A density functional theory study of partial oxidation of propylene on Cu2O(001) and CuO(001) surfaces

•Propylene epoxidation mechanism on Cu2O(001) and CuO(001) surfaces is investigated using DFT method.•Acrolein is found to be a thermodynamically more favorable product for both surfaces especially over CuO surface.•The more basic property of the surface oxygen increases the probability of acrolein...

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Bibliographic Details
Published in:Applied surface science 2015-11, Vol.355, p.660-666
Main Authors: Düzenli, Derya, Atmaca, Deniz Onay, Gezer, Miray Gülbiter, Onal, Isik
Format: Article
Language:English
Subjects:
Acroleins
Barriers
Bridging
COPPER OXIDE
Cu2O
CuO
CUPROUS OXIDE
Density functional theory
Epoxidation
Formations
MATHEMATICAL ANALYSIS
Oxide surface
PARTIAL OXIDATION
Propylene
Propylene oxide
Surface chemistry
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Summary:•Propylene epoxidation mechanism on Cu2O(001) and CuO(001) surfaces is investigated using DFT method.•Acrolein is found to be a thermodynamically more favorable product for both surfaces especially over CuO surface.•The more basic property of the surface oxygen increases the probability of acrolein formation over CuO(001) surface. This work theoretically investigates propylene epoxidation reaction on Cu2O(001) and CuO(001) surfaces using periodical DFT method to determine the active copper species within the reaction mechanism. The transition states and energy profiles are calculated for the formation of surface intermediates such as oxametallopropylene (OMP) over Cu2O(001) and oxygen bridging (OB) over CuO(001) and allylic H-stripping reaction (AHS) over both surfaces as well as for formation of products. Propylene oxide (PO) and acetone are obtained through OMP and OB surface intermediates and acrolein generation is observed through allylic H-stripping reaction (AHS). The calculations revealed that the corresponding surface intermediates for epoxidation reaction need to overcome an activation barrier of 13kcal/mol over CuO surface whereas they occur without an energy barrier over Cu2O surface indicating the higher activity of Cu+ species. Acrolein is also found to be a thermodynamically more favorable product for both surfaces especially over CuO surface due to the presence of more surface oxygen atoms on which the basicity has been evaluated by the adsorption of sulfur dioxide. This indicates that the lattice oxygen inherent in both surface types does not participate in PO production.
ISSN:0169-4332
1873-5584
DOI:10.1016/j.apsusc.2015.07.155