V3.047O7, a new high-pressure oxide with the simpsonite structure

Abstract

Reaction between α-V₂O₅ and NaN₃ has been studied at pressures from 5.0 to 6.0 GPa and temperatures from 600 to 800°C using Toroid high-pressure chambers. A new oxide, V_3.047O₇ (VO_2.297), isostructural with simpsonite, Al₄Ta₃O₁₃(OH), has been detected in samples with the initial composition 0.2NaN₃ · V₂O₅ after high-temperature, high-pressure processing at p = 5.0 GPa and t = 800°C for 2 min. The crystal structure of the oxide has been refined by the Rietveld method using X-ray powder diffraction data: a = 7.35136(2) Å, c = 4.51462(2) Å, V = 211.294(1) ų, Z = 2, sp. gr. P3. Each vanadium atom in this structure is coordinated by six oxygens in the form of a [VO₆] octahedron. The synthesized oxide is a second compound with the simpsonite structure. We have measured the infrared transmission and Raman spectra of V_3.047O₇. Electrical measurements have demonstrated that the material is a semiconductor.