Revealing the Nature of Active Sites on Pt-Gd and Pt-Pr Alloys during the Oxygen Reduction Reaction.

For large-scale applications of hydrogen fuel cells, the sluggish kinetics of the oxygen reduction reaction (ORR) have to be overcome. So far, only platinum (Pt)-group catalysts have shown adequate performance and stability. A well-known approach to increase the efficiency and decrease the Pt loading is to alloy Pt with other metals. Still, for catalyst optimization, the nature of the active sites is crucial. In this work, electrochemical scanning tunneling microscopy (EC-STM) is used to probe the ORR active areas on Pt5Gd and Pt5Pr in acidic media under reaction conditions. The technique detects localized fluctuations in the EC-STM signal, which indicates differences in the local activity. The in situ experiments, supported by coordination-activity plots based on density functional theory calculations, show that the compressed Pt-lanthanide (111) terraces contribute the most to the overall activity. Sites with higher coordination, as found at the bottom of step edges or concavities, remain relatively inactive. Sites of lower coordination, as found near the top of step edges, show higher activity, presumably due to an interplay of strain and steric hindrance effects. These findings should be vital in designing nanostructured Pt-lanthanide electrocatalysts.