The structural genesis of a complex (MoVW)5O14 oxide during thermal treatments and its redox behavior at elevated temperatures

The structural genesis of a Mo0.68V0.23W0.09 oxide with Mo5O14-like structure has been examined. A precursor prepared by spray-drying of mixed aqueous metal salt solutions was calcined in air and subsequently treated in helium at different temperatures. X-ray diffraction, HRTEM, 51V magic angle spinning (MAS) NMR, ESR, UV/vis DR spectroscopy and oxygen and hydrogen adsorption measurements have been applied to monitor the preparation procedure. It was found that a structure closely related to that of Mo5O14 already appears at nano-scale level after calcination of the spray-dried precursor in air at 350 °C. At this stage, the material comprises of crystalline particles less than 3 nm in size stabilized by an amorphous matrix. Further heating causes nanostructural rearrangements that lead to the formation of the final Mo0.68V0.23W0.09 oxide with phase-pure polycrystalline structure. Molybdenum and tungsten ions are hexavalent and coordinated in an octahedral environment. Furthermore, vanadium is present as V4+ and V5+ ions occupying octahedral and highly distorted trigonal pyramidal sites, respectively. According to the results of H2 and O2 adsorption the crystalline ternary oxide does not possess accessible micropores. Oxygen pulses at 450 °C and reductive treatment with pure hydrogen at 300 °C did not cause noticeable changes of the bulk structure thus indicating a remarkable structural stability of the complex MoVW oxide under redox conditions at elevated temperature.