In this PhD TiO2 gas phase photocatalysis is investigated in all its facets. Work has been done on the level of the reactor as well as the catalyst and structural as well as electronic improvements have been proposed. Apart from actual experiments, also theoretical models and a techno-economic assessment have been carried out. The first main achievement is the development of a cost and material-efficient immobilization method and testing procedure. The design, based on glass bead supports packed around a lamp in a cylindrical glass reactor tube, offers the advantages of good immobilization, efficient light utilization, intimate contact with gaseous pollutants and a catalyst weight gain by a factor of 25 compared to self-supporting pellets. The reactor is used for performing a cost effectiveness analysis on six different commercial photocatalytic materials. The second achievement is the fundamental insight that is gathered in the driving factors for gas phase photocatalytic reactions. Structural properties such as large surface area and accessible pores seem to dominate over electronic properties. This knowledge is exploited in the development of well-immobilized, spacious T1O2 thin films. These films are prepared by depositing a thin, conformal TiO2 layer onto sacrificial carbonaceous templates by means of atomic layer deposition. After calcination, the sacrificial template is removed, TiO2 is crystallized into the anatase phase and the as-deposited continuous TiO2 layer has transformed into an interconnected network of nanoparticles. This way open thin films are prepared with surface area enhancement factors of up to 260 with regard to a dense, flat TiO 2 film. Thus obtained films exhibit superior photocatalytic activity compared to a commercial reference film. The final achievement is the extension of TiO2 photoactivity toward the visible light region of the spectrum. This is done by exploiting surface plasmon resonance effects of gold-silver alloy nanoparticles. Surface plasmon resonance can be regarded as a collective oscillation of free electrons in a metal. This way incident (visible) light energy can be 'captured' in the resonance and subsequently transferred to T1O2. First, a theoretical model is established that enables to predict the plasmon resonance wavelength of such alloy nanoparticles, based on the combined effect of particle size and alloy composition. It is shown that the feature of alloying presents high wavelength tunability of the visible light response. Next, alloy nanoparticles are deposited on TiO2. Thus obtained plasmonic photocatalysts are tested towards their self-cleaning performance in the degradation of stearic acid located at the catalyst-air interface. The highest quantum efficiency is obtained when the resonance wavelength of the plasmonic catalyst exactly matches that of the incident light. This is demonstrated for the case of Au 0.3Ag0.7, nanoparticles on TiO2 under 490 nm illumination, provided by LEDs.
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- Chemical engineering;Nanoscience;Chemistry