Unexpected Behavior of the Surface Composition of PtRh Alloys during Chemical Reaction

The changes in the surface composition of a Pt(50)Rh(50)(100) alloy due to an ongoing 2H(2) + O(2)--2H(2)O chemical reaction have been studied in situ. Exploiting the high-energy resolution and surface sensitivity of synchrotron radiation core-level spectroscopy it was possible to monitor the population of the two transitions metals atoms at the gas-surface interface. Sequences of fast high-resolution core-level spectra of the Rh3d(5/2), Pt4f(7/2), and O1s core levels showed a continuous exchange of atoms between the first and subsurface layers. An unexpected Pt surface enrichement was found under slightly oxidizing conditions, opposite to what found in a highly oxidizing atmosphere.