This thesis describes experimental work on electrochemical sensing mechanisms. Chapter 1 and Chapter 2 provide an introduction to electrochemical and surface science techniques as well as nano-carbon materials which are of interest in electroanalysis and sensing.Chapter 3 and Chapter 4 focus on electrochemical processes at liquid | liquid | electrode triple phase boundary systems. In Chapter 3 the electrochemical behaviour of CoPc (cobalt phthalocyanine) dissolved into an organic water –insoluble liquid and deposited as microdroplets on a graphite electrode is studied. Both cation and anion transfer are observed at the liquid | liquid phase boundary. Chapter 4 describes redox processes of a highly hydrophobic anthraquinone derivative where preferential transfer of protons and pH sensitivity are observed. Both systems, CoPc and anthraquinone derivative, are investigated towards CO2 sensitivity. In Chapter 3 and 4 graphite electrodes are employed, but in Chapter 5 graphitic carbon nanoaprticles are employed with a surface functionalisation to provide binding capability to DNA fragments. Layer-by-layer deposition of DNA-carbon nanoparticle composite film electrodes is demonstrated and the electrochemical properties of the films are investigated. A novel type of DNA hybridisation sensing mechanism based on a nano-gap generator – collector electrode system is proposed.Chapters 6 and 7 are dedicated to gas sensing with a novel electrochemical system based on ionomer spheres in contact to the working electrode. In Chapter 6 Dowex ionomer particles are impregnated with carbon nanoparticles which are functionalised with DOPA to provide redox activity and Faradaic current responses. The effect of ionomer type and gas composition is studied. In Chapter 7 Prussian blue nanoparticles are immobilised onto the ionomer particle surface to provide a sensing system with peroxide sensitivity.Overall, this thesis contributes to sensing of bio-molecules and of gases. By introducing new types of interfaces (triple phase boundary, ionomer contacts, carbon nanoparticle redox systems) it is shown that sensitivity and selectivity can be tailored. In future these types of sensor prototypes could be further developed for specific applications.
|Date of Award||1 Jan 2012|
|Supervisor||Frank Marken (Supervisor)|