Topochemical intercalation reactions of ZrSe3
Topochemical intercalation reactions of ZrSe3
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DOI：
10.1016/j.jssc.2022.123436
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发表时间：
2022-07
影响因子：
3.3
通讯作者：
M. Elgaml;S. Cassidy;S. Clarke
中科院分区：
文献类型：
--
作者：
M. Elgaml;S. Cassidy;S. Clarke
碱金属和碱土金属通过软化学途径插入zrse3中注入电子，对硒化物-硒化物成键有显著影响。低温（- 78°C）下由金属氨溶液制备的zrse3的K、Rb和Cs插层与高温（850°C）下得到的相关多晶相形成对比。低温合成的kxzrse3结晶为正晶型cmc21，高温合成的多晶型结晶为immm。在完全不同的条件下制备的两种结构的不同之处在于zrse3层的相对位移。相比之下，csxzrse3在低温和高温下均表现为非晶多晶，而在两种温度下均形成单一的rbxzrse3多晶不晶。由于Ca2+的强溶剂化作用，从液氨中插入Ca有利于溶剂的共插层。由于相邻zrse3层相对位移的灵活性，该化合物具有严重的断裂。
Intercalation of alkali and alkaline earth metals into ZrSe3via soft chemical routes injects electrons and has a significant effect on the selenide-selenide bonding. K, Rb and Cs intercalates of ZrSe3prepared at low temperatures (−78 °C) from metal ammonia solutions contrast with related polymorphs obtained at high temperature (850 °C). KxZrSe3synthesised at low temperatures crystallises in orthorhombicCmc21, while the polymorph obtained at high temperatures crystallises inImmm.The two structures prepared under drastically different conditions differ by relative shifting of ZrSe3layers. In contrast, CsxZrSe3shows theImmmpolymorph at low temperature and theCmc21polymorph at high temperatures, while a single RbxZrSe3polymorph inImmmis formed at both temperatures. Intercalation of Ca from liquid ammonia facilitates the co-intercalation of the solvent because of the strong solvation of Ca2+. This compound has severe faulting due to the flexibility in the relative shifts of adjacent ZrSe3layers.