Hydrogen and Ammonia Co-Adsorption on M(1 1 1) and Pd3M(1 1 1) (M = Pd, Ru, Ag, Au, Cu) Surfaces

Ammonia (NH₃) represents a promising zero-emission fuel in hydrogen fuel cells. Membrane reactors for NH₃ decomposition based on Pd-alloys have demonstrated high NH₃ conversion, high hydrogen diffusivity, and high hydrogen selectivity, which allows for the production of high-purity H₂ without the need for gas separation or purification. However, it is observed that Pd-alloy membranes are to a various degree prone to H₂ flux inhibition in the presence of NH₃. Hence, finding proper means to tailor the surface adsorption properties through, e.g., alloying is imperative to further improve the technology. In the current work, hydrogen and ammonia co-adsorption phenomena on <i>M</i>(1 1 1) and Pd₃<i>M</i>(1 1 1) (<i>M</i> = Pd, Ru, Ag, Au, Cu) surfaces are studied using density functional theory calculations. It is shown that the surface adsorption properties are strongly dependent on the surface composition, which can be linked to the corresponding electronic structure at the membrane surface.