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Synthesis, characterization, and reactivity of oxide-supported molybdenum oxide

Thesis/Dissertation ·
OSTI ID:6110229

Molybdenum oxide was supported on silicon oxide, aluminum oxide, and magnesium oxide with the use of Mo({eta}{sup 3}-C{sub 3}H{sub 5}){sub 4}, Mo{sub 2}({eta}{sup 3}-C{sub 3}H{sub 5}){sub 4}, MoCl{sub 5}, (NH){sub 4}Mo{sub 7}O{sub 24}{center dot}4H{sub 2}O, H{sub 2}(MoO{sub 3}C{sub 2}O{sub 4}){center dot}2H{sub 2}O precusors. Oxidized samples were characterized with laser Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The molybdenum carbonyl species formed by uv photoreduction of Mo{sup 6+}/SiO{sub 2} in CO were studied with infrared spectroscopy and temperature programmed decomposition. The relationship between Mo/SiO{sub 2} structure and catalytic behavior was studied with the structure sensitive partial oxidation of methanol. For the systems studied, the structures of the hydrated molybdate submonolayer surface species were found to be independent of the molybdenum precursor used for preparation. These structures were governed by the pH dependent polymerization chemistry of molybdate anions and the isoelectric point of the hydrated support oxides. Acidic molybdena was only weakly held on silica because of the low isoelectric point of the support, resulting in the formation of octahedrally-coordinated polymolybdates. Alumina, with a slightly basic isoelectric point, led to the formation of molybdate tetrahedra at low molybdenum loadings and polymolybdate at higher loadings. Molybdate tetrahedra were observed on basic magnesia at all loadings studied. The formation of crystalline molybdenum compounds was governed by the preparation procedure, the molybdenum content, the calcination temperature, and the support impurities.

Research Organization:
Texas Univ., Austin, TX (United States)
OSTI ID:
6110229
Country of Publication:
United States
Language:
English

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