Journal of Physical Chemistry B, Vol.104, No.34, 8145-8152, 2000
Studies on the behavior of mixed-metal oxides: Structural, electronic, and chemical properties of beta-FeMoO4
The structural and electronic properties of iron molybdate (FeMoO4) have been studied using synchrotron-based time-resolved X-ray diffraction (TR-XRD), X-ray absorption near-edge spectroscopy (XANES), and first-principles density functional (DFT-GGA) calculations. The beta phase of FeMoO4 is stable in a large range of temperatures (25-800 degrees C). For beta-FeMoO4, the results of Reitveld refinement and DFT-GGA calculations give a crystal structure in which Fe is in an almost octahedral environment while Mo is tetracoordinated. The Mo L-lI-edge XANES spectra of beta-FeMoO4 exhibit a line shape that is typical of oxides in which Mo is in a tetrahedral environment. The valence electronic structure of beta-FeMoO4 is characterized by an intense peak with Fe 3d character near the top of the valence band. The iron molybdate displays a good chemical affinity for H-2, H2S, and SO2. H-2-TPR (temperature programmed reduction) spectra for beta-FeMoO4 show consumption of hydrogen and evolution of water (beta-FeMoO4 + H-2,(gas) --> H2Ogas + FeMoOx) between 600 and 850 degrees C. Upon exposure to H2S at moderate temperatures (50-250 degrees C), there is formation of sulfides and sulfates on the oxide. H2S exposure at elevated temperatures (350-450 degrees C) leads to formation of FeMoSx compounds without SOx species (beta-FeMoO4 + H2,Sgas --> H2Ogas + FeMoSx). beta-FeMoO4 is a good sorbent for sulfur dioxide. The adsorption of SO2 on beta-FeMoO4 at room temperature produces SO3 and SO4 groups without dissociation of SO2. A correlation is found between changes in the electronic and chemical properties of beta-FeMoO4, beta-NiMoO4, and beta-MgMoO4. beta-NiMoO4 exhibits a large density of metal states near the top of its valence band and a substantial reactivity toward H-2 and H2S. beta-MgMoO4 displays completely opposite trends, and beta-FeMoO4 is an intermediate case between the two extremes.