Electronic structure and oxygen vacancies in PdO and ZnO: validation of DFT models

PdO is one of the most important catalytic materials currently used in the industry. In redox catalytic reactions involving PdO, the bulk phase is an additional source of oxygen. This leads to strong transformations not only at the surface of PdO but also in the near sub-surface and bulk regions. The redox process is, therefore, governed not only by the extent of PdO d-band filling, but also depends on the material properties of the PdO crystal—the ease with which its structure can be deformed. Methane oxidation is of key industrial interest, and therein the rate of CH4 conversion depends strongly on the reversible oxygen defects formation on the surface and in the bulk of the catalyst. The present study gives a first insight into these complex phenomena at the atomistic level. Comparison of different density functional theory (DFT) approaches and their capacity to reproduce experimental values of the heat of formation as well as the band gap of the PdO are discussed in detail. Results from DFT calculations for an oxygen vacancy creation in the bulk and on the surface of PdO are presented and compared at the level of accuracy of the implemented approaches with defect calculations for ZnO. Many different modeling approaches based on functionals and pseudopotentials (non-modified PP and empirically tuned) have been evaluated in their aptness to capture key PdO properties. It was shown that simulations with the PP-115 pseudopotential gave the closest possible agreement to the relevant PdO thermodynamic data and energy of oxygen vacancy formation.