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1.
Photoactive nanocomposite thin films on glass and thermosensitive substrates
Nives Vodišek, 2019, doctoral dissertation

Abstract: Photocatalysis is a well-known process for the last few decades; it is predominantly used for water and air purification, but also for self-cleaning and antibacterial surfaces. The photocatalytic process is one of the advanced oxidation processes, where semiconductors are mainly used as photocatalysts. The most known and used semiconductor is nanosized titania, which can non-selectively decompose organic matters. One of the side effects of nano TiO2 under UV irradiation is photoinduced hydrophilicity, which furthermore improves the self-cleaning effect. The main drawback of TiO2 is that for its activation UV light is needed, which represents only 5 percent of the solar spectrum. Consequently, actinic irradiance power is low and the response of photocatalyst is limited. Novel approaches are being introduced to improve TiO2 response to visible light such as doping, coupling, modification of surface morphology and others. The thesis consists of five principal chapters. The first chapter is focused on a short literature review and explanation of some basic terms and principles that are related to this thesis. The aim of the research was to prepare transparent photocatalytically active thin films on glass and thermosensitive substrates. Four thermosensitive substrates were used: polyvinyl chloride (PVC) foil, polymethyl methacrylate (PMMA) sheet and polyester (PES) fabric coated with a polyvinyl and acrylic coating, with (D1) or without (D2) an additional polyvinylidene fluoride topcoat. The synthesis of films was modified with the introduction of zirconium aiming at improving the photocatalytic activity of the TiO2 films, and the final films had a SiO2 phase present for increased mechanical robustness. The third chapter is dedicated to the experimental part of the thesis. The detailed process of synthesis is described. The sol-gel process was used to prepare initial Ti-Zr sols, colloidal aqueous solutions with TiO2 and ZrO2 nanoparticles derived from titanium and zirconium alkoxides. The four different Ti-Zr sols were prepared with 0, 5, 10 and 20 molar % of Zr according to Ti. The depositing solution was prepared by mixing Ti-Zr sol, SiO2 sol binder, 1-propanol and 2-propoxyethanol, and then thin films were deposited by dip-coating technique. After the deposition, samples did not require high-temperature calcination since the photocatalytic anatase phase was present already after drying the deposited layers. Coated glass slides were put into a furnace at 150 °C, while samples on thermosensitive substrates were just treated by a heat gun. Samples in powder and thin film form were characterized by UV-Vis, FTIR-ATR and laser beam deflection spectroscopy, X-ray diffraction, scanning electron microscopy and thermal analysis. One of the main aspects of the photocatalyst is its activity. Photocatalytic activity of the thin films was determined, either quantitatively by the formation of fluorescent hydroxyterephthalic acid, one of the first degradation products of terephthalic acid deposit, or qualitatively by a visual-based method where degradation of resazurin ink was observed. Two additional methods were used on glass samples, electron paramagnetic resonance, and degradation of methyl stearate by observing the change in water contact angle under UVA irradiation. Mechanical stability of films on various substrates is an essential factor, describing how successful was immobilization of the photocatalytic materials on the substrate. It was determined by the pencil hardness test, i.e., Wolff-Wilborn method. In the fourth chapter, titled “Results and Discussion,” the most important part of the thesis is placed. Materials characterization and associated discussion of the results are divided into three major parts: i) powder samples characterization; ii) characterization of thin films on a glass substrate, and iii) characterization of films on thermosensitive substrates. In the conclusions, the main findings of the Ph.D. research work are summarized. One of our initial hypotheses was disapproved, thin films were not more active with a higher content of zirconium. However, they were more durable. All the obtained films were transparent and photoactive, despite the low-temperature synthesis procedure. Besides commonly used glass substrate, immobilization on thermosensitive substrates was also successful.
Keywords: glass substrate, immobilization, nanocomposite, nanomaterials, PES, photocatalysis, PMMA, PVC, self-cleaning surfaces, silica, plastic substrates, thin films, titania, zirconia
Published in RUNG: 14.10.2019; Views: 4958; Downloads: 191
.pdf Full text (6,23 MB)

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Development of Advanced TiO2/SiO2 Photocatalyst for Indoor Air Cleaning
Andraž Šuligoj, 2015, doctoral dissertation

