Shanghai Institute of Applied Physics , Chinese Academy of Sciences , 2019 Jia Luo Road , Shanghai 201800 , China.
University of Chinese Academy of Sciences , 2019 Jia Luo Road , Shanghai 201800 , China.
Inorg Chem. 2018 Jun 18;57(12):6778-6782. doi: 10.1021/acs.inorgchem.8b00954. Epub 2018 Jun 5.
Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO)(HO)Cl]Cl·HO. The structure of TMC is composed of zigzagging cationic layers [Th(MoO)(HO)Cl] with Cl as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th center in TMC are vulnerable to competition with F, due to the formation of more favorable Th-F bonds compared to Th-OH. This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.
搜索具有阴离子交换能力的阳离子扩展材料，得到了一种独特的钍钼酸氯（TMC），其化学式为[Th（MoO）（HO）Cl]Cl·HO。TMC 的结构由交错的阳离子层[Th（MoO）（HO）Cl]组成，Cl 作为层间电荷平衡阴离子。TMC 在 AF（A = Na、K 和 Cs）溶液中浸泡后，形成碱土金属钍氟化物，而不是进行离子交换。通过 SEM-EDS、PXRD、FTIR 和 EXAFS 光谱的结合，阐明了 AF 固定化的机制。观察到 TMC 中与 Th 中心配位的四个水分子由于形成更有利的 Th-F 键而容易与 F 竞争，而不是 Th-OH。这导致通过再结晶形成碱土金属钍氟化物的途径从单晶到多晶的转变。
