RESUMO
By carefully mixing Pd metal nanoparticles with CeO2 polycrystalline powder under dry conditions, an unpredicted arrangement of the Pd-O-Ce interface is obtained in which an amorphous shell containing palladium species dissolved in ceria is covering a core of CeO2 particles. The robust contact that is generated at the nanoscale, along with mechanical forces generated during mixing, promotes the redox exchange between Pd and CeO2 and creates highly reactive and stable sites constituted by PdOx embedded into CeO2 surface layers. This specific arrangement outperforms conventional Pd/CeO2 reference catalysts in methane oxidation by lowering light-off temperature by more than 50°C and boosting the reaction rate. The origin of the outstanding activity is traced to the structural properties of the interface, modified at the nanoscale by mechanochemical interaction.
RESUMO
Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria-based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high-energy milling of CeO2-ZrO2 powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities.