The work presented in this thesis is concerned with electrodes modified with carbon nanotubes. Carbon nanotubes have been characterised with special emphasis on the oxygenated species generated from cutting in acid mixtures. Several different techniques have been used for the analysis, especially infrared spectroscopy (IR) in combination with X-ray spectroscopy (XPS) analysis and transmission electron microscopy (TEM) in combination with atomic force microscopy (AFM). TEM analyses were used to reveal the morphological differences between various nanotube cutting times. The lengths of the nanotube were found to decrease with increasing cutting time. Electrochemical measurements were performed on carbon nanotube modified electrodes using nanotubes of different cutting time. The peak separation of ferricyanide redox reaction was found to depend strongly on the length of nanotube and also on the orientation of nanotube at the interface. Whilst at the randomly dispersed, the peak separation showed a decrease with decreasing nanotube length, vertically aligned nanotubes showed no dependence of the peak separation on the nanotube length. Electrochemical results together with spectroscopy measurements show that the highly electroactive edge planes were located on the carbon nanotubes and the oxygenated species in the ends of the nanotubes from cutting in acid mixtures were responsible for the good electrochemical properties. Bamboo-shaped carbon nanotube is a morphological variation of multi-walled carbon nanotubes where the graphite planes are formed at an angle to the axis of the tube. Glassy carbon electrodes modified with bambootype carbon nanotubes showed greater electrochemical signal compared with electrodes modified with singlewalled carbon nanotubes due to the edge planes of graphite located at regular intervals along the walls of the bamboo-shaped carbon nanotube, thus confirming the importance of the ends of nanotube in controlling the kinetics of electron transfer events. Effect of nanotube orientation was studied using ferrocenemethylamine attached to randomly dispersed and vertically aligned nanotubes. The electron transfer kinetics was found to depend strongly on the orientation of the nanotube with the electron transfer at the randomly dispersed slower than vertically aligned. Results were addressed using the analogy that the ends of the nanotubes are like the ends of the tubes can be described as edge-plane-like whilst the tube walls are basal-plane-like. Difference in electron transfer kinetics suggested that the electron transfer in nanotubes could occur via two different pathways: through the edge plane-like opening of the nanotube or by hopping across the walls of the nanotube. Triton X-100 was used to dialyse the acid cut nanotubes. XPS analysis of dialysed nanotubes was compared with non-dialysed nanotubes. A reduced concentration of sulfate ions was found in the dialysesd sample. Nitrate ion (407 eV) was removed after dialysis. Amino groups (400 ev) and protonated amino-group (402 eV) both seemed to be removed slowly by dialysis. Theses ions could be ascribed to residual ions trapped inside nanotubes from cutting in acid mixtures. The electrochemical response of ferrocenemethylamine was also studied. The electron transfer rate constants were rate constants were higher at dialysed nanotube assembly than non-dialysed, which was attributed to doping effect incurred from cutting. Electron transfer between nanotube and gold electrode surface was studied by attaching nanotubes to linker length of 6, 8, and 11 carbons. The results were exploited to rationalise the role of the chemical structure of the nanotubes in facilitating electron transfer from the redox species to the electrode surface that was otherwise suppressed without the presence of nanotubes. The observed redox activity was a consequence of resonant electron transfer from the LUMO of the acceptor to the HOMO of the donor under the influence of an applied voltage, assuming the nanotube modified electrode behaves similarly to the metal-molecule-metal junction mode.

