La qualité de l’air que nous respirons à l’intérieur des espaces clos est devenue une préoccupation environnementale majeure. Il est aujourd’hui avéré que la présence de microorganismes dans l’air intérieur peut avoir des conséquences néfastes sur la santé humaine. Les systèmes de ventilation, lorsqu’ils sont mal entretenus, peuvent être eux-mêmes la source de bioaérosols suite à la contamination de leurs filtres. Afin de pallier ce problème, des filtres photocatalytiques ont été développés et testés dans des centrales de traitement d’air (CTA). Ce projet de thèse s’intéresse donc au devenir des microorganismes aérosolisés dans des filtres photocatalytiques. La première étape a consisté à étudier les mécanismes de dégradation par photochimie et photocatalyse d’une bactérie modèle, Escherichia coli (E. coli), en suspension dans l’eau sous irradiation UV-A ou UV-C. Ces deux traitements sont plus efficaces sous UV-C et engendrent des dommages oxydatifs au niveau de la membrane externe et des acides nucléiques bactériens. Le dosage de sous-produits chimiques permet de conclure que la photocatalyse UV-C est plus efficace pour dégrader irréversiblement les bactéries. La seconde étape a été consacrée à l’étude de l’inactivation de spores d’Aspergillus niger et de bactéries E. coli dans les filtres Ahlstrom. Nos résultats confirment l’intérêt d’utiliser des filtres photocatalytiques dans les CTA en comparaison avec les filtres non photocatalytiques. L’utilisation de filtres à haute efficacité, afin d’optimiser le temps de contact entre les microorganismes et le dépôt de dioxyde de titane, permet d’augmenter l’efficacité de dégradation du procédé photocatalytique / Indoor Air Quality (IAQ) has become of particular concern from an environmental and health and safety point of view. It is now proven that the presence of microorganisms in indoor air can have hazardous consequences on human health. HVAC systems, when poorly maintained, can themselves become source of bioaerosols when their filters are contaminated. To tackle this issue, photocatalytic filters have been developed and tested within HVAC systems. The aim of this PhD thesis is to look at the behaviour of microorganisms aerosolized through photocatalytic filters. The first step consisted of analysing the photochemistry and photocatalysis degradation mechanisms of a model bacterium, Escherichia coli (E. coli), in suspension in water under UV-A or UV-C radiation. These two treatments were proven to be more efficient under UV-C radiation and led to oxidative damages to outer membrane and nucleic acids. The measurement of chemical by-products allowed us to conclude that UV-C photocatalysis is more effective in damaging bacteria in an irreversible manner. The second step focused on the analysis of the inactivation of Aspergillus niger spores and E. coli bacteria within Ahlstrom filters. Our results confirm the benefits of using photocatalytic filters in HVAC systems instead of non-photocatalytic filters. The use of high efficiency filters to optimise the contact between the microorganisms and the titanium dioxide deposit, allows an increase in the damaging efficiency of the photocatalytic process

D.Phil. (Chemistry) / Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water-pollution control. Among the many organic pollutants are dyes and emerging pollutants such as natural organic matter (NOM). Dyes such as Eosin Yellow (EY), an anionic xanthene fluorescent dye, can originate from many sources such as textile industrial processes, paper pulp industries and agricultural processes. Most dyes are problematic because they are resistant to conventional chemical or biological water-treatment methods and therefore persist in the environment. NOM consists of a highly variable mixture of products found in water and soils. NOM is formed as a result of the decomposition of plant and animal material and is a precursor to the formation of disinfection by-products (DBP) during water disinfection. These organic compounds cause undesirable colour, taste and odour in water. NOM affects the capacity of other treatment processes to effectively remove organic micro-pollutants or inorganic species that may be present in the water. Its removal also uses up chemicals and energy and so it is expensive to treat. Titanium dioxide (TiO2) has emerged as one of the most fascinating materials in the modern era due to its semiconducting and catalytic properties. TiO2 is a large band-gap semiconductor that exists mainly in the anatase (band gap 3.2 eV) and rutile (band gap 3.0 eV) phases. Its response to UV light has led to increased interest in its application in the photocatalysis research field. It has been investigated extensively for its super hydrophilicity and use in environmental remediation and solar fuel production. In spite of extensive efforts to apply TiO2 for environmental remediation, photocatalytic activity in the visible region has remained quite low hence the ultimate goal of this research was to fabricate highly photoactive catalysts composed of non-metal, platinum-group metal (PGM) co-doped TiO2 and carbon nanotubes (CNTs) and to apply them for water purification using solar radiation...

