Scheelite Catalysts for Thermal Mineralization of Toluene: A Mechanistic Overview

Toluene, a highly stable aromatic hydrocarbon, is utilized as a benchmark molecule for thermal mineralization by the catalytic community. Mostly, the catalysts used for toluene mineralization either use platinum group metals (PGM) as catalysts or are regulated by a plasma incinerator. Though these catalysts/processes promise better efficiency and lower reaction temperature, they are neither cost-effective nor do they produce thermally stable byproducts. However, most of the metal-oxide catalysts used for toluene degradation are less efficient owing to incomplete mineralization and formation of stable intermediates, which results in higher mineralization temperature. The present work showcases tungsten- and molybdenum-based Scheelites [BaXO₄ (X = W, Mo, and Mo_0.5W_0.5)], which have been utilized for toluene mineralization at ∼200 °C. The intermediates formed during adsorption and thermal reaction are deciphered as a function of temperature using in situ FT-IR studies including their kinetic behavior. These surface intermediates formed over the Scheelite catalysts under an oxidative/inert atmosphere elucidate the toluene mineralization mechanism as a function of temperature/time. The surface active sites for these oxide catalysts for both adsorption and formation of reaction intermediates are deciphered using detailed X-ray photoelectron spectroscopy (XPS) studies. It shows the effective role of the oxidation states of constituent oxides M-O (M = Mo/ W) in the reaction mechanism. Mineralization of toluene in a nonoxidative atmosphere shows a Mars and Van Krevelen (MVK) type of mechanism, suggesting participation of lattice oxygen for the catalytic reaction. To the best of our knowledge, this work represents one of the lowest temperatures achieved for toluene mineralization using oxide catalysts. The identification of reaction intermediates can guide further optimization efforts to minimize the mineralization temperature.