In situ oxidation study of MgO(1 0 0) supported Pd nanoparticles

We have investigated the oxidation behavior of Pd nanoparticles grown epitaxially on MgO(1 0 0) single crystal substrates. We find that the interaction of oxygen with octahedral Pd nanoparticles at 500 K can be subdivided in three stages: above 10⁻⁶ mbar O₂ pressure, the particles start to flatten; above 10⁻³ mbar, the particles begin to shrink laterally and to be less truncated at the corners. The formation of epitaxial bulk PdO sets in at oxygen pressures above 0.1 mbar, which is accompanied by a continuous shrinkage of the Pd particles. Our results point to a novel nanoparticle oxidation mechanism: the Pd particles act as dissociation centers for O₂ and serve at the same time as source for Pd atoms resulting in epitaxial PdO growth on MgO(1 0 0).