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Title: Electrochemical studies at carbon-based electrodes
Author: Gan, Kok Dian Patrick
ISNI:       0000 0004 6061 8507
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2015
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Carbon electrodes have found widespread use in electrochemistry due to its broad versatility and low cost amongst other advantages. Recent innovations in carbon materials have added new dimensions to their utility in electrochemical applications. This thesis aims to investigate aspects of carbon materials, in particular boron-doped diamond (BDD) and nanocarbon composites, mainly for electrochemical analysis and energetics studies. The electrochemical behaviour of estradiol and other endocrine disrupting compounds was examined on the BDD electrode with different surface pretreatments, as well as on a nanocarbon-modified BDD electrode. It was shown that the precise control of surface chemical termination enabled the electrode to be tuned to exhibit diffusional or adsorptive voltammetry at oxidised and hydrogenated BDD interfaces respectively. Adsorption effects were also observed on the modified electrode leading to significant pre-concentration of the analyte onto the nanocarbon and a corresponding lowering of the limit of detection by ca three orders of magnitude to nanomolar levels. Surface modification of the BDD electrodes was then explored using a simple and convenient dropcast technique to deposit microcrystalline copper phthalocyanine onto the electrode. The influence of the surface chemical termination towards the interaction with the modifier compound was demonstrated in relation to the oxygen reduction reaction. Hydrogen terminated BDD modified in such a manner was able to significantly decrease the overpotential for the cathodic reaction by ca 500 mV when compared to the unmodified electrode while modified oxidised BDD showed no such electrocatalysis, signifying greater interaction of the phthalocyanine modifier with the hydrogenated surface. The lack of a further conversion of the peroxide product was attributed to its rapid diffusion away from the triple phase boundary (comprising the phthalocyanine microcrystallite, aqueous solution and BDD electrode) at which the reaction is expected to exclusively occur. Next carbon composites were studied in the form of carbon paste electrodes (CPEs). The practicality of a nanocarbon paste was established by cyclic voltammetry with several well-characterised redox systems commonly used to test electrode activity and was found to exhibit comparable behaviour to the more typical graphitic formulation. Reversible uptake of some analytes was observed at the CPEs, giving rise to complex double peak voltammetry. This uptake phenomenon was then further examined at the nanocarbon paste electrode to monitor the transfer of species between two dissimilar liquid phases. The interfacial behaviour gave rise to voltammetric peaks which were assigned to species originating from the aqueous, binder and carbon phases respectively and this enabled the measurement of Gibbs energies of transfer between oil and aqueous phases. Finally the effect of different ionic liquids as binder for carbon-ionic liquid composite electrodes was studied. Some ionic liquids were demonstrated to offer benefits in comparison to oil in the fabrication of carbon paste type electrode due to an increased adsorption of analytes. The ionic “liquid” (with a melting point above room temperature) n-octyl-pyridinium hexafluorophosphate [C8py][PF6] was shown to be useful in combination with carbon nanotubes as a composite electrode or as a modifier to a screen-printed electrode to significantly enhance the sensitivity of electrochemical detection via adsorptive stripping voltammetry. Overall the carbon-based electrodes studied have demonstrated excellent utility as electrode materials in the areas of electrochemical sensing and energetics investigations.
Supervisor: Ford, John S. ; Compton, Richard G. Sponsor: Singapore-Peking-Oxford Research Enterprise Scholarship
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Carbon composites ; Electrodes ; Carbon