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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 x 10(-8) to 5 x 10(-5) mbar, the (112) surface undergoes a massive rearrangement and (113)and (335)-type facets are formed. Further increase of the O-2 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 O-2 and 623 K. Kinetic barriers for the formation of the PdO bulk oxide are observed to be reduced compared to low index Pd surfaces. (Less)

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