Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 21, Pages 6065-6068Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201712728
Keywords
density functional calculations; electrochemistry; scanning tunneling microscopy; surface dynamics
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Funding
- Deutsche Forschungsgemeinschaft [Pe 497/4, MA 1618/15]
- Alexander-von-Humboldt Society
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Coadsorbed anions are well-known to influence surface reactivity and dynamics at solid-liquid interfaces. Here we demonstrate that the chemical nature of these spectator species can entirely determine the microscopic dynamic behavior. Quantitative insitu video-STM data on the surface diffusion of adsorbed sulfur atoms on Cu(100) electrodes in aqueous solution covered by bromide and chloride spectators, respectively, reveal in both cases a strong exponential potential dependence, but with opposite sign. This reversal is highly surprising in view of the isostructural adsorbate arrangement in the two systems. Detailed DFT studies suggest an anion-induced difference in the sulfur diffusion mechanism, specifically an exchange diffusion on the Br-covered surface. Experimental evidence for the latter is provided by the observation of Cu vacancy formation in the Br system, which can be rationalized by a side reaction of the sulfur exchange diffusion.
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