Coadsorbate‐Induced Reversal of Solid–Liquid Interface Dynamics
| Autor: | Björn Rahn, Olaf M. Magnussen, Rui Wen, Johannes Stremme, Lukas Deuchler, E. Pehlke, A. Franke |
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| Rok vydání: | 2018 |
| Předmět: |
Surface diffusion
Aqueous solution Materials science General Chemistry 02 engineering and technology General Medicine 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Catalysis law.invention 0104 chemical sciences chemistry.chemical_compound Adsorption chemistry law Chemical physics Bromide Vacancy defect Scanning tunneling microscope Diffusion (business) Isostructural 0210 nano-technology |
| Zdroj: | Angewandte Chemie. 130:6173-6176 |
| ISSN: | 1521-3757 0044-8249 |
| Popis: | 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 in situ 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. |
| Databáze: | OpenAIRE |
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