Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

ABSTRACT

Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO4)(H2O)4Cl]Cl·H2O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO4)(H2O)4Cl]+ 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 Th4+ center in TMC are vulnerable to competition with F-, due to the formation of more favorable Th-F bonds compared to Th-OH2. This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.