Phase equilibria in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system, Crystal structures and properties of new triple molybdates Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6

• Subsolidus phase relations in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system were determined.
• Two new compounds, Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6, were obtained.
• The Cs2ZnZr(MoO4)4 structure belongs to the KAl(MoO4)2 type.
• Cs2ZnZr2(MoO4)6 is isostructural to Cs2MnZr2(MoO4)6 and contains a 3D framework of vertex-sharing MoO4 tetrahedra and (Zn, Zr)O6 octahedra.
• .Cs2ZnZr2(MoO4)6 undergoes a first-order phase trnsition at 723 K with considerable increasing its ionic conductivity

Subsolidus phase relations in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system were determined and two new compounds, Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6, were obtained. The structure of Cs2ZnZr(MoO4)4 (a=5.7919(1) Å, c=8.0490(3) Å; space group P  3¯m1; Z=0.5; R=0.0149) belongs to the layered glaserite-like KAl(MoO4)2 structure type where the octahedral Al3+ positions are statistically occupied by 0.5 Zn2++0.5 Zr4+. The second triple molybdate, Cs2ZnZr2(MoO4)6 (a=13.366(1) Å, c=12.253(3) Å, space group R  3¯, Z=3, R=0.0324), is isostructural to Cs2MnZr2(MoO4)6 and Cs2M2Zr(MoO4)6 (M=Al, Fe) and contains a mixed 3D framework built of МоO4 tetrahedra and (Zn, Zr)O6 octahedra sharing common vertices. Cesium cations are located in large channels of the framework. The latter compound undergoes a first-order phase transition at 723 K with considerable increasing its ionic conductivity.

Crystal structure Cs2ZnZr2(MoO4)6 and electrophysical properties for paper “Phase equilibria in the Cs2MoO4–ZnMoO4–Zr(MoO4)2 system, Crystal structures and properties of new triple molybdates Cs2ZnZr(MoO4)4 and Cs2ZnZr2(MoO4)6” by Galina D. Tsyrenova, Sergey F. Solodovnikov, Nadezhda N. Popova, Zoya A. Solodovnikova, Erzhena T. Pavlova, Dmitry Yu. Naumov, Bogdan I. Lazoryak.Figure optionsDownload as PowerPoint slide