Adsorption properties of transition metal atoms on strongly correlated NiO(001) surfaces with surface oxygen vacancies

• First-principles study on the adsorption of transition metals on defective NiO(001).
• The adsorption of transition metals (TMs) has been systematically examined.
• The results demonstrate a significant role of surface vacancies in the adsorption.
• We have discussed about the adsorption of TMs on defective NiO films on metals.

Using first-principles density functional theory combined with on-site Coulomb repulsion U, we have systematically studied the adsorption properties of transition metal (TM) atoms on strongly correlated NiO(001) surfaces with Fs centers (surface O vacancies). For the TM atoms, the adsorption on Fs centers is 1.26–3.18 eV more stable compared to positions near the surface O sites of defect-free NiO(001) surfaces. This indicates that Fs centers play an important role in the binding of TM atoms on O-defective NiO(001) surfaces. An analysis of the electronic structures and the charge redistribution for the adsorption of TM atoms on defective NiO(001) has been performed. The TM atoms are negatively charged, with charges ranging from −0.29 to −0.73 |e||e|. The TM-related states caused by interactions between TMs and surface defect states are found in the gap region of NiO. These results provide important information about controlling and understanding the adsorption properties of TM atoms on metal-supported ultrathin NiO films with surface defects like Fs centers.