Theoretical Study of Propylene Epoxidation over Cu₂O(111) Surface: Activity of O^2–, O^–, and O₂^– Species

Propylene epoxidation catalyzed by cuprous oxide in the presence of oxygen species is important in both technology and scientific fields, and the active specieslattice oxygen (O2–), adsorbed atomic oxygen (O–), or adsorbed molecular oxygen (O2–)plays a significant role in the catalytic reaction. In the present work, the mechanism of propylene epoxidation and dehydrogenation on a Cu2O­(111) facet with different oxygen species has been studied through density functional theory (DFT) calculations with a Hubbard U correction in detail. The whole reaction processes of propylene oxidation includes two different routes: allylic hydrogen stripping (AHS) reactions and propylene epoxidation reactions. Acrolein can be generated by two H-stripping reactions in the AHS path, and propylene oxide (PO) is formed through the oxametallacycle propylene (OMP) intermediate. The calculated results show that the adsorbed atomic oxygen (O–) is the most active oxygen species for the selective oxidation of propylene because it has the strongest basicity among these three oxygen species, whereas the adsorbed molecular oxygen (O2–) has the highest selectivity for the PO formation among these three different oxygen species because of its relatively low basic properties and moderate oxidation compared to those of atomic oxygen (too active oxidation) or lattice oxygen (less oxidation due to the closed-shell nature of the oxide system). Moreover, a microkinetic simulation was used to confirm the above DFT calculation results. The aim of the present study is to give a guide in choosing the most efficient active oxygen species for PO formation, which should be the one with the moderate oxidant