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

Abstract

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.

Keywords

• Platinum
• High-entropy alloys
• Surface free energy
• Surface segregation
• Oxygen reduction reaction
• Model catalyst study