Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 29, Pages 9066-9069Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b04903
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- Deutsche Forschungsgemeinschaft [MA1618/15]
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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.
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