Pt-surface stabilization by high-entropy alloys for enhancing oxygen reduction reaction property: Single-crystal model catalyst study

In this work, we study the oxygen reduction reaction (ORR) properties of Pt-containing 3d transition-metal high-entropy alloy (Pt-HEA) surfaces, focusing on the constituent alloying elements. The surface Pt and underlying Cr-Mn-Co-Ni(111) (Pt/Cr-Mn-Co-Ni(111)) stacked lattice layers, which are synthesized through the vacuum deposition of the underlying alloy and surface Pt stacking layers on Pt(111) substrate, exhibit high pristine ORR activity and structural stability under potential-cycle loading, compared to Pt/Cr-Co-Ni, Pt/Mn-Co-Ni, and Pt/Co-Ni(111) surfaces. The outperformed ORR properties are attributed to the effective suppression of the surface segregation of Cr. This study demonstrates that not only the “high-entropy” effect induced by increasing the numbers of constituent elements but also the “chemical affinity” of Pt and the individual HEA constituent elements determine the ORR performances of Pt-HEA

Surface microstructures and oxygen evolution properties of cobalt oxide deposited on Ir(111) and Pt(111) single crystal substrates

Abstract We investigated the oxygen evolution reaction (OER) activity changes of cobalt oxide (CoOx) thin films on Ir(111) and Pt(111) substrates by repeated OER measurements in 0.1 M KOH. Atomic force microscopy and X‐ray photoelectron spectroscopy analysis of the as‐prepared CoOx/Ir(111) and CoOx/Pt(111) showed similar surface morphologies of the CoOx thin films and almost the same OER overpotentials, which were estimated to be around 430 mV. However, after three OER measurements, the overpotential of CoOx/Ir(111) decreased by 70 mV, whereas that of CoOx/Pt(111) increased slightly. Structural analysis showed that CoOx/Ir(111) revealed the island‐like nanostructures of CoOx dispersed on Ir(111) surface, accompanied by the generation of CoOOH. In contrast, for CoOx/Pt(111), the Pt(111) substrate remains covered by the CoOx thin film. The results suggest that the interaface at CoOx (CoOOH) nano‐islands and Ir(111) substrate are responsible for reducing the OER overpotential