Olga V Yakubovich, Galina V Kiriukhina, Anatoly S Volkov, Olga V Dimitrova
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These one-periodic structural fragments [Zn(PO<sub>4</sub>)<sub>3</sub>]<sup>7-</sup> define the prismatic habitus of the crystals. The negatively charged zincophosphate chains are balanced by Na<sup>+</sup> cations, disposed in an open space between the chains, and somewhat `diluted' with Zn<sup>2+</sup>, Ca<sup>2+</sup> and Mn<sup>2+</sup> ions as impurities. A rare case of the Na/Zn occupation of one structural site was found in the structure. Theoretical calculations of possible pathways of alkali metal ion migration through the structure and activation energies revealed that the Li-substituted counterpart Li<sub>5</sub>Zn[Zn(PO<sub>4</sub>)<sub>3</sub>] can be considered as a potential solid electrolyte.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":" ","pages":"62-68"},"PeriodicalIF":1.3000,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A rare case of Na/Zn isomorphism in the crystal structure of non-centrosymmetric zincophosphate Na<sub>5</sub>Zn[Zn(PO<sub>4</sub>)<sub>3</sub>].\",\"authors\":\"Olga V Yakubovich, Galina V Kiriukhina, Anatoly S Volkov, Olga V Dimitrova\",\"doi\":\"10.1107/S2052520624011156\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A microporous zincophosphate with the idealized formula Na<sub>5</sub>Zn[Zn(PO<sub>4</sub>)<sub>3</sub>] was obtained through high-temperature hydrothermal synthesis and characterized by scanning electron microscopy, microprobe analysis and X-ray diffraction. The orthorhombic compound, which crystallizes in non-centrosymmetric space group Pna2<sub>1</sub> with unit-cell parameters a = 12.9901 (2), b = 16.2647 (3), c = 5.2158 (1) Å and Z = 4, is characterized by a new structure type. Each ZnO<sub>4</sub> tetrahedron shares all O atoms with four phosphate tetrahedra to form groups of five polyhedra, that are further linked via oxygen-bridging contacts of Zn- and P-centered tetrahedra in chains aligned in the c-axis direction. These one-periodic structural fragments [Zn(PO<sub>4</sub>)<sub>3</sub>]<sup>7-</sup> define the prismatic habitus of the crystals. The negatively charged zincophosphate chains are balanced by Na<sup>+</sup> cations, disposed in an open space between the chains, and somewhat `diluted' with Zn<sup>2+</sup>, Ca<sup>2+</sup> and Mn<sup>2+</sup> ions as impurities. A rare case of the Na/Zn occupation of one structural site was found in the structure. Theoretical calculations of possible pathways of alkali metal ion migration through the structure and activation energies revealed that the Li-substituted counterpart Li<sub>5</sub>Zn[Zn(PO<sub>4</sub>)<sub>3</sub>] can be considered as a potential solid electrolyte.</p>\",\"PeriodicalId\":7320,\"journal\":{\"name\":\"Acta crystallographica Section B, Structural science, crystal engineering and materials\",\"volume\":\" \",\"pages\":\"62-68\"},\"PeriodicalIF\":1.3000,\"publicationDate\":\"2025-02-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta crystallographica Section B, Structural science, crystal engineering and materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2052520624011156\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/12/18 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta crystallographica Section B, Structural science, crystal engineering and materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2052520624011156","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/12/18 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
通过高温水热合成得到了理想分子式为Na5Zn[Zn(PO4)3]的微孔磷酸锌,并通过扫描电镜、探针分析和x射线衍射对其进行了表征。该正交化合物在非中心空间群Pna21中结晶,晶胞参数a = 12.9901 (2), b = 16.2647 (3), c = 5.2158 (1) Å, Z = 4,具有新的结构类型。每个ZnO4四面体与四个磷酸四面体共享所有的O原子,形成五个多面体的基团,这些多面体通过Zn和p中心四面体的氧桥接接触进一步连接在c轴方向排列的链上。这些单周期结构碎片[Zn(PO4)3]7-决定了晶体的棱柱形习性。带负电荷的磷酸锌链被Na+阳离子平衡,放置在链之间的开放空间中,并被Zn2+、Ca2+和Mn2+离子作为杂质“稀释”。在结构中发现了Na/Zn占据一个结构位点的罕见情况。通过结构和活化能对碱金属离子迁移可能途径的理论计算表明,锂取代的对应物Li5Zn[Zn(PO4)3]可以被认为是一种潜在的固体电解质。
A rare case of Na/Zn isomorphism in the crystal structure of non-centrosymmetric zincophosphate Na5Zn[Zn(PO4)3].
A microporous zincophosphate with the idealized formula Na5Zn[Zn(PO4)3] was obtained through high-temperature hydrothermal synthesis and characterized by scanning electron microscopy, microprobe analysis and X-ray diffraction. The orthorhombic compound, which crystallizes in non-centrosymmetric space group Pna21 with unit-cell parameters a = 12.9901 (2), b = 16.2647 (3), c = 5.2158 (1) Å and Z = 4, is characterized by a new structure type. Each ZnO4 tetrahedron shares all O atoms with four phosphate tetrahedra to form groups of five polyhedra, that are further linked via oxygen-bridging contacts of Zn- and P-centered tetrahedra in chains aligned in the c-axis direction. These one-periodic structural fragments [Zn(PO4)3]7- define the prismatic habitus of the crystals. The negatively charged zincophosphate chains are balanced by Na+ cations, disposed in an open space between the chains, and somewhat `diluted' with Zn2+, Ca2+ and Mn2+ ions as impurities. A rare case of the Na/Zn occupation of one structural site was found in the structure. Theoretical calculations of possible pathways of alkali metal ion migration through the structure and activation energies revealed that the Li-substituted counterpart Li5Zn[Zn(PO4)3] can be considered as a potential solid electrolyte.
期刊介绍:
Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.