With an ever-increasing human population, the importance in having sustainable energy resources is becoming increasingly evident, as the current energy habits have brought about massive atmospheric pollution in the form of CO2 emissions, resulting in a rise in the average global temperature. To battle the effects of climate change, many alternative energy resources have been investigated. Among these, photocatalytic conversion of CO2 to renewable hydrocarbon fuels such as methane and methanol is one of the most desirable, as it provides the opportunity to utilize the sun’s energy to convert CO2 to renewable fuels. The work in this study is primarily focused on developing a batch photoreactor system to improve the integrity of photocatalytic experiments and using that system to test the performance of Er-doped solid solutions of ZnO/GaN (ZG) towards photocatalytic reduction of CO2. To upgrade the abilities from previous photoreactor systems, a novel photoreactor was deigned in SolidWorks and fabricated in-house. The photoreactor was designed to increase surface area at the gas-solid interface, improve utilization of the light source, and promote larger mass transfer rates of reactants to the catalyst surface. These goals were accomplished by immobilizing the catalyst on a transparent porous support, incorporating a threaded mount on top of the photoreactor for mounting an interchangeable LED to illuminate the catalyst bed, and recirculating the gas mixture through a closed loop system with a compressor, respectively. Pure and Er-doped ZG photocatalyst samples were synthesized through the nitridation of Zn/Ga/CO3 layered double hydroxide (LDH) precursors. Erbium was chosen as a dopant to potentially enhance the photocatalyst by utilizing its upconversion photoluminescence properties. The LDH precursors were synthesized using a coprecipitation method. Levels of erbium doping were varied by [Er]/[Zn] = 0, 0.025, 0.05, and 0.10. ZnO/GaN solid solutions were chosen for their low bandgap energy so that visible light, roughly 40% of the solar spectrum [1], can be used to activate the catalyst. Diffuse reflectance spectroscopic data of the pure and Er-doped ZG samples were measured and used to calculate the bandgap energy. Bandgap values of EG = 2.53, 2.52, 2.56, and 2.56 eV were obtained for the [Er]/[Zn] = 0, 0.025, 0.05, and 0.10 samples, respectively. XRD data of the LDH samples indicated the formation of Zn/Ga/CO3 LDH and the Zn(OH)2, β-Ga2O3, α-GaOOH, and ZnGa2O4 impurity phases. Moreover, the broadening of the diffraction peaks in the Er-doped LDH samples suggested Er3+ ions substituted the Ga3+ ions in the LDH structure. XRD data of the pure and Er-doped ZG samples revealed strong peaks at 2θ = 31.86, 34.37, and 36.31°, indicating the formation of a solid solution of ZnO and GaN. Additionally, peaks at 2θ = 29.27, 48.79, and 57.86° indicate the formation of the secondary phase of Er2O3 in the Er-doped samples. Consequently, it was concluded that the Er3+ ions did not go into the crystal structure of the oxynitride solid solution. These findings were supported by the SEM images revealing hexagonal nanoplates and nanoprisms that coincide with the solid solution along with additional nanostructures corresponding to the Er2O3 phase. During photocatalytic experiments with the pure and Er-doped ZG samples, CO2, and UV light (405 nm nominal wavelength), hydrocarbon production was observed to increase with increasing [Er/Zn]. However, results from control experiments with no catalyst while varying the nominal LED wavelength and the o-ring material suggested that hydrocarbon formation was partially or entirely the result of the o-ring photochemically degrading in the presence of UV light. An o-ring comprised of a silicone material yielded zero hydrocarbon formation in the presence of UV light, while this was not the case for o-ring materials of Viton® and Kalrez®. These findings can be applied to other research groups that plan to perform photocatalytic experiments in a photoreactor with o-rings while using a UV light source.

Philosophiae Doctor - PhD / The aim of this study was to design and build an electrohydraulic discharge reactor in such a way that the synthetic immobilized TiO2 nanophotocatalytic components could be integrated, for the production of active species such as OH radicals, ozone and hydrogen peroxide, as a cocktail to clean drinking water without the addition of chemicals. The research objectives include: • To design and construct the different AOP prototypes based on various electrode configurations and compare their operation. • To optimize the discharge parameters and conditions of the best AOP system. • To determine the effectiveness of the best prototype for the degradation of methylene blue as model pollutant. • To compare the designed AOP system with the Sodis method for the disinfection of contaminated river water. • To prepare supported TiO2 nanoparticles via electro spinning, followed by combustion and study the effect on the morphology of TiO2 nanoparticles. • To determine the stability and robustness of composite nano-crystalline TiO2 photocatalysts by sonication • To determine the enhanced effect of combining the composite TiO2 in the AOP system on degradation of methylene blue under the same conditions. • To detect the active species promoting disinfection.

