Local Activity and Selectivity Hotspots in Cu‐Pt Model Thin‐Film Electrocatalysts for Oxygen Reduction

ABSTRACT While state‐of‐the‐art alloy catalysts for the oxygen reduction reaction (ORR), a key process for future sustainable energy provision, rely on platinum‐rich materials, alloys containing less noble metals may play an increasingly important role. In particular, Cu–Pt systems are among state‐of‐the‐art electrocatalysts for O 2 electro‐reduction, demonstrating high activity and selectivity for the four‐electron pathway. This study explores the behavior of Cu–Pt model thin film alloy catalysts using electrochemical scanning tunneling microscopy (EC‐STM), a technique capable of detecting active sites and areas for surface catalytic processes under reaction conditions. Our findings indicate that the nature of active centers changes depending on whether the final product is H 2 O or H 2 O 2, which can also be generated in parallel. Active centers are located on the (111) terraces for the four‐electron ORR and shift to step defects if the hydrogen peroxide generation starts. On the other hand, the grain boundaries do not seem to contribute to the sample activity. These findings can be used in designing the shape of nanoparticles for improved nanostructured materials for energy applications.