Investigation of the oxygen coverage effect on the direct epoxidation of propylene over copper through DFT calculations.

The direct epoxidation of propylene is one of the most important selective oxidation reactions in industry. The development of high-performance copper-based catalysts is the key to the selective oxidation technology and scientific research of propylene. The mechanism of propylene's partial oxidation catalyzed by Cu(111) under different oxygen coverage conditions was studied using density functional theory calculations and microkinetic modeling. We report here in detail two parallel reaction pathways: dehydrogenation and epoxidation. The transition states and energy distributions of the intermediates and products were calculated. The present results showed that propylene oxide (PO) selectivity was high under low oxygen coverage, and increasing the oxygen coverage would decrease the PO selectivity but increase the PO activity, and there was an inverse relationship between PO selectivity and activity. Increasing oxygen coverage would reduce the energy barrier for the C-O bond formation of CHO due to the weaker adsorption strength of CH, thus decreasing the PO formation selectivity. On the other hand, increasing oxygen coverage would reduce the energy barrier for the possible reaction steps of propylene epoxidation in general, and thus increasing the catalytic activity. It might be proposed that the active site for propylene epoxidation is the metallic copper or partially oxidized copper in terms of the change of PO formation selectivity with oxygen coverage.