An electrochemical and Raman spectroscopic study of silver, gold, palladium and platinum electrodes
An electrochemical and Raman spectroscopic study of silver, gold, palladium and platinum electrodes
Initial studies of pyridine adsorption by simultaneous differential capacitance measurement and Raman spectroscopy have led to the proposal of a model for pyridine adsorption, where ring reorientation occurs at specific potentials in the range -200 mV to -700 mV (vs SCE). Furthermore, results have conclusively shown that within this potential range, surface enhanced Raman scattering (SERS) spectra are truly representative of the surface as a whole, because of their identity with diminished SERS (DSERS) spectra and the similarity of potential modulation spectra from SERS, DSERS and smooth silver surfaces. Observation of a potential dependent Raman spectrum from a smooth, unanodised silver surface represents a significant step forward in the detection of very weak Raman signals, emitting at an estimated rate of only 36 photons per second. SERS spectroscopy was employed to study ferricyanide adsorption at roughened gold electrodes and smooth palladium hydride electrodes. Additionally, potential modulation spectroscopy with a Raman spectrograph was used to investigate the electroreduction of ferricyanide ions, in aqueous solution at smooth platinum and palladium electrodes. SERS spectra showed that specific adsorption of ferricyanide occurred in all XCl (X = Li+, Na+, K+, Cs+) solutions, maximum adsorption was observed in the case of sodium and potassium ions. The potential dependence and frequency shifts of the cyanide stretching modes was taken as evidence for specific adsorption of an ion pair of the form [XFe(CN)6]2-. Potential modulation experiments were more difficult to perform, but results suggested that both ferricyanide and ferrocyanide ions were adsorbed during oxidation/reduction at platinum and palladium electrodes.
University of Southampton
1985
Graves, Pierre Robert
(1985)
An electrochemical and Raman spectroscopic study of silver, gold, palladium and platinum electrodes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Initial studies of pyridine adsorption by simultaneous differential capacitance measurement and Raman spectroscopy have led to the proposal of a model for pyridine adsorption, where ring reorientation occurs at specific potentials in the range -200 mV to -700 mV (vs SCE). Furthermore, results have conclusively shown that within this potential range, surface enhanced Raman scattering (SERS) spectra are truly representative of the surface as a whole, because of their identity with diminished SERS (DSERS) spectra and the similarity of potential modulation spectra from SERS, DSERS and smooth silver surfaces. Observation of a potential dependent Raman spectrum from a smooth, unanodised silver surface represents a significant step forward in the detection of very weak Raman signals, emitting at an estimated rate of only 36 photons per second. SERS spectroscopy was employed to study ferricyanide adsorption at roughened gold electrodes and smooth palladium hydride electrodes. Additionally, potential modulation spectroscopy with a Raman spectrograph was used to investigate the electroreduction of ferricyanide ions, in aqueous solution at smooth platinum and palladium electrodes. SERS spectra showed that specific adsorption of ferricyanide occurred in all XCl (X = Li+, Na+, K+, Cs+) solutions, maximum adsorption was observed in the case of sodium and potassium ions. The potential dependence and frequency shifts of the cyanide stretching modes was taken as evidence for specific adsorption of an ion pair of the form [XFe(CN)6]2-. Potential modulation experiments were more difficult to perform, but results suggested that both ferricyanide and ferrocyanide ions were adsorbed during oxidation/reduction at platinum and palladium electrodes.
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Published date: 1985
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Local EPrints ID: 460746
URI: http://eprints.soton.ac.uk/id/eprint/460746
PURE UUID: 19d15d9a-0b85-4d01-b2ce-a559822c5af0
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Date deposited: 04 Jul 2022 18:29
Last modified: 04 Jul 2022 18:29
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Author:
Pierre Robert Graves
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