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4089607 
Journal Article 
DFT+U Investigation of Propene Oxidation over Bismuth Molybdate: Active Sites, Reaction Intermediates, and the Role of Bismuth 
Getsoian, AB; Shapovalov, V; Bell, AT 
2013 
Yes 
Journal of Physical Chemistry C
ISSN: 1932-7447
EISSN: 1932-7455 
117 
14 
7123-7137 
WOS:000317552200026 
The mechanism by which propene is selectively oxidized to acrolein over bismuth molybdate has been investigated using the DFT+U variant of density functional theory. In agreement with experiment, the kinetically relevant step is found to be the initial abstraction of hydrogen by lattice oxygen. Several candidate lattice oxygen sites have been examined, the most active of which is found to be a bismuth-perturbed molybdenyl Mo=O oxygen. Hydrogen abstraction generates an allyl radical intermediate, which can diffuse freely across the catalyst surface and ultimately binds to a second molybdenyl oxygen to form an ally, alkoxy intermediate. A second hydrogen is abstracted from this intermediate to produce acrolein. Calculations suggest that only molybdenum centers are reduced during the reaction. However, presence of bismuth in the catalyst is essential for providing the requisite structural and electronic environment at the active site.