>Magister Scientiae - MSc / In recent times, the occurrence and presence of complex recalcitrant toxic contaminants in water and wastewater is increasing and consequently contributes to the non-availability of clean and safe drinking water. Water treatment is complex, time demanding and energy intensive due to the physico-chemical structural complexity and diversity of the pollutants. Non-availability of good drinking water has negatively affected human health and the ecosystem. Over the years, numerous conventional treatment techniques were used to degrade and remove these pollutants, but investigations indicated that some of the pollutants are not susceptible to conventional treatment. Advanced oxidation technology, among which heterogeneous photocatalysis (involving the use of a semiconductor) has emerged as one of the more promising techniques to remediate contaminated water. Titanium dioxide (TiO2) semiconductor photocatalysis is considered to be a good option due to its cost effectiveness, chemical and thermal stability, and inertness in the area of wastewater reclamation and re-use. However the post separation of the titania particles poses a threat to the wastewater remediation. Hence there is a need to develop a supported high surface area photocatalyst that will resolve the post separation challenge. This present study aimed to prepare high surface area TiO2 anatase nanocrystals supported on a stainless steel mesh. These new composite materials were used to remove methylene blue (MB) from aqueous solutions. The supporting procedure involved the thermal decomposition of a sol gel solution coated upon stainless steel mesh. The nanocrystalline anatase phase was formed by thermal decomposition on a stainless steel mesh coated with 8 % PAN/DMF/TiO2 sol gel formation calcined at varying temperatures of 300 °C, 400 °C, 500 °C and 600 °C. The heating rate of 50 °C/min and independent holding time of 1 h, 2 h, 3 h and 4 h were applied to find the optimum supporting conditions. The synthesised TiO2 nanocomposites materials were characterised using the following analytical techniques: XRD, HRSEM, EDS, HRTEM, SAED, FTIR and UV-Vis absorption spectroscopy materials were characterised, and the results indicate that synthesised TiO2 nanocrystals were in the anatase form, polycrystalline in nature, and contained additional carbon-carbon bonds from the polymer used during preparation with TiO2 particle sizes range from 13.6 nm to 2285 nm.

This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

Three studies were performed to obtain fundamental mechanistic information on the TiO2 catalyzed photooxidations of organic substrates irradiated at 350 nm in dilute aqueous solutions under oxygenated conditions: (a) The photodecomposition of three haloethers, 2-chloroethyl ether, 4-chlorophenyl phenyl ether, and 4-bromophenyl phenyl ether, was investigated in an aqueous media at pH 7.0. (b) A comparative study of structure-reactivity was conducted on para-substituted phenols whose substituents range from electron-withdrawing to electron-donating in an aqueous media at pH 3.0. (c) The initial rates of the TiO2 catalyzed photodegratation of phenol were studied in an aqueous media at pH 1.0, 3.0, 5.0, 7.0, 9.0, 11.0, and 13.7 and a pH effect profile was obtained and compared to the removal efficiency after four hours of irradiation. Controls were carried out throughout the three studies in the absence of light and under anoxic conditions, as well as without the semiconductor to evaluate the role of photolysis. The Langmuir-Hinshelwood model was employed in an attempt to characterize and evaluate differences in reactivity.

Visible light-driven photocatalysis has shown considerable potential in the area of clean and renewable energy, as well as in wastewater treatment. This thesis describes the synthesis, characterization and applicability of a visible-light active photocatalyst, bismuth oxybromide (BiOBr). The photocatalytic activity of BiOBr was investigated through its preparation via hydrothermal and solvothermal synthesis routes under various conditions. Hydrothermal catalyst was prepared using non template based method while for solvothermal synthesis CTAB was used as a template. Parameters of temperature and time of thermal treatment were optimized for each synthesis method and overall tests for catalyst dosage and recyclability were performed. An overall optimal route leading to high photocatalytic performance was also proposed based on the obtained results. Studies were also conducted to examine the applicability of optimally synthesized BiOBr in drinking water applications by studying catalyst-mediated disinfection of E. coli and degradation of phenol. Favourable results were obtained, confirming the prospective application of BiOBr as a viable photocatalyst for disinfection. Furthermore, the potential of enhancing BiOBr to further improve its performance is described through synthesis of a novel PdCl2/BiOBr based photocatalyst. Overall, the performance of BiOBr under various conditions in this study establishes its potential as a holistic photocatalyst and merits further development.

