Formation and Diffusion of Subsurface Adsorbates at Electrodes
journal contributionposted on 07.07.2018 by Björn Rahn, Olaf M. Magnussen
Any type of content formally published in an academic journal, usually following a peer-review process.
We report direct observation of the formation of a subsurface species at metal electrodes in liquid electrolytes and of its migration within the solid’s surface layer, below a chemisorbed electrochemical double layer. Using in situ video-rate scanning tunneling microscopy, we find for adsorbed sulfide on bromide-covered Ag(100) electrodes reversible transitions between adsorption sites on top of the surface and within a vacancy in the first Ag layer. In the latter state, the sulfide surface diffusion can be enhanced by orders of magnitude, which we attribute to vacancy-mediated diffusion underneath the bromide adlayer. The high dynamics within the surface layer, indicated by these observations, may open up alternative pathways in electrocatalytic reactions and growth processes.