Oxygen interaction with the Pd(112) surface: From chemisorption to bulk oxide formation

We investigated the interaction of oxygen with the Pd(112) surface from ultrahigh vacuum up to 5 mbars oxygen partial pressure in a temperature range from 523 to 673 K. We combined in situ surface x-ray diffraction with scanning tunneling microscopy, high-resolution core-level spectroscopy, and low-energy electron diffraction. A structural model of the clean Pd(112) is proposed based on the x-ray-diffraction data. The morphology of the Pd(112) surface is strongly influenced by the oxidation conditions: at 673 K, upon exposure to oxygen at pressures from 2×10^-8 to 5×10^-5 mbar, the (112) surface undergoes a massive rearrangement and (113)- and (335)-type facets are formed. Further increase of the O₂ partial pressure leads to a new rearrangement into (111)- and (113)-type facets. This is in contrast to the previous observation that (112) facets are stabilized on MgO supported Pd nanoparticles under oxygen exposure [P. Nolte, A. Stierle, N. Kasper, N. Y. Jin-Phillipp, N. Jeutter, and H. Dosch, Nano Lett. 11, 4697 (2011)]. Based on the core-level spectroscopy and scanning tunneling microscopy measurements, the transition from chemisorbed oxygen to surface oxide formation was identified to take place at pressures of 10^-3 mbar O₂ and 623 K. Kinetic barriers for the formation of the PdO bulk oxide are observed to be reduced compared to low index Pd surfaces.