In-situ and model infrared studies of the electrochemical interface
In-situ and model infrared studies of the electrochemical interface
The aim of this thesis was to investigate the structure of the electrochemical double layer interface using UHV and in situ spectroelectrochemical techniques. The UHV technique involved the use of a probe molecule, carbon monoxide, and different solvent molecules e.g. water and acetonitrile, to build a double layer. The RAIRS technique was used to probe the metal-adsorbate as well as the adsorbate vibrational modes. The data obtained from these experiments would hopefully provide information on the structure and bonding and the influence of charge on the interface. The in situ spectroelectrochemical techniques would provide a comparison between the model and experimental results. The close relationship between electrode potential and UHV work function measurements has been extensively discussed by Sass and enables unification of the two datasets.
The UHV experiments completed show a pronounced effect on the probe molecule (carbon monoxide) on co-adsorption with a solvent. The co-adsorption of carbon monoxide with trimethylamine results in a shift in the carbon -metal stretching frequency, indicative of a change in adsorption site from the linearly bound carbon monoxide to the bridge band carbon monoxide. This shift is thought to be due to the increased dipole coupling stabilisation of the multifold carbon monoxide species with the dipole moment of the absorbed trimethylamine.
The electrochemical investigations demonstrate the effect of temperature on a relatively simple electrochemical reaction of carbon monoxide oxidation in acid solutions. The main conclusion is that as the temperature of the electrode increases the potential at which the electrooxidation of carbon monoxide occurs decreases. The observed peak multiplicity in the cyclic voltammograms due to carbon monoxide oxidation are thought to be due to the oxidation of the carbon monoxide from a variety of linear adsorption environments on the platinum surface.
University of Southampton
Wilson, Natalie Elizabeth
1999
Wilson, Natalie Elizabeth
Wilson, Natalie Elizabeth
(1999)
In-situ and model infrared studies of the electrochemical interface.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The aim of this thesis was to investigate the structure of the electrochemical double layer interface using UHV and in situ spectroelectrochemical techniques. The UHV technique involved the use of a probe molecule, carbon monoxide, and different solvent molecules e.g. water and acetonitrile, to build a double layer. The RAIRS technique was used to probe the metal-adsorbate as well as the adsorbate vibrational modes. The data obtained from these experiments would hopefully provide information on the structure and bonding and the influence of charge on the interface. The in situ spectroelectrochemical techniques would provide a comparison between the model and experimental results. The close relationship between electrode potential and UHV work function measurements has been extensively discussed by Sass and enables unification of the two datasets.
The UHV experiments completed show a pronounced effect on the probe molecule (carbon monoxide) on co-adsorption with a solvent. The co-adsorption of carbon monoxide with trimethylamine results in a shift in the carbon -metal stretching frequency, indicative of a change in adsorption site from the linearly bound carbon monoxide to the bridge band carbon monoxide. This shift is thought to be due to the increased dipole coupling stabilisation of the multifold carbon monoxide species with the dipole moment of the absorbed trimethylamine.
The electrochemical investigations demonstrate the effect of temperature on a relatively simple electrochemical reaction of carbon monoxide oxidation in acid solutions. The main conclusion is that as the temperature of the electrode increases the potential at which the electrooxidation of carbon monoxide occurs decreases. The observed peak multiplicity in the cyclic voltammograms due to carbon monoxide oxidation are thought to be due to the oxidation of the carbon monoxide from a variety of linear adsorption environments on the platinum surface.
This record has no associated files available for download.
More information
Published date: 1999
Identifiers
Local EPrints ID: 464079
URI: http://eprints.soton.ac.uk/id/eprint/464079
PURE UUID: 11c17443-b15c-4fbf-a331-e18ffeaa71f7
Catalogue record
Date deposited: 04 Jul 2022 21:02
Last modified: 04 Jul 2022 21:02
Export record
Contributors
Author:
Natalie Elizabeth Wilson
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