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In situ Raman spectroscopy studies of the interface between silver(111) electrodes and alkaline NaF electrolytes

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Savinova,  Elena R.
Physical Chemistry, Fritz Haber Institute, Max Planck Society;
Boreskov Institute of Catalysis;

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Kraft,  Peter
Physical Chemistry, Fritz Haber Institute, Max Planck Society;

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Pettinger,  Bruno
Physical Chemistry, Fritz Haber Institute, Max Planck Society;

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Doblhofer,  Karl
Physical Chemistry, Fritz Haber Institute, Max Planck Society;

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Citation

Savinova, E. R., Kraft, P., Pettinger, B., & Doblhofer, K. (1997). In situ Raman spectroscopy studies of the interface between silver(111) electrodes and alkaline NaF electrolytes. Journal of Electroanalytical Chemistry, 430(1-2), 47-56. doi:10.1016/S0022-0728(97)00086-7.


Cite as: https://hdl.handle.net/21.11116/0000-0008-B51A-F
Abstract
The electrochemical interface between Ag(111) single crystal and NaF + NaOH electrolytes at various pH values has been studied
using cyclic voltammetry and in situ Raman spectroscopy. Submonolayer oxidation starts well below bulk silver oxide formation at
potential about -0.6V vs. HglHgO electrode at pH 11. Two potential-dependent Raman bands v1 at 540 to 560cm-1 and v2 at 803 to
819 cm-1 in basic NaF electrolytes are attributed to Ag-OH stretching and AgO-H bending vibrations of electrochemisorbed hydroxide
species. Strong isotope effect is observed in D20 solutions, v2 being shifted to values of 550 to 570cm-1. Fluoride stabilizes the adsorption of hydroxide species. A multistep scheme is proposed that describes the mechanism of formation of hydroxide/oxide species at the considered silver-electrode surface.