Abstract: TiO2 - SiO2 composites were synthesized by low-temperature sol-gel impregnation method, using four different titania sources (P-25 from Degussa, PC500 from Millennium, CCA 100 AS and CCA 100 BS from Cinkarna, later denoted as AS and BS, respectively) and deposited on aluminium and glass carriers. Ordered and disordered mesoporous silicas were impregnated with ce{TiO2} in powder or suspension form in the Ti : Si molar ratio 1 : 1. Structure, size, band gap, chemical composition and specific surface area of nanoparticles were determined by X-ray diffraction (XRD), scanning (SEM) and transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DR-UV-vis), Fourier transform infrared spectroscopy (FT-IR) and ce{N2} physisorption. Additionally, quantity of surface hydroxyl groups, surface acidity and mechanical stability of the coatings were determined by temperature programmed Fourier transform infrared spectroscopy (TPD-IR) and Wolff-Wilborn method, respectively. The photocatalytic activity of TiO2 and TiO2 - SiO2 composites was evaluated in the photodegradation of toluene and formaldehyde, as model VOCs, under UVA light irradiation in lab-made photoreactor system with two different regimes; batch and plug-flow mode. These two VOCs are being considered as examples of two of the six major classes of indoor air contaminants. Adsorption properties of the samples with toluene, have shown that the addition of mesoporous silica was beneficial. The increase of the adsorption of the bare AS TiO2 (9.5 %) was higher in the case of ordered silica, SBA-15 (2.8 times for AS/SBA15 to 26.8 %) than disordered SiO2 KIL-2 (2.4 times for AS/KIL2 to 22.7 %) although it was significant in both types of mesoporous silica supports (over 20 %). Adsorption was found to be dependent mostly on the quantity of surface Si-OH groups. Regarding the photocatalytic activities towards toluene degradation, the results with pure TiO2 showed the fastest kinetics in case of sample AS followed by PC500 and P25. The observed behaviour was ascribed to smaller particle size, and consequently higher specific surface area. Grafting titania onto silica showed the importance of structural parameters. Most importantly, if the pore structure of bare TiO2 collapsed, this resulted in decreased activity. On the other hand, retainment of the pore structure improved the distribution of nanoparticles, crystallinity and optical properties, which resulted in improved photocatalytic activity. In the degradation of formaldehyde, it was found that adsorption and degradation abilities of the materials were much more dependent on the structural properties of the samples, i.e., the pore structure. This was explained as a consequence of the different degradation mechanisms of both pollutants. Toluene degradation is governed by the oxidation through photogenerated holes - direct oxidation, whereas in the degradation of formaldehyde, the major oxidative species are OH radicals. In addition, the same as in toluene oxidation, the activity was dependent mainly on the number of crystal defects and the band gap values, that is the oxidation and reduction potentials of the catalysts. The degradation efficiency was increased from 88 % in pure AS TiO2 to 97 % when this titania was grafted onto colloidal silica (7C). An important highlight of the thesis is synthesis of a novel photocatalyst, labelled AS7C, which comprises an acidic colloidal suspension AS as TiO2 source and colloidal silica, using a low-temperature sol-gel impregnation method. This sample used all the above mentioned properties that improve photocatalytic activity towards both pollutants. Mechanical stability of the samples was also tested. The tests showed that binder, in the form of colloidal SiO2 (in size of 25 nm) in combination with colloidal titania of appropriate size - 6 nm, produced the highest mechanical stability of the coatings, which also showed excellent photocatalytic activity. Stability of the coatings, using AS as titania source, was greatly improved. The Wolff-Wilborn test on AS coating showed no mechanical resistance, while with the optimal (in terms of photocatalytic performance) addition of 7C SiO2 binder stability was excellent (F, which is in the middle of 6B-6H hardness scale). This sample (AS7C) was also tested for release of aerosols, during operation of the reactor, which could be harmful for human health at longer exposure times. It was found that aerosols are formed, probably as a consequence of detachment of nanoparticles in the first period of photodegradation test. However, their formation in consecutive tests was greatly reduced. Last but not least, a pilot plug-flow reactor was constructed to test the photocatalyst's efficiency in one-pass degradation of toluene. Sample AS7C was able to degrade toluene at conditions applied (v= 400 mL/min, m(catalyst) = 1049 mg, C(0) = 1 ppmv), which means that the out-flow from reactor was clean of the pollutant and any possible intermediates, comprising only of humid air and CO2. Deactivation of the catalyst was found at higher air flow and higher initial concentration of the pollutant. However, the concentrations of pollutants in living conditions are few orders of magnitude lower, hence this is a promising result.
Keywords: Air remediation, TiO2 photocatalysis, Immobilization, Thin layers, TiO2/SiO2 composites
Published in RUNG: 31.08.2015; Views: 9620; Downloads: 228
.pdf Full text (33,47 MB)

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