The effect of rare earth oxides (RE=Ce, La, Gd, and Dy) doping of alumina support in NiO/γ-Al2O3 system was investi-gated on its catalytic performance in oxidative dehydrogenation (ODH) of cyclohexane. The physicochemical properties of various samples were followed up through N2 physisorption, temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and potentiometric acid-base titration techniques. In the parent NiO/γ-Al2O3 catalyst, Ni species were found to be strongly interacted with alumina surface. Addition of rare earth dopants toγ-Al2O3 in the catalyst system affected the nickel-alumina interaction and resulted in significant modifications in the catalytic performances in the ODH reaction. The results re-vealed the beneficial role of both La2O3 and Gd2O3 doping in enhancing the ODH catalytic activity and selectivity to cyclohexene. H2-TPR and XPS results indicated that majority of Ni species in NiO/La2O3 modifiedγ-Al2O3 were more weakly interacted with La2O3 and alumina whereas both NiO like species and nickel aluminate were present on the surface. Doping with cerium or dyspro-sium increased the nickel-support interaction and led to a decrease in surface nickel concentration. In case of doping with Ce, surface concentration of cerium oxide was higher than those of the other RE oxides; the doped catalyst reached its steady state activity faster than the other catalysts. The acid-base results suggested that RE metals were interacted most likely with acidic surface hydroxyl groups. The degree of nickel-alumina interaction decreased in the following order: LaAl>GdAl>CeAl>DyAl.
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