Transient stuctures of PdO during CO oxidation over Pd(100)

In situ high-energy surface X-ray diffraction was employed to determine the surface structure dynamics of a Pd(100) single crystal surface acting as a model catalyst to promote CO oxidation. The measurements were performed under semi-realistic conditions, i.e. 100 mbar total gas pressure and 600 K sample temperature. The surface structure was studied in detail both in a steady gas ow and in a gradually changing gas composition with a time resolution of 0.5 sec. Our results show that \sqroot-PdO(101) surface oxide forms in a close to stoichiometric O2 and CO gas mixture as the mass-spectrometry indicates a transition to a highly active state with the reaction rate limited by the CO mass transfer to the Pd(100) surface. Using a low excess of O2 in the gas stoichiometry, islands of bulk oxide grow epitaxially in the same (101) crystallographic orientation of the bulk PdO unit cell according to a Stranski-Krastanov type of growth. The morphology of the islands is analyzed quantitatively. Upon further increase of the O2 partial pressure a polycrystalline Pd oxide forms on the surface