Influence of step geometry on the reconstruction of stepped platinum surfaces under coadsorption of ethylene and CO

We demonstrate the critical role of the specific atomic arrangement at step sites in the restructuring processes of low-coordinated surface atoms at high adsorbate coverage. By using high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we have investigated the reconstruction of Pt(332) (with (111)-oriented triangular steps) and Pt(557) surfaces (with (100)-oriented square steps) in the mixture of CO and C₂H₄ in the Torr pressure range at room temperature. CO creates Pt clusters at the step edges on both surfaces, although the clusters have different shapes and densities. A subsequent exposure to a similar partial pressure of C₂H₄ partially reverts the clusters on Pt(332). In contrast, the cluster structure is barely changed on Pt(557). These different reconstruction phenomena are attributed to the fact that the 3-fold (111)-step sites on Pt(332) allows for adsorption of ethylidyne- a strong adsorbate formed from ethylene- that does not form on the 4-fold (100)-step sites on Pt(557).