Formation of Ce³⁺ at the cerium dioxide (1 1 0) surface by doping

The formation of Ce³⁺ ions in CeO₂ is key for its applications. We present density functional theory (DFT) studies of doping of the CeO₂ (1 1 0) surface with +5 cations, Ta and Nb, as a route to formation of Ce³⁺. We use DFT corrected for on-site Coulomb interactions (DFT + U, U = 5 eV) and hybrid DFT (HSE06 functional). With both methods we find formation of Ce³⁺ ions due to the extra electron from the dopant residing on a single Ce site, confirming the DFT + U description of these systems. Doping with Nb and Ta activates the surface to NO₂ reduction - there is no interaction with the undoped surface but the Ce³⁺ ion in the doped surface interacts strongly with NO₂.