La protection de l'environnement est devenue un enjeu majeur. La photocatalyse hétérogène, technique photochimique d'oxydation avancée, présente l'avantage d'oxyder de très nombreux contaminants de l'eau. Le catalyseur le plus utilisé est le dioxyde de titane (TiO2) pour des raisons d'efficacité, stabilité et de faible coût de production. Notre objectif dans cette thèse est de mieux maîtriser les propriétés de surface des photocatalyseurs à partir de deux nouveaux concepts. Le premier est basé sur le contrôle du caractère hydrophile ou hydrophobe de la surface. Le second consiste à utiliser de l'argile comme support du catalyseur ou sous forme de matériau composite. Une première manière de contrôler la surface consiste à la modifier par greffage de différentes molécules organiques de type organosilanes telles que l'hexadecyltrichlorosilane (HTS, hydrophobe) et le N-(6-aminohexyl)-aminopropyl-triméthoxysilane (AHAPS, hydrophile). Une autre manière de contrôler la surface de titane consiste à l'immobiliser sur un support. Le support choisi est l'argile en raison de leur grand pouvoir d'adsorption et de rétention des polluants. La préparation du système s'effectuait en deux voies : la copréciptation et le sol gel. A la fin de chaque partie des tests photocatalytiques ont été faite pour évaluer l'efficacité du système préparé / Protecting the environment has become a major issue. The heterogeneous photocatalysis , photochemical advanced oxidation technology has the advantage of oxidizing many contaminants from water . The most commonly used catalyst is titanium dioxide (TiO2) for reasons of efficiency, stability and low cost of production. Our goal in this thesis is to better control the surface properties of the photocatalysts from two new concepts. The first is based on the control of the hydrophilic or hydrophobic character of the surface. The second is the use of clay as catalyst support or as a composite material. A first way is to control the surface to modify the graft of different organic molecules such as organosilanes such hexadecyltrichlorosilane ( HTS , hydrophobic ) and N- (6- aminohexyl ) aminopropyl - trimethoxysilane ( AHAPS , hydrophilic ) . Another way of controlling the surface of the titanium is immobilized on a support. The selected material is clay because of their large adsorption capacity and retention of pollutants. System preparation was carried out in two methods: the copreciptation and sol/gel. At the end of each part, a the photocatalytic tests were conducted to evaluate the effectiveness of the system developed

Dans l’air intérieur, de nombreux composés organiques volatils sont présents, parmi lesquels le formaldéhyde, composé cancérogène. Sa présence dans l’air intérieur s’explique par son utilisation abondante dans les matériaux d’ameublement et de décoration. L’objectif est de concevoir un procédé d’épuration, propre, sûr et capable d’éliminer le formaldéhyde de l’air intérieur. Le choix s’est tourné vers un épurateur d’air autonome. Afin de protéger les utilisateurs, le dispositif doit piéger et dégrader complètement les polluants de l’air sans émettre de sous-produits. L’absorption a été choisie comme méthode de piégeage et la photocatalyse comme technique de dégradation. L’épurateur pilote couplant absorption et photocatalyse a été testé en laboratoire et un modèle a été construit pour prédire son efficacité à dégrader en continu le formaldéhyde. L’épurateur dimensionné pour une situation réelle se révèle avoir un encombrement réduit, compatible avec son installation dans un bureau / In indoor air, many volatile organic compounds are present, including formaldehyde. The presence of this carcinogenic compound in indoor air is due to its abundant use in furniture and decoration materials. The objective of this work is to design a purification device, clean, safe and capable of removing formaldehyde from indoor air. The choice turned to a stand-alone air purifier. To protect users, the device must trap and completely degrade air pollutants without emitting by-products. Absorption was chosen as trapping method and photocatalysis as degradation technique. The cleaner coupling absorption and photocatalysis has been tested in the laboratory and a model was built to predict its efficiency to continuously degrade formaldehyde. The purifier designed for a real situation appears to have a small volume. An efficient, compact, quiet and attractively designed device is an advantage for this air purification solution is accepted and adopted by users