Dynamics of Pd monomers and dimers adsorbed on the (001) surfaces of strongly correlated nickel oxides

• Ab-initio calculations on effects of oxide supports on the dynamics of Pd monomers and dimers on NiO(001).
• The surface diffusion of Pd monomers occurred by a hopping process.
• The surface diffusion of Pd dimers occurred by rotational and sliding processes.
• The dynamic properties and the sintering of Pd on NiO(001) were compared with those of Pd on MgO(001).

The adsorption and diffusion of Pd monomers and dimers on the (001) surfaces of strongly correlated nickel oxides were investigated using density functional theory combined with the on-site Coulomb repulsion U. The results were compared with those of Pd on nonmagnetic MgO(001). For the Pd monomer, the most stable adsorption site was found to be near the surface O atom. The surface diffusion of the Pd monomer occurred by a hopping process over surface hollow sites. The diffusion energy barrier was 0.21 eV, which was lower than that for Pd on MgO(001). In the case of the Pd dimer, the smallest and stable cluster, the most stable adsorption structure had a flat geometry, with both Pd atoms sitting above the neighboring surface O atoms. The surface diffusion of the Pd dimer occurred by rotational and sliding processes, in contrast to that of the Pd dimer on MgO(001). The diffusion energy barriers ranged from 0.33 to 0.36 eV. The values for the surface diffusion of Pd dimers on NiO(001) were lower than those of Pd on MgO(001). This suggests that Pd dimers move more rapidly on NiO(001) than on MgO(001), and that the sintering of Pd clusters closely related to catalytic activities can occur more easily compared to that of Pd on MgO(001).