Theoretical study of environmental dependence of oxygen vacancy formation in CeO2

Density functional methods were used to study the environmental dependence of O vacancy formation in CeO2. It was found that an O vacancy in the 2+ charged state has the lowest formation energy for a wide range of Fermi energies (EF) from 0 to ∼1.9eV, while a neutral vacancy becomes the most stable at higher EF values. The O vacancy formation energy can be strongly affected by temperature (T) and the partial pressure of oxygen (PO2). The effect of T and PO2 on the equilibrium compositions of reduced ceria (CeO2−x) was also calculated and showed qualitative agreement with gravimetric experiments.