Sodalite-like Rare-Earth Carbonates: a Study of Structural Transformation and Diluted Magnetism
Sodalite-like Rare-Earth Carbonates: a Study of Structural Transformation and Diluted Magnetism
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类方钠石稀土碳酸盐：结构转变和稀磁的研究
DOI：
10.1039/c5dt03314d
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发表时间：
2016
影响因子：
4
通讯作者：
Zheng Yan-Zhen
中科院分区：
文献类型：
--
作者：
Wang Yanyan;Han Tian;Ding You-Song;Zheng Zhiping;Zheng Yan-Zhen
通过从NaCO3或大气二氧化碳中引入适量CO32−作为模板，成功合成了一系列具有类钠石（SOD-like）分子筛拓扑结构的新型稀土碳酸盐RE3(OH)6(CO3)Cl （RE = Dy, Er， Y）。单晶x射线衍射结果表明，该结构为RE3(OH)63+阳离子骨架，由顶点共享的立方体[RE4(μ3-OH)4]构成类似sod的拓扑结构。CO32 -阴离子封闭6环开口，Cl -阴离子位于通道内，实现电荷平衡。在370℃下煅烧后，原位化合物RE3(OH)6(CO3)Cl转变为新相RE3O4Cl。有趣的是，RE3O4Cl的结构代表了一种新的类似sod的开放框架，与RE3(OH)6(CO3)Cl中CO32−的去除有关。通过热重分析（TGA）、元素分析、x射线光电子能谱和磁性研究对样品进行了表征。此外，Dy0.0068Y2.9932(OH)6(CO3)Cl和Dy0.0068Y2.9932 o4 Cl的Dy/Y摩尔比高达1/440，Er0.19Y2.81(OH)6(CO3)Cl的Er/Y摩尔比为1/15的稀释样品均表现出单离子效应。
A series of novel rare earth carbonates, RE3(OH)6(CO3)Cl (RE = Dy, Er, Y), with sodalite-like (SOD-like) zeolite topologies have been successfully synthesized by introducing an appropriate amount of CO32− from NaCO3 or atmospheric carbon dioxide as a template. Single-crystal X-ray diffraction reveals that the structure consists of the RE3(OH)63+ cationic framework with a SOD-like topology built from vertex-sharing [RE4(μ3-OH)4] cubes. The CO32− anions seal the 6-ring opening and Cl− anions situated in the channels to achieve charge balance. After calcination at 370 °C, the compound RE3(OH)6(CO3)Cl in situ transforms into a new phase formulated as RE3O4Cl. Interestingly, the structure of RE3O4Cl represents a new SOD-like open framework, associated with the removal of the CO32− from RE3(OH)6(CO3)Cl. The samples are characterized by thermogravimetric analysis (TGA), elemental analysis, X-ray photoelectron spectroscopy and magnetic studies. Furthermore, single-molecule magnet behaviours can be observed for the diluted samples of Dy0.0068Y2.9932(OH)6(CO3)Cl and Dy0.0068Y2.9932O4Cl with a Dy/Y molar ratio of up to 1/440 as well as Er0.19Y2.81(OH)6(CO3)Cl with an Er/Y ratio of 1/15, showing dominant single-ion effects.