Behavior of Molybdenum⁻Vanadium Mixed Oxides in Selective Oxidation and Disproportionation of Toluene

This study deals with the behavior of molybdenum⁻vanadium (Mo/V) mixed oxides catalysts in both disproportionation and selective oxidation of toluene. Samples containing different Mo/V ratios were prepared by a modified method using tetradecyltrimethylammonium bromide and acetic acid. The catalysts were characterized using several techniques: nitrogen adsorption⁻desorption isotherms, X-Ray diffraction (XRD), ammonia temperature-programmed desorption (TPD-NH₃), temperature-programmed reduction by hydrogen (H₂-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier-transform infrared-spectroscopy (FTIR) and ultraviolet-visible spectroscopies (UV⁻VIS). The XRD results evidenced the presence of orthorhombic α-MoO₃ and V₂O₅ phases, as well as monoclinic β-MoO₃ and V₂MoO₈ phases, their abundance depending on the Mo to V ratio, while the TPD-NH₃ emphasized that, the total amount of the acid sites diminished with the increase of the Mo loading. The TPR investigations indicated that the samples with higher Mo/V ratio possess a higher reducibility. The main findings of this study led to the conclusion that the presence of strong acid sites afforded a high conversion in toluene disproportionation (Mo/V = 1), while a higher reducibility is a prerequisite to accomplishing high conversion in toluene oxidation (Mo/V = 2). The catalyst with Mo/V = 1 acquires the best yield to xylenes from the toluene disproportionation reaction, while the catalyst with Mo/V = 0.33 presents the highest yield to benzaldehyde.