A series of activated alumina-supported vanadium oxide catalysts with various V2O5 loadings ranging from 5 to 25 wt% have been prepared by wet impregnation technique. A combination of various physicochemical techniques such as BET surface area, oxygen chemisorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR), thermal gravimetric analysis (TGA), and Fourier transform infrared (FTIR) were used to characterize the chemical environment of vanadium on the alumina surface. Oxygen uptakes were measured at 370 degreesC with prereduction at the same temperature, which appears to yield better numerical values of dispersion and oxygen atom site densities. XRD and FTIR results suggest that vanadium oxide exists in a highly dispersed state below 15 wt% V2O5 loading and in the microcrystalline phase above this loading level. TPR profiles of V2O5/Al2O3 catalysts exhibit only a single peak at low temperature up to 15 wt% V2O5. It is suggested that the low-temperature reduction peak is due to the reduction of surface vanadia, which has been ascribed to the tetrahedral coordination geometry of the V ions. TPR Of V2O5/Al2O3 at higher vanadia loadings exhibited three peaks at reduction temperatures, indicating that bulk-like vanadia species are present for these catalysts only at higher vanadia loadings, with V ions in an octahedral coordination. The TPR profiles Of V2O5/Al2O3 catalysts indicate that at loadings lower than 15% vanadia forms isolated surface vanadia species, while two-dimensional structure and V2O5 crystallites become prevalent in highly loaded (>15% V2O5) systems. Liquid-phase oxidation of ethylbenzene to acetophenone has been employed as a chemical probe reaction to examine the catalytic activity. Ethylbenzene oxidation results reveal that 15% V2O5/Al2O3 is more active than higher vanadia loading catalysts. (C) 2003 Elsevier Inc. All rights reserved.