AB5 hydrogen storage alloys have been intensively studied due to its superior ability to store hydrogen and release at ambient conditions. It is also a major component in the negative electrode of Ni-MH batteries. However, it has poor high rate capability and cycle life stability. Carbon nanotubes (CNTs) were found to store a tremendous amount of hydrogen, owing to the fact that they possess very large surface areas. It is because the hydrogen storage capacity is in general highly dependent on the surface area of the storing materials. The aim of this project has been to investigate the effect on electrochemical behaviours of Ab5 negative electrode in Ni-MH batteries by adding carbon nanotubes. The research also studied the influence of the ball milling treatments applied to both the Ab5 and CNTs. La0.59Ce0.27Nd0.08Pr0.06 (Ni0.76Mn0.08Al0.01Co0.15)5 AB5 alloy powder was used as active material in the negative electrode in the Ni-MH batteries, CNTs were used as additive, nickel powers as conductor in a three-electrode cell. Electrodes with compositions of AB5 + x wt.% CNTs (x=0, 5, 10) were studied. Activation, high rate capability and cycle life stability were investigated. The three-electrode cell in an open container with 6 M of KOH as electrolyte was connected to charge/discharge machine where galvanostatically charging and discharging took place. Hydrogenation of ball milled and as-received AB5 alloy powders were examined by conventional volumetric method. Morphology of AB5 and CNTs was examined by scanning electron microscopy (SEM) and transition electron microscopy (TEM), respectively. The phase identification and crystal lattice parameters were analysed by multi-purpose X-ray diffraction before and after ball milling treatments for both materials. The chemical composition of Ab5 alloy powders was tested using ICP chemical method. The results show the addition of CNTs in negative electrode in a Ni-MH battery enhanced the specific discharge capacity remarkably. A maximum discharge capacity of 252 mAh/g was observed for electrode with low energy ball-milled (LEBM) Ab5 with 5 wt.% of CNTs. This was due to the superior properties and great surface area of CNTs which allow more hydrogen to be stored and diffused onto the surface. Not only CNTs could act as a hydrogen reservoir in the negative electrode, it also acted as a conductor by building a conductive network between active material and nickel powders, and hence an increase in discharge capacity. However, the milling on CNTs alone will not improve the electrochemical properties of the electrode. In contrary, the activation profiles, high rate capability and cycle stability have been enhanced significantly when Ab5 alloy powders were ball-milled. The possible explanation is the smaller particle size and rough surface (and hence large surface area) obtained after ball milling induces a better hydrogen diffusion between the particles, as a result of shorter distance between particles after ball milling. Ball milling treatments on AB5 alloy powders did not improve the hydrogen absorption capacity. A highest value of 1.27 wt.% was observed for LEBM alloy powders. Ball milled samples have a slightly lower plateau pressure as compared with that of as-received alloy powders. In addition, only 4% of the maximum absorption capacity was lost after 10 repeated absorption and desorption cycles due to pulverisation of the particle over cycling. It can be concluded that LEBM Ab5 with addition of 5 wt.% CNTs, can significantly improve the electrochemical properties of negative electrode in Ni-MH batteries.

Thesis (PhD)--Macquarie University (Division of Environmental & Life Sciences, Dept. of Chemistry & Biomolecular Sciences), 2005. / Typescript. Includes bibliographical references.

Guided by increasing legislation, the analysis of food borne toxins, including mycotoxins, seeks to address market related demands for the development of analytical systems to monitor this threat to food security and human health. This Thesis is directed at the assessment of the application of electrochemistry for direct electroanalysis and characterisation of the mycotoxin citrinin (CIT) in aqueous media as well as fundamental investigations of the surface of polished and oxidised glassy carbon electrodes (GCE). This study provides the first known account of CIT detection through electrochemical methods. Although electrochemically active, CIT current responses (Ip) were highly irreproducible at polished GCE with a coefficient of variation (C.V.) of 20.16 %. As stability of Ip across multiple electrode preparations is a key requirement in electroanalysis, investigations were directed at attaining stability in CIT Ip. Achieving stability in CIT Ip was investigated via two approaches, including: accounting for Ip variability between electrode preparations as a result of variable GCE surface conditions as a post-data-acquisition analysis and secondly, removing Ip variability through modification of GCE. Accounting for variability in Ip was investigated through the application of double layer capacitance as an indicator of the activity of an electrode, and in so doing serving as a relative mediator of Ip responses between electrodes. Application of this procedure dropped CIT C.V. to a third of starting value across polished GCE (C.V. = 7.18 %), chemically oxidised GCE (Pi-GCE, C.V = 8.47 %) and functionalised multi-walled carbon nanotube modified GCE (fMWCNT, C.V. = 25.79 %) and was effective with analysis of structurally distinct molecules, 2,4-dimethylaniline (2,4-DMA) and 1,2,4-trihydroxybenzene (Triol). Furthermore, it afforded the ability to determine discreet solution overlapping data sets of Ip. Stabilising Ip through GCE surface modification was achieved by anodic electro-oxidation of GCE and allowed for direct electroanalysis of CIT and subsequent characterisation and analysis of CIT in complex media as it reduced C.V. of CIT Ip to 0.73 %. Fundamental investigations of the electrode surface condition are described such that the source of variability could be identified and the interactions of CIT with the electrode understood. Two surface oxidation techniques were applied in modification of GCE; anodic electro-oxidation (EOx GCE) and chemical oxidation using piranha solution (Pi-GCE), analysis of which has previously not been reported. Fundamental analyses to determine surface morphology and chemistry of Pi-GCE, EOx-GCE and polished GCE were conducted using high resolution scanning electron microscopy (HRSEM), scanning electrochemical microscopy (SECM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) and via electroanalytical methods. These studies showed that both oxidation procedures introduced a variety of oxide species at GCE surface, and further that the extent of those species was similar with total % O being 27.67 % and 33.47 % at Pi-GCE and EOx-GCE respectively. Although chemically similar, each surface was morphologically distinct. Electrochemical analyses at the surfaces revealed Pi-GCE to behave more similarly to polished GCE than EOx-GCE. As CIT responses were found to be stable at EOx-GCE (C.V. = 0.73 %) as opposed to Pi-GCE (C.V. = 22.87 %), stability of CIT Ip was likely to be as a result of a physical interaction with electrode morphology rather than interaction on a chemical basis. Morphological analyses revealed polished GCE and Pi-GCE to be highly morphologically irregular at the micro-scale. Although comparatively smooth, the surface morphology of EOx-GCE does not account for the stability of Ip. This study thus proposed a theory to describe the mechanism by which the limited conductivity and porosity of EOx-GCE allow for it to provide a relatively stable surface area within the oxide layer, adjacent to the electrode surface, and thus provided a stable platform for electroanalysis. Voltammetric characterization of CIT at EOx-GCE revealed that anodic oxidation in aqueous media involved an uneven number of electrons to protons via an ECE mechanism. This was illustrated to be nt = 2e- accompanied by the transfer of 1H⁺ per molecule oxidised. A proposed reaction scheme for the initial stages of CIT oxidation was suggested to involve both hydroxyl and carboxyl moieties of the CIT molecule. CIT oxidation was shown to arise as a result of a relatively complex mass transport regime which included both adsorptive and diffusive derived Ip₁. The LOD in buffered aqueous media was found to be 16 nM, a highly competitive result in relation to chromatographic techniques. Further application of EOx-GCE in complex media illustrated that CIT associates non-specifically with the components of food samples, primarily proteins. As a result of this, extraction of CIT from such media is mandatory. Liquid-liquid extraction illustrated a recovery in CIT Ip₁ and in so doing provided a means of accurately and sensitively detecting CIT from food samples with an LOD of 20 nM. These responses were corroborated by HPLC analyses on the same extractions and illustrate the applicability of electroanalysis as an analytical technique.

