Solid‐State Ion Migration in the Preyssler‐Type Phosphotungstate for the Preparation of the Dipotassium Cation‐Encapsulated Derivative

Abstract

The heat‐driven solid‐state transformations of K salts of the Na‐encapsulated Preyssler‐type phosphotungstates, K14[P5W30O110Na(side)(H2O)] and K14[P5W30O110Na(center)], are reported herein. K14[P5W30O110Na(side)(H2O)] contains one Na+ in one of the side cavities and a coordinating H2O molecule while K14[P5W30O110Na(center)] contains one Na+ in the central cavity. The heating of K14[P5W30O110Na(side)(H2O)] produces [P5W30O110Na(center)]14–, [P5W30O110K(center)]14–, and [P5W30O110K(side)2]13–. [P5W30O110K(center)]14– and [P5W30O110K(side)2]13– contain mono‐K+ in the central cavity and di‐K+ in both side cavities, respectively. The heating of potassium salt of [P5W30O110Na(center)]14– produces [P5W30O110K(center)]14– and [P5W30O110K(side)2]13–. These results indicate that heating, at 200–500 °C, causes the migrations of Na+ and K+, without the collapse of the molecule. K14[P5W30O110Na(side)(H2O)] was successfully converted to K12Na[P5W30O110K(side)2] by repeated solid‐state heating, which was periodically interrupted by dissolution, in H2O, and drying.

Synthesis and Structural Characterization of Multi‐Molybdenum‐Substituted Preyssler‐type Phosphotungstates

“…The K‐encapsulated Preyssler compound, [P 5 W 30 O 110 K(H 2 O)] 14− , has been reported by Sun et al [44] . We have reported that heating the K salt of Na‐encapsulated anion, K 14 [P 5 W 30 O 110 Na(H 2 O)], produced mono‐K‐ and di‐K‐encapsulated anions, such as [P 5 W 30 O 110 K] 14− and [P 5 W 30 O 110 K 2 ] 14− [45] …”

“…14À , has been reported by Sun et al [44] We have reported that heating the K salt of Naencapsulated anion, K 14 [P 5 W 30 O 110 Na(H 2 O)], produced mono-Kand di-K-encapsulated anions, such as [P 5 W 30 O 110 K] 14À and [P 5 W 30 O 110 K 2 ] 14À . [45] For the [P 5 W 30-x Mo x O 110 Na(H 2 O)] 14À , several profiles assignable to the Mo-substituted species were observed (Figures 4, S8, S9, and S10). The ESI-MS results of the [P 5 W 28.9 Mo 2.1 O 110 Na-(H 2 O)] 14À showed profiles assignable to mono-Mo-, di-Mo-, and We conclude that we could isolate the mixtures of [P 5 W 30-…”

“…[27][28][29][30] The Preyssler-type phosphotungstates, [P 5 W 30 O 110 Z n + (H 2 O)] (15À n)À , are constructed using five PO 4 tetrahedra surrounded by thirty WO 6 octahedra, which create a doughnut-shaped structure with an internal cavity space that can encapsulate a cation (Z n + ) in the molecule (Figure 1). Cations such as Na + , [31,32] lanthanide, [4,13,[33][34][35][36] actinide cations, [33][34][35][37][38] Ca 2 + , [4,33,37,39] Y 3 + , [4,33,37] Bi 3 + , [4,19,21,33,39] Ag + , [28][29][30][40][41][42] or K + , [5,6,[43][44][45] can be encapsulated, and the replacement of the encapsulated cation is widely used to tune the properties of the Preyssler compound. An alternative method to tune the properties is the substitution of framework W atoms.…”

Ultrahigh Proton Conduction via Extended Hydrogen-Bonding Network in a Preyssler-Type Polyoxometalate-Based Framework Functionalized with a Lanthanide Ion

“…K 14 [P 5 W 30 O 110 K]·24H 2 O was prepared as follows: K 14 [P 5 W 30 O 110 Na­(H 2 O)] was heated in a conventional muffle oven to 673 K with a heating rate of 10 K min –1 , and the final temperature was kept for 100 h. The resulting solid (10.0 g) containing [P 5 W 30 O 110 K] 14– , [P 5 W 30 O 110 K 2 ] 13– , and [P 5 W 30 O 110 Na] 14– in a ca. 35:60:5 ratio was recrystallized from 100 mL of hot water (358 K), and white crystals (3.53 g) containing [P 5 W 30 O 110 K] 14– and [P 5 W 30 O 110 K 2 ] 13– in a ca. 90:10 ratio were obtained.…”

Preparation of ZnO/TiO2 Nanocomposite Sensitized Mangosteen Rind (Garcinia mangostana L) Dye for Light Harvesting Efficiency in Solar Cell

“…To improve the efficiency of the TiO 2 electrode, some modification was performed, such as the formation of the nanocomposite. There are several TiO 2 based composites were reported, such as TiO 2 /SiO 2 (Nguyen et al 2007), TiO 2 /Al 2 O 3 (Zhang et al, 2003), TiO 2 /CaCO 3 (Lee et al, 2006), TiO 2 /SnO 2 (Pham et al, 2021), non-metallic elements (Khan et al, 2021) and polyoxometalates (Gu et al, 2020;Wihadi & Sadakane, 2020).…”