emphasizing but not limited to the electrical, magnetical and optical features -Materials related to information technology and energy and environmental sciences. The journal publishes feature articles from experts in the field upon invitation. Solid State Sciences - your gateway to energy-related materials.