Studies of Photocatalytic Processes at Nanoporous TiO2 Film Electrodes by Photoelectrochemical Techniques and Development of a Novel Methodology for Rapid Determination of Chemical Oxygen Dphotocatalemand
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In this work, a series of simple, rapid and effective photoelectrochemical methodologies have been developed and successfully applied to the study of kinetic and thermodynamic characteristics of photocatalytic oxidation processes at TiO2 nanoparticulate films. As an application of the systematic studies of photocatalytic processes by photoelectrochemical techniques, a rapid, direct, absolute, environmental-friendly and accurate COD analysis method was successfully developed. In this work, the TiO2 nanoparticles colloid was prepared by the sol-gel method. The TiO2 nanoparticles were immobilized onto ITO conducting glass slides by dip-coating method. Thermal treatment was carried out to obtain nanoporous TiO2 films of different structures. At low calcination temperature (below 600°C), nanoporous TiO2 films of pure anatase phase were prepared. At high calcination temperature (above 600°C), nanoporous TiO2 films of mixed anatase and rutile phases were obtained. At these film electrodes, the work was carried out. By employing steady state photocurrent method and choosing phthalic acid as the model compound, the photocatalytic activity of the TiO2 nanoporous films calcined at various temperatures and for different lengths of time was evaluated. It was found that the films with mixed anatase and rutile phases calcined at high temperature exhibited high photocatalytic activity. Based on semiconductor band theory, a model was proposed, which explained well this finding. By employing linear sweep voltammetry (under illumination) and choosing glucose (an effective photohole scavenger) as a model compound, the characteristics of the photocatalytic processes at nanoparticulate semiconductor electrodes were investigated. Characteristics of the nanoporous semiconductor electrodes markedly different from bulk semiconductor electrodes were observed. That is, within a large range of electrode potentials above the flat band potential the electrodes behaved as a pure resistance instead of exhibiting variable resistance expected for bulk semiconductor electrodes. The magnitude of the resistance was dependent on the properties of the electrodes and the maximum photocatalytic oxidation rate at TiO2 surface determined by the light intensity and substrate concentration. A model was proposed, which explained well the special characteristics of particulate semiconductor electrodes (nanoporous semiconductor electrodes). This is the first clear description of the overall photocatalytic process at nanoparticulate semiconductor electrodes. The investigation set a theoretical foundation for employing photoelectrochemical techniques to study photocatalytic processes. By using the transient technique (illumination step method analogous to potential step method in conventional electrochemistry), the adsorption of a number of strong adsorbates on both low temperature and high temperature calcined TiO2 nanoporous films was investigated. Similar adsorption characteristics for different adsorbates on different films were observed. In all the cases, three different surface bound complexes were identified, which was attributed to the heterogeneity of TiO2 surface. The photocatalytic degradation kinetics of the pre-adsorbed organic compounds of different chemical nature was also studied by processing the photocurrent-time profiles. Two different photocatalytic processes, exhibiting different rate characteristics, were observed. This was, again, attributed to the heterogeneity of the TiO2 surface corresponding to heterogeneous adsorption characteristics. The catalytic first order rate constants of both fast and slow processes were obtained for different organic compounds. It was found that for different adsorbates of different chemical nature the magnitudes of rate constant for the slow kinetic process were very similar, while the magnitudes of rate constant for the fast process were significantly affected by the photohole demand characteristics of different adsorbates. Photohole demand distribution that depends on the size and structure of the adsorbed molecules was believed to be responsible for the difference. By employing steady state photocurrent method, the photocatalytic degradation kinetic characteristics of both strong adsorbates and weak adsorbates of different chemical structures were compared at pure anatase TiO2 nanoporous TiO2 films as well as at anatase/rutile mixed phase TiO2 nanoporous film electrodes. At the former electrodes for all the different organic compounds studied, the photocatalytic reaction rate increased linearly with concentration at low concentrations. Under such conditions, it was demonstrated that the overall photocatalytic process was controlled by diffusion and was independent of the chemical nature of organic compounds. However, the linear concentration range and the maximum photocatalytic reaction rate at high concentrations were significantly dependent on the chemical nature of the substrates. This was explained by the difference in the interaction of different organic compounds with TiO2 surface, the difference in their photohole demand distributions at the TiO2 surface and the difference in their nature of intermediates formed during their photocatalytic mineralization. In contrast, at the latter electrodes for the photocatalytic oxidation of different organic compounds the linear ranges (diffusion control concentration range) and the maximum reaction rates at high concentration were much larger than at the former electrodes and much less dependent on the chemical nature of the organic compounds. The spatial separation of photoelectrons and photoholes (due to the coexistence of rutile phase and anatase phase) and the increase in the lifetime of photoelectrons and photoholes are responsible for the excellent photocatalytic activity of the electrodes. By employing the thin-layer photoelectrochemical technique (analogous to the thin-layer exhaustive electrolytic technique), the photocatalytic oxidation of different organic compounds at the mixed phase TiO2 nanoporous electrodes were investigated in a thin layer photoelectrochemical cell. It was found that the charge derived from exhaustive oxidation agreed well with theoretical charge expected for the mineralisation of a specific organic compound. This finding was true for all the compounds investigated and was also true for mixtures of different organic compounds. The photocatalytic degradation kinetics of different organic compounds of different chemical identities in the thin layer cell was also investigated by the photoelectrochemical method. Two kinetic processes of different decay time constants were identified, which were attributed to the degradation of preadsorbed compounds and the degradation of compounds in solution. For the degradation of compounds in solution, a change in the overall control step from substrate diffusion to heterogeneous surface reaction was observed. For different organic compounds, the variation of the rate constant was determined by the photohole demand rather than by the chemical identities of substrates. The kinetics of the fast kinetic process, on the other hand, was greatly affected by the adsorption properties of the substrates. For the strong adsorbates, the rate was much larger than for weak adsorbates. However, the rate constant of the process was independent of the chemical identities of the substrates and the variation of the constant was also determined by the photohole demand. Based on the principles of exhaustive photoelectrocatalytic degradation of organic matter in a thin layer cell, a novel, rapid, direct, environmental-friendly and absolute COD analysis method was developed. The method was tested on synthetic samples as well as real wastewater samples from a variety of industries. For synthetic samples with given compositions the COD values measured by my method agree very well with theoretical COD value. For real samples and synthetic samples the COD values measured by my method correlated very well with those measured by standard dichromate COD analysis method.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environmental and Applied Science
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photocatalytic oxidation process