Ammoxidation of 2-chlorotoluene (2-CLT) has been carried out over vanadates and supported vanadates in the temperature range 350-450 degrees C. The catalysts were characterized by XRD, XPS, FT-IR, and Raman and surface area measurement. A maximum yield of 76% of 2-CLBN was obtained at a temperature of 425 degrees C and a 2-CLT:NH3:air mole ratio of 1:8:22. DFT computations suggest that the reaction follows a Mars-van Krevelen (MVK) type of redox mechanism. The catalyst is first reduced by ammonia, producing an imine species. The 2-CLT molecule is also adsorbed through a vanadyl oxygen to produce a CH2=C6H5 species. This moiety is adsorbed over the catalyst through an imine formed on the surface to produce 2-chlorobenzonitrile. XPS spectra of fresh and spent catalysts confirm reduction of the catalyst during ammoxidation. (C) 2016 Elsevier Inc. All rights reserved.