We applied the PBE+U method to investigate the mechanism of ethane oxidative dehydrogenation reaction (ODH) on the MoO3(010) surface. Our systematic study shows that ethylene generation is energetically a favorable pathway from the horizontal C2H6 adsorption. The vertical adsorption of C2H6 leads to the aldehyde generation along the α-oxidative dehydrogenation pathway (α-ODH). However, along the β-ODH pathway, the ethylene oxide formation is identified as the final product but may transform to produce ethylene from the CH2CH2O intermediate. The formation energy of oxygen vacancy (ΔEf v) of all types of oxygen atoms of the MoO3(010) surface are characterized with the on-site Coulomb correction, being reasonably consistent with the HSE results. The U correction leads to the mismatching between the dz 2 orbital of Mo and pz orbitals of the terminal oxygen and consequently weakens the Mo–O chemical bond. Therefore, the weakened Mo–O chemical bond can increase the possibility of forming the oxygenated species, such as aldehyde and ethylene oxide.
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