Synthesis, optical properties and electronic structures of polyoxometalates K{sub 3}P(Mo{sub 1-x}W{sub x}){sub 12}O{sub 40} (0=<x=<1)

Various compositions of solid solutions K{sub 3}P(Mo{sub 1-x}W{sub x}){sub 12}O{sub 40} (0=<x=<1) were prepared using two solid state synthetic routes. The crystallite size was determined by linewidth refinements of X-ray diffraction patterns using the Warren-Averbach method, and the grain siz...

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Published inJournal of solid state chemistry Vol. 177; no. 12
Main Authors Goubin, F., Guenee, L., Deniard, P., Koo, H.-J., Whangbo, M.-H., Montardi, Y., Jobic, S.
Format Journal Article
LanguageEnglish
Published United States 01.12.2004
Subjects
ELECTRONIC STRUCTURE
GRAIN SIZE
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPOUNDS
OPTICAL PROPERTIES
OXIDES
PHOSPHORUS COMPOUNDS
POTASSIUM COMPOUNDS
SOLID SOLUTIONS
TUNGSTEN COMPOUNDS
X-RAY DIFFRACTION
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Summary:Various compositions of solid solutions K{sub 3}P(Mo{sub 1-x}W{sub x}){sub 12}O{sub 40} (0=<x=<1) were prepared using two solid state synthetic routes. The crystallite size was determined by linewidth refinements of X-ray diffraction patterns using the Warren-Averbach method, and the grain size distribution by laser scattering experiments. Optical properties were determined by diffuse reflectance measurements in the UV-visible range. The optical gap E{sub g} was found to increase exponentially from {approx}2.5 to {approx}3.30eV with increasing x, and is systematically shifted to a higher energy when the grain size decreases. The relation between E{sub g} and x was analyzed by calculating the HOMO-LUMO gaps of the [P(Mo{sub 1-x}W{sub x}){sub 12}O{sub 40}]{sup 3-} anions on the basis of tight-binding electronic structure calculations.
ISSN:0022-4596
1095-726X
DOI:10.1016/j.jssc.2004.08.046