Reaction network for the total oxidation of toluene over CuO–CeO 2/Al 2O 3

Abstract

The total oxidation of toluene was studied over a CuO–CeO 2/γ-Al 2O 3 catalyst in a Temporal Analysis of Products (TAP) setup in the temperature range 673–923 K in the presence and absence of dioxygen and at various degrees of reduction of the catalyst. The reaction rate significantly decreases over a mildly reduced catalyst. Under vacuum and at high-temperature, mild reduction also occurs in the absence of toluene. In the presence of dioxygen, the catalyst activity is determined by weakly bound surface lattice oxygen atoms and adsorbed oxygen species, the lifetime of which is close to 1 s. The weakly bound oxygen is highly reactive and is only found over a fully oxidized catalyst. The formation of products containing 18O during the isotope-exchange experiments with 18O 2 indicates that both lattice and adsorbed oxygen are involved in (a) reoxidation of mildly reduced copper oxide and (b) abstraction of hydrogen atoms and scission of C–C bonds. Isotopic labeling with C 6H 5– 13CH 3 and C 6H 5–CD 3 indicates the following reaction paths: adsorption of toluene on the active site, containing Cu 2+ with 4–5 adjacent surface lattice oxygen atoms; the simultaneous abstraction of H from the methyl and the phenyl group followed by the abstraction of the methyl carbon and next the destruction of the aromatic ring.