Solid Solution Formation between Vanadium(V) and Tungsten(V) Oxide Phosphate
作者： Subrata Chandra Roy , Robert Glaum , Dinar Abdullin , Olav Schiemann , Nguyen Quang Bac
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摘要: The solid solutions (V1–xWx)OPO4 with β-VOPO4 structure type (0.0 ≤ x 0.01) and αII-VOPO4 (0.04 0.26) were obtained from mixtures of VVOPO4 WVOPO4 by conventional state reactions solution combustion synthesis. Single crystals up to 3 mm edge length chemical vapor transport (CVT) (800 700 °C, Cl2 as a transporting agent). crystal refinements at = 0.10 [a 6.0503(2) A, c 4.3618(4) R1 0.021, wR2 0.058, 21 parameters, 344 independent reflections] 0.26 6.0979(2) 4.2995(1) 0.030, 0.081, 346 confirm the (P4/n, Z 2) mixed occupancy V/W for metal site. Due specific redox behavior W5+ V5+, should be formulated (VIVxVV1–2xWVIx)OPO4. valence states vanadium tungsten are confirmed XPS measurements. V4+ d1 configuration was identified EPR spectroscopy magnetic Electronic spectra show IVCT(V4+ V5+) LMCT(O2– V5+). (V0.74W0.26)OPO4 powders exhibit semi-conducting (Eg 0.7 eV).
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