Mechanism of Selective Oxidation of Propene to Acrolein on Bismuth Molybdates from Quantum Mechanical Calculations

In order to provide a basis for understanding the fundamental chemical mechanisms underlying the selective oxidation of propene to acrolein by bismuth molybdates, we report quantum mechanical studies (at the DFT/B3LYP/LACVP** level) of various reaction steps on bismuth oxide (Bi 4 O 6 /Bi 4 O 7 ) and molybdenum oxide (Mo 3 O 9 ) cluster models. For CH activation, we find a low-energy pathway on a Bi V site with a calculated barrier of Δ H ⧧ = 11.0 kcal/mol (Δ G ⧧ = 30.4 kcal/mol), which is ∼3 kcal/mol lower than the experimentally measured barrier on a pure Bi 2 O 3 condensed phase. We find this process to be not feasible on Bi III (it is highly endothermic, Δ E = 50.9 kcal/mol, Δ G = 41.6 kcal/mol) or on pure molybdenum oxide (prohibitively high barriers, Δ E ⧧ = 32.5 kcal/mol, Δ G ⧧ = 48.1 kcal/mol), suggesting that the CH activation event occurs on (rare) Bi V sites on the Bi 2 O 3 surface. The expected low concentration of Bi V could explain the 3 kcal/mol discrepancy between our calculated barrier and experiment. We present in detail the allyl oxidation mechanism over Mo 3 O 9, which includes the adsorption of allyl to form the π-allyl and σ-allyl species, the second hydrogen abstraction to form acrolein, and acrolein desorption. The formation of σ-allyl intermediate is reversible, with forward Δ E ⧧ (Δ G ⧧ ) barriers of 2.7 (9.0 with respect to the π-allyl intermediate) kcal/mol and reverse barriers of 21.6 (23.7) kcal/mol. The second hydrogen abstraction is the rate-determining step for allyl conversion, with a calculated Δ E ⧧ = 35.6 kcal/mol (Δ G ⧧ = 37.5 kcal/mol). Finally, studies of acrolein desorption in presence of gaseous O 2 suggest that the reoxidation significantly weakens the coordination of acrolein to the reduced Mo IV site, helping drive desorption of acrolein from the surface.