Abstract
The catalytic selective oxidation on vanadium antimonate oxides partially doped with titanium was studied. Solids with nominal composition VSbO 4, V 0.8SbTi 0.2O 4 and VSb 0.8Ti 0.2O 4 were prepared by solid-state reaction. The solids were characterised by sorptometry, X-ray diffraction (XRD), temperature programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). Catalytic tests were carried out in a fixed-bed reactor using toluene and air as reactants. It was found that partial substitution of V or Sb by Ti produces changes in the unit-cell composition and the redox properties of the solids. A possible role for V and Sb in the reaction mechanism of partial oxidation was established. Vanadium sites (V 4+) are involved in the incorporation of gaseous oxygen as lattice oxygen and hold the Sb sites in an oxidation state (Sb 5+) high enough to insert the lattice oxygen in the hydrocarbon molecule. A relationship between activity and V 4+/Sb 5+ ratio of the unit-cell was found. The selectivity to benzaldehyde is correlated with the redox properties of the solids while the selectivity to total oxidation products could be interpreted by the site isolation theory.
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