Potassium Ion Conductivity in the Cubic Labyrinth of a Piezoelectric, Antiferromagnetic Oxoferrate(III) Tellurate(VI)

Abstract

Orange-colored crystals of the oxoferrate tellurate K12+6xFe6Te4−xO27 [x=0.222(4)] were synthesized in a potassium hydroxide hydroflux with a molar water–base ratio n(H2O)/n(KOH) of 1.5 starting from Fe(NO3)3 ⋅ 9H2O, TeO2 and H2O2 at about 200 °C. By using (NH4)2TeO4 instead of TeO2, a fine powder consisting of microcrystalline spheres of K12+6xFe6Te4−xO27 was obtained. K12+6xFe6Te4−xO27 crystallizes in the acentric cubic space group I (Formula presented.) 3d. [FeIIIO5] pyramids share their apical atoms in [Fe2O9] groups and two of their edges with [TeVIO6] octahedra to form an open framework that consists of two loosely connected, but not interpenetrating, chiral networks. The flexibility of the hinged oxometalate network manifests in a piezoelectric response similar to that of LiNbO3.The potassium cations are mobile in channels that run along the <111> directions and cross in cavities acting as nodes. The ion conductivity of cold-pressed pellets of ball-milled K12+6xFe6Te4−xO27 is 2.3×10−4 S ⋅ cm−1 at room temperature. Magnetization measurements and neutron diffraction indicate antiferromagnetic coupling in the [Fe2O9] groups.