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  Co-adsorption of fluoride and hydroxide ions on Ag(111) in alkaline electrolytes: Electrochemical and SHG studies

Danckwerts, M., Savinova, E. R., Horswell, S. L., Pettinger, B., & Doblhofer, K. (2003). Co-adsorption of fluoride and hydroxide ions on Ag(111) in alkaline electrolytes: Electrochemical and SHG studies. Zeitschrift für Physikalische Chemie, 217(5), 557-572. doi:10.1524/zpch.217.5.557.20458.

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10.1524_zpch.217.5.557.20458.pdf (Publisher version), 165KB
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10.1524_zpch.217.5.557.20458.pdf
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2003
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De Gruyer
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 Creators:
Danckwerts, Matthias1, Author           
Savinova, Elena R.1, Author           
Horswell, Sarah L.1, Author           
Pettinger, Bruno1, Author           
Doblhofer, Karl1, Author           
Affiliations:
1Physical Chemistry, Fritz Haber Institute, Max Planck Society, ou_634546              

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Free keywords: Ag(111; Second Harmonic Generation (SHG); Fluoride; Hydroxide; Co-adsorption; Surface oxide; Alkaline electrolyte
 Abstract: Hydroxide (OH–) adsorption at Ag(111)/alkaline electrolyte interfaces is the initial step leading to the formation of surface oxide. We investigate how OH– anion adsorption is influenced by co-adsorption of supporting electrolyte anions (F–). Pure NaF and NaOH as well as mixed electrolytes ranging from pH=5.8 to 14 are investigated. The rotational anisotropy of the second harmonic generation (SHG) signal is measured to distinguish adsorptive processes from structural changes on the Ag surface. Our results clearly show a crossover from F–-dominated to OH–-dominated adsorption, while both species remain charged upon adsorption. At more positive potentials, but below the reversible potential of bulk oxide growth, OH is discharged leading to sub-monolayer oxide build-up, whereas in acidic electrolyte, Ag is dissolved. At intermediate pH, the formation of a structured OH–/F– co-adsorbed layer is proposed.

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Language(s): eng - English
 Dates: 2003
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 17732
DOI: 10.1524/zpch.217.5.557.20458
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Title: Zeitschrift für Physikalische Chemie
  Alternative Title : Z. Phys. Chem.
Source Genre: Journal
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Pages: - Volume / Issue: 217 (5) Sequence Number: - Start / End Page: 557 - 572 Identifier: ISSN: 0044-3336