Abstract
The interaction of hydrogen with bimetallic surfaces is assessed and discussed using structurally well defined PdAu and PtRu single crystal surfaces as model systems. The description is based on a correlation between the hydrogen adsorption behavior and the presence and abundance of specific bimetallic nanostructures. The latter are determined quantitatively by high resolution scanning tunneling microscopy. Following the changes in the hydrogen adsorption behavior on surfaces with systematically varied composition and thus varying concentrations of specific structural elements and adsorption ensembles allows a direct correlation between structural and chemical properties and thus to identify the adsorption characteristics of individual adsorption ensembles. This provides a structural basis for parallel theoretical studies, which are essential for a systematic understanding of the complex changes in the adsorption properties.Based on results from experimental studies and calculations, the role of electronic strain and ligand effects, including lateral and vertical ligands, as well the influence of geometric ensemble effects on the hydrogen adsorption characteristics are discussed. The distinct differences between surfaces modified by a monolayer or monolayer islands of a second metal and mixed surfaces such as surface alloys or alloy surfaces are discussed in these terms.