CO$_{2}$ activation on TiO$_{2}$-supported Cu$_{5}$ and Ni$_{5}$ nanoclusters: Effect of plasma-induced surface charges

Surface charging is an important factor in many plasma-surface interactions and in particular in plasma catalysis. In this study, we investigated the effect of excess electrons induced by plasma on the adsorption properties of CO$_{2}$ on titania-supported Cu$_{5}$ and Ni$_{5}$ clusters using spin polarized and dispersion corrected density functional theory. In addition, the effect of excess electrons on the deposition of Ni and Cu nanoclusters as well as on CO$_{2}$ adsorption on a pristine anatase TiO$_{2}$ ($101$) slab was studied. Our results indicate that CO2 binds more strongly with a negatively charged surface. Increasing the surface charge density leads to a pronounced increase of the adsorption energy. Additionally, we also employed DFT+U calculations for cross-checking the results while accounting for the strong on-site Coulomb interactions, and the same trends are found.