Fabrication, characterisation and electroanalysis at 1-dimensional nanostructures

Integrated nanowire electrodes that permit direct, sensitive and rapid electrochemical based detection of chemical and biological species are a powerful emerging class of sensor devices. As critical dimensions of the electrodes enter the nanoscale, radial analyte diffusion profiles to the electrode dominate with a corresponding enhancement in mass transport, steady-state sigmoidal voltammograms, low depletion of target molecules and faster analysis. To optimise these sensors it is necessary to fully understand the factors that influence performance limits including: electrode geometry, electrode dimensions, electrode separation distances (within nanowire arrays) and diffusional mass transport. Therefore, in this thesis, theoretical simulations of analyte diffusion occurring at a variety of electrode designs were undertaken using Comsol Multiphysics®. Sensor devices were fabricated and corresponding experiments were performed to challenge simulation results. Two approaches for the fabrication and integration of metal nanowire electrodes are presented: Template Electrodeposition and Electron-Beam Lithography. These approaches allow for the fabrication of nanowires which may be subsequently integrated at silicon chip substrates to form fully functional electrochemical devices. Simulated and experimental results were found to be in excellent agreement validating the simulation model. The electrochemical characteristics exhibited by nanowire electrodes fabricated by electronbeam lithography were directly compared against electrochemical performance of a commercial ultra-microdisc electrode. Steady-state cyclic voltammograms in ferrocenemonocarboxylic acid at single ultra-microdisc electrodes were observed at low to medium scan rates (≤ 500 mV.s-1). At nanowires, steady-state responses were observed at ultra-high scan rates (up to 50,000 mV.s-1), thus allowing for much faster analysis (20 ms). Approaches for elucidating faradaic signal without the requirement for background subtraction were also developed. Furthermore, diffusional process occurring at arrays with increasing inter-electrode distance and increasing number of nanowires were explored. Diffusion profiles existing at nanowire arrays were simulated with Comsol Multiphysics®. A range of scan rates were modelled, and experiments were undertaken at 5,000 mV.s-1 since this allows rapid data capture required for, e.g., biomedical, environmental and pharmaceutical diagnostic applications.

Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

Environmental and biological characteristics of lagoons on the southwest coast of Ireland

Coastal lagoons are defined as shallow coastal water bodies partially separated from the adjacent sea by a restrictive barrier. Coastal lagoons are protected under Annex I of the European Habitats Directive (92/43/EEC). Lagoons are also considered to be “transitional water bodies” and are therefore included in the “register of protected areas” under the Water Framework Directive (2000/60/EC). Consequently, EU member states are required to establish monitoring plans and to regularly report on lagoon condition and conservation status. Irish lagoons are considered relatively rare and unusual because of their North Atlantic, macrotidal location on high energy coastlines and have received little attention. This work aimed to assess the physicochemical and ecological status of three lagoons, Cuskinny, Farranamanagh and Toormore, on the southwest coast of Ireland. Baseline salinity, nutrient and biological conditions were determined in order to provide reference conditions to detect perturbations, and to inform future maintenance of ecosystem health. Accumulation of organic matter is an increasing pressure in coastal lagoon habitats worldwide, often compounding existing eutrophication problems. This research also aimed to investigate the in situ decomposition process in a lagoon habitat together with exploring the associated invertebrate assemblages. Re-classification of the lagoons, under the guidelines of the Venice system for the classifications of marine waters according to salinity, was completed by taking spatial and temporal changes in salinity regimes into consideration. Based on the results of this study, Cuskinny, Farranamanagh and Toormore lagoons are now classified as mesohaline (5 ppt – 18 ppt), oligohaline (0.5 ppt – 5 ppt) and polyhaline (18 ppt – 30 ppt), respectively. Varying vertical, longitudinal and transverse salinity patterns were observed in the three lagoons. Strong correlations between salinity and cumulative rainfall highlighted the important role of precipitation in controlling the lagoon environment. Maximum effect of precipitation on the salinity of the lagoon was observed between four and fourteen days later depending on catchment area geology, indicating the uniqueness of each lagoon system. Seasonal nutrient patterns were evident in the lagoons. Nutrient concentrations were found to be reflective of the catchment area and the magnitude of the freshwater inflow. Assessment based on the Redfield molar ratio indicated a trend towards phosphorus, rather than nitrogen, limitation in Irish lagoons. Investigation of the decomposition process in Cuskinny Lagoon revealed that greatest biomass loss occurred in the winter season. Lowest biomass loss occurred in spring, possibly due to the high density of invertebrates feeding on the thick microbial layer rather than the decomposing litter. It has been reported that the decomposition of plant biomass is highest in the preferential distribution area of the plant species; however, no similar trend was observed in this study with the most active zones of decomposition varying spatially throughout the seasons. Macroinvertebrate analysis revealed low species diversity but high abundance, indicating the dominance of a small number of species. Invertebrate assemblages within the lagoon varied significantly from communities in the adjacent freshwater or marine environments. Although carried out in coastal lagoons on the southwest coast of Ireland, it is envisaged that the overall findings of this study have relevance throughout the entire island of Ireland and possibly to many North Atlantic coastal lagoon ecosystems elsewhere.