Reactivity of Pd–MO2 encapsulated catalytic systems for CO oxidation

In this study, we present an investigation aimed at characterizing and understanding the synergistic interactions in encapsulated catalytic structures between the metal core (i.e., Pd) and oxide shell (i.e., TiO2, ZrO2, and CeO2). Encapsulated catalysts were synthesized using a two-step procedure involving the initial colloidal synthesis of Pd nanoparticles (NPs) capped by various ligands and subsequent sol–gel encapsulation of the NPs with porous MO2 (M = Ti, Zr, Ce) shells. The encapsulated catalytic systems displayed higher activity than the Pd/MO2 supported structures due to unique physicochemical properties at the Pd–MO2 interface. Pd@ZrO2 exhibited the highest catalytic activity for CO oxidation. Results also suggested that the active sites in Pd encapsulated by an amorphous ZrO2 shell structure were significantly more active than the crystalline oxide encapsulated structures at low temperatures. Furthermore, CO DRIFTS studies showed that Pd redispersion occurred under CO oxidation reaction conditions and as a function of the oxide shell composition, being observed in Pd@TiO2 systems only, with potential formation of smaller NPs and oxide-supported Pd clusters after reaction. This investigation demonstrated that metal oxide composition and (in some cases) crystallinity play major roles in catalyst activity for encapsulated catalytic systems.