Thermal Evolution and Instability of CO-Induced Platinum Clusters on the Pt(557) Surface at Ambient Pressure.

Carbon monoxide (CO) is one of the most-studied molecules among the many modern industrial chemical reactions available. Following the Langmuir-Hinshelwood mechanism, CO conversion starts with adsorption on a catalyst surface, which is a crucially important stage in the kinetics of the catalytic reaction. Stepped surfaces show enhanced catalytic activity because they, by nature, have dense active sites. Recently, it was found that surface-sensitive adsorption of CO is strongly related to surface restructuring via roughening of a stepped surface. In this scanning tunneling microscopy study, we observed the thermal evolution of surface restructuring on a representative stepped platinum catalyst, Pt(557). CO adsorption at 1.4 mbar CO causes the formation of a broken-step morphology, as well as CO-induced triangular Pt clusters that exhibit a reversible disordered-ordered transition. Thermal instability of the CO-induced platinum clusters on the stepped surface was observed, which is associated with the reorganization of the repulsive CO-CO interactions at elevated temperature.