Thesis (M. Phil.)--University of Hong Kong, 1984.

published_or_final_version / Chemistry / Master / Master of Philosophy

Thesis (Ph. D.)--West Virginia University, 1999. / Title from document title page. Document formatted into pages; contains xv, 207 p. : ill. (some col.) Includes abstract. Includes bibliographical references (p. 203-207).

Thesis (M.S.)--Ohio University, March, 2006. / Title from PDF t.p. Includes bibliographical references (p. 57-58)

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) <i>n</i>-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.

The aim of this project is to develop strategies for fabrication of carbon electrode surfaces with a view to creating stable and versatile monolayer systems for sensing and other applications. Glassy carbon (GC) electrodes have been successfully modified with versatile monolayers via the electrochemical reduction of aryl diazonium salts. The surfaces modified with diazonium salt monolayers were properly characterised by electrochemistry, AFM and XPS. The rates of heterogeneous electron transfer through organic monolayers on GC, Pyrolysed Photoresist Films (PPF) and gold surfaces have been studied using ferrocene as the redox probe. The diazonium salt monolayers created on GC surfaces demonstrated very stable ability and can serve as a good alternative to alkanethiol selfassembled monolayers on gold electrodes for sensing purposes. Tripeptide Gly-Gly-His modified GC electrodes have been successfully used as the electrochemical copper sensors and were found to be extremely stable. PPF has proved to be a good alternative to the GC electrode for the commercialisation of the fabricated electrochemical sensors. The most important and difficult task of this project is to fabricate glucose biosensors and immunosensors on carbon electrodes. The rigid and conjugated molecular wires (MW) as the efficient conduit for electron transfer, and a molecule with poly(ethylene glycol) chains (PEG) as an insulator for reducing the non-specific protein adsorption were successfully synthesised and introduced in the sensing systems. MW modified on GC electrodes can be used to explore the deeply buried active site of glucose oxidase to achieve direct electron transfer of GOx from the active centre FAD through the MW to the underlying GC electrode, and to fabricate third generation biosensors. The interface comprising mixed monolayers of MW and PEG has the ability to facilitate efficient electron transfer. A label-free immunosensor system has been successfully developed for electrochemical detection of biomolecular pairs such as biotin/antibiotin with low detection limitation based on mixed monolayers of MW and PEG modified GC electrode surfaces. In addition, a displacement assay has shown that the free biotin can compete with the attached biotin for binding antibiotin. SWNTs can be used as an alternative to MW to fabricate another label-free immunosensor system due to the high efficiency of electron transfer that SWNTs have demonstrated.