Regulating socketed geometry of nanoparticles on perovskite oxide supports for enhanced stability in oxidation reactions

Heterogeneous catalysts with highly dispersed active particles on supports often face stability challenges during high-temperature industrial applications. The ex-solution strategy, which involves in situ extrusion of metals to form socketed particles, shows potential for addressing this stability issue. However, a deeper understanding of the relationship between the socketed geometry of these partially embedded nanoparticles and their catalytic performance is still lacking. Here, in situ transmission electron microscopy and theoretical calculations are utilized to investigate the oxygen-induced ex-solution process of Pd-doped LaAlO₃ with varying concentrations of La vacancies (La_xAl_0.9Pd_0.1O_3-δ). We find that the socketed geometry of Pd-based particles can be tuned by manipulating the levels of La deficiencies in the oxide support, which in turn influences the catalytic performance in high-temperature oxidation reactions. As for the socketed particles, the balance between particle size and outcrop height is crucial for determining the oxidation activity and sinter-resistance behavior. Consequently, the optimized catalyst, La_0.8Al_0.9Pd_0.1O_3-δ, exhibits superior catalytic performances, particularly high stability (still working after aging at 1000 °C for 50 h) and water resistance in various combustion reactions (e.g., CH₄ oxidation and C₃H₈ oxidation).