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  On the mechanism of Ag(111) sub-monolayer oxidation: a combined electrochemical, in situ SERS and ex situ XPS study

Savinova, E. R., Zemlyanov, D., Pettinger, B., Scheybal, A., Schlögl, R., & Doblhofer, K. (2000). On the mechanism of Ag(111) sub-monolayer oxidation: a combined electrochemical, in situ SERS and ex situ XPS study. Electrochimica Acta, 46(2-3), 175-183. doi:10.1016/S0013-4686(00)00571-5.

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 Creators:
Savinova, Elena R., Author
Zemlyanov, D., Author
Pettinger, Bruno1, Author              
Scheybal, Andreas2, Author              
Schlögl, Robert2, Author              
Doblhofer, Karl1, Author              
Affiliations:
1Physical Chemistry, Fritz Haber Institute, Max Planck Society, ou_634546              
2Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, ou_24023              

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Free keywords: Ag(111); Sub-monolayer oxidation; Alkaline electrolyte; Surface enhanced Raman spectroscopy (SERS); X-ray photoelectron spectroscopy (XPS); ultraviolet photoelectron spectroscopy (UPS)
 Abstract: In the present work in situ surface enhanced Raman spectroscopy (SERS), ex situ X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) are used to study the interface between a Ag(111) electrode and an alkaline electrolyte. Formation of a number of potential-dependent adsorbates is observed above the point of zero charge (Epzc) of the Ag electrode. These are: OH groups (OHadsγ−) and oxide-like species (Oadsδ−). Electrochemisorbed hydroxide species show by the appearance of Raman bands at 540–560 cm−1 and at 803–819 cm−1, attributed to Ag–OH stretching and AgO–H bending vibrations respectively. Strong isotope shift of the Raman bands towards lower frequencies is observed in D2O solutions, proving their assignment. The Oadsδ− and OHadsγ− species are characterised by the O 1s peaks at ca. 529.5 and 531.6, respectively. Formation of the above-mentioned species is verified also by the UP spectra of the emersed electrodes, showing the bands at 3.0 eV typical for the oxide-like adsorbates and 9.0 and 11.1 eV for hydroxo-groups. The OHadsγ− and Oadsδ− species are negatively charged, as evidenced by the adsorption of Na+ on the Ag electrode positive to the Epzc. A mechanism of the Ag(111) sub-monolayer oxidation is suggested on the basis of combined evidence from cyclic voltammetry, in situ SERS, ex situ XPS and UPS.

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Language(s): eng - English
 Dates: 1999-11-262000-05-022000-11-01
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 1332
DOI: 10.1016/S0013-4686(00)00571-5
 Degree: -

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Title: Electrochimica Acta
  Abbreviation : Electrochim. Acta
Source Genre: Journal
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Publ. Info: Oxford, UK : Pergamon-Elsevier Science Ltd
Pages: 9 Volume / Issue: 46 (2-3) Sequence Number: - Start / End Page: 175 - 183 Identifier: ISSN: 0013-4686
CoNE: https://pure.mpg.de/cone/journals/resource/954925396434