Interaction of Li, Na and K overlayers with Pt(111): Structure and fundamental properties

In this computational study, the adsorption of alkali metal atoms on Pt(111) is studied by periodic electronic structure calculations based on density functional theory. This study is motivated by the promoting role of alkali metal atoms in several reactions in electro- and heterogeneous catalysis. In a systematic approach, we first study the explicit interaction of the atoms with the Pt(111) surface focusing on structural and electronic details of the alkali interaction with the metal substrate, also as a function of the adsorbate coverage. Furthermore, we contrast our findings with corresponding results for the anionic counterpart, the adsorption of halogen atoms, identifying common and diverse trends. • Li, Na and K adatoms interact with Pt(111) via adsorption while substitutive insertion into the lattice is energetically less favorable. • The considered adatoms are positively charged and lower the work function of Pt(111). • As the result the adatoms have a significant impact on the catalytic properties of Pt.