Computational Design of PtM (M = Au, Ir, Pd, Rh, and Ru) Binary Alloys for Enhanced Ammonia Oxidation Electrocatalysis

The electrochemical ammonia oxidation reaction (AOR) shows considerable potential for its applications in waste removal and the production of clean energy. While Pt remains the most investigated catalyst for this reaction, its limitations have prompted research into Pt‐based bimetallic alloys. This study investigates both uniform and mixed PtM (M = Au, Ir, Pd, Rh, and Ru) alloys as catalysts for the AOR using density functional theory (DFT). A systematic selection method is used to choose suitable surfaces for testing. The findings indicate that the Oswin–Salomon mechanism is preferred across all surfaces for N 2 (g) formation. Additionally, the results demonstrate that mixed alloys exhibit superior catalytic activity compared to uniform alloys for the AOR. It is found that the atoms in the topmost layer of the alloy are the most significant factor in influencing catalytic activity. Furthermore, the linear relationship between the ‐band center and adsorption energy of key intermediate *NH 2 is confirmed in this work, highlighting the effect of the secondary metal on the electronic structure of the catalyst. The findings provide theoretical insights for the design of high‐performance Pt alloys for AOR and serve as a general guideline for modulating the reactivity of binary alloys for electrocatalysis.