Mechanism of selective oxidation of propene to acrolein on bismuth molybdates from quantum mechanical calculations

Sanja Pudar, Jonas Oxgaard, Kimberly Chenoweth, Adri C.T. Van Duin, William A. Goddard

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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 4O 6/Bi 4O 7) and molybdenum oxide (Mo 3O 9) cluster models. For CH activation, we find a low-energy pathway on a Bi v site with a calculated barrier of ΔH‡ -11.0 kcal/mol (ΔG‡ = 30.4 kcal/mol), which is ∼3 kcal/mol lower than the experimentally measured barrier on a pure Bi 2O 3 condensed phase. We find this process to be not feasible on Bi III (it is highly endothermic, ΔE = 50.9 kcal/mol, ΔG = 41.6 kcal/mol) or on pure molybdenum oxide (prohibitively high barriers, ΔE‡ = 32.5 kcal/mol, ΔG‡ = 48.1 kcal/mol), suggesting that the CH activation event occurs on (rare) Biv sites on the Bi 2O 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 3O 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 ΔE‡ (ΔG‡) 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 ΔE‡ = 35.6 kcal/mol (ΔG‡ = 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.

Original languageEnglish (US)
Pages (from-to)16405-16415
Number of pages11
JournalJournal of Physical Chemistry C
Issue number44
StatePublished - Nov 8 2007

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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