A surface enhanced Raman spectroscopic study of electrode/electrolyte interface
A surface enhanced Raman spectroscopic study of electrode/electrolyte interface
Studies by surface enhanced Raman spectroscopy (SERS) of the ferri/ferrocyanide couple have shown the ferricyanide ion to be strongly bound to the surface of a gold electrode. Investigations of the 250 - 650 cm-1 region yield four bands due to the ferricyanide ion, and these are interpreted as being due to a significant distortion of the ion upon the surface. Studies of the cyanide stretching region show that the interpretation of band shapes in this region must be done with care, as the solution species is detected, even in 10mM solutions. The addition of 10mM KC1 is shown to cause large shifts in the band positions due to ion pairing. Fourier transform Raman spectroscopy is shown to be applicable to such systems, and no wavelength dependence of the surface enhanced Raman mechanism is found. SERS is used to study the (pyridinylmethylene)-hydrazinecarbothioamide class of electrode modifiers on gold, and it is found that the 2- substituted isomer is adsorbed at an angle to the surface, whilst the 4- substituted isomer is adsorbed parallel to the surface. No interaction with cytochrome-c can be detected by SERS. The pH dependence of two corrosion inhibitors (benzotriazole and 2-mercaptobenzothiazole) have been studied by SERS on copper and silver electrodes. The anion present in neutral solutions is shown to protonate in acid solutions, leading to a lowering in protection efficiency for benzotriazole. Competitive adsorption of these two compounds shows 2-mercaptobenzothiazole to be adsorbed most strongly.
University of Southampton
1988
Lowry, Roy Brian
(1988)
A surface enhanced Raman spectroscopic study of electrode/electrolyte interface.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Studies by surface enhanced Raman spectroscopy (SERS) of the ferri/ferrocyanide couple have shown the ferricyanide ion to be strongly bound to the surface of a gold electrode. Investigations of the 250 - 650 cm-1 region yield four bands due to the ferricyanide ion, and these are interpreted as being due to a significant distortion of the ion upon the surface. Studies of the cyanide stretching region show that the interpretation of band shapes in this region must be done with care, as the solution species is detected, even in 10mM solutions. The addition of 10mM KC1 is shown to cause large shifts in the band positions due to ion pairing. Fourier transform Raman spectroscopy is shown to be applicable to such systems, and no wavelength dependence of the surface enhanced Raman mechanism is found. SERS is used to study the (pyridinylmethylene)-hydrazinecarbothioamide class of electrode modifiers on gold, and it is found that the 2- substituted isomer is adsorbed at an angle to the surface, whilst the 4- substituted isomer is adsorbed parallel to the surface. No interaction with cytochrome-c can be detected by SERS. The pH dependence of two corrosion inhibitors (benzotriazole and 2-mercaptobenzothiazole) have been studied by SERS on copper and silver electrodes. The anion present in neutral solutions is shown to protonate in acid solutions, leading to a lowering in protection efficiency for benzotriazole. Competitive adsorption of these two compounds shows 2-mercaptobenzothiazole to be adsorbed most strongly.
This record has no associated files available for download.
More information
Published date: 1988
Identifiers
Local EPrints ID: 460741
URI: http://eprints.soton.ac.uk/id/eprint/460741
PURE UUID: 53ce1342-1d2f-49de-aa42-8ac3cf4a594b
Catalogue record
Date deposited: 04 Jul 2022 18:28
Last modified: 04 Jul 2022 18:28
Export record
Contributors
Author:
Roy Brian Lowry
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics