Ab initio calculations of the chemisorption of atomic H and O on Pt and Ir metal and on bimetallic Pt _x Ir _y surfaces

Abstract Understanding the chemisorption of atoms on precious metal surfaces is of substantial interest for the rational design of heterogeneous and electrochemical catalysts. In this study, we report density functional theory (DFT) investigations of the chemisorption of atomic H and O on bimetallic Pt x Ir y (111) surfaces for bifunctional anode catalyst materials in polymer electrolyte membrane (PEM) fuel cells. We found that for both adsorbates, the adsorption on the Pt(111) surface is in general less exothermic than on the Ir(111) surface. Our study has revealed that chemisorption on the bimetallic surfaces becomes more stable with increasing number of Ir surface atoms at the adsorption site. While for hydrogen atoms the ONTOP sites yield the most negative adsorption energies, the chemisorption of oxygen atoms appears to be most stable on the FCC sites for both the mono- and bimetallic surfaces. Using the ab initio thermodynamics approach, we calculated phase diagrams for the chemisorption of H and O atoms on these metal surfaces in order to transfer our findings to finite temperature and pressure conditions. Our theoretical results may provide an improved understanding of the hydrogen oxidation reaction (HOR) and oxygen evolution reaction (OER) on intermetallic Pt x Ir y (111) surfaces and may be helpful for the rational design of new bifunctional PEM fuel cell anode catalyst materials.