Effects of Dopants on the Structural, Electronic, and Energetic Properties of (ZrO2)16 Clusters

The integration of dopants into ZrO2-based clusters provides the possibility to modulate their physicochemical properties, making small clusters promising candidates for various applications, such as catalysis. However, the synergistic interactions between doping and adsorption of single atoms into ZrO2 remain poorly understood. Therefore, in this study, we investigate the influence of lanthanum (La) doping and rhodium (Rh) single-atom adsorption on the physicochemical properties of (ZrO2)16 clusters using density functional theory calculations combined with data science approaches. We found that both doping and adsorption processes lead to minor local structural changes. La doping induces minimal distortions while preserving the overall stability of the cluster, as evidenced by consistent binding energy values. Rh adsorption has a preference to bind near the O-La moieties. In contrast, the electronic structure is majorly affected by Rh adsorption, by narrowing the HOMO-LUMO energy gap, and enhancing the reactivity of those modified Zr16O32 clusters. Furthermore, Hirshfeld charge analysis reveals a significant charge redistribution following La doping, which is enhanced by the adsorption of a single Rh atom, resulting in localized electronic changes.