Os produtos lácteos são tidos como os alimentos mais perfeitos para o homem devido ao seu alto valor nutritivo. Entretanto, esses produtos vêm refletidos na elevada carga orgânica de efluente gerado. Os Processos Oxidativos Avançados (POA) são métodos químicos baseados na geração de radicais hidroxilas, que promovem a oxidação de compostos orgânicos. O uso de semicondutores no tratamento de efluentes tem sido de grande interesse devido à sua alta eficiência, estabilidade fotoquímica, natureza não-tóxica e baixo custo, especialmente quando a luz do sol é usada como fonte de irradiação. O uso de Óxido de Zinco (ZnO), por exemplo, além de mais econômico, absorve uma fração maior de espectro UV e tem melhor desempenho em pH neutro. Este estudo consistiu em avaliar a aplicação e eficiência da fotocatálise heterogênea (POA) solar com ZnO em termos de percentual de degradação de Carga Orgânica Total (COT) para um posterior tratamento biológico aerado visando melhorar as condições de despejo do efluente de modo a preservar o ecossistema e economia dos recursos naturais. O sistema POA consistiu de um volume fixo de efluente de 3L, de uma chapa metálica 800 x 250 mm revestida com uma formulação de tinta contendo ZnO, um reservatório de vidro, uma bomba centrífuga e aberto para absorção de radiações UV solar. Os resultados foram obtidos e analisados a partir do método de planejamento de experimentos em termos de percentual de degradação de COT. O melhor resultado apresentou um percentual de degradação de COT de 31,5% onde os níves das variáveis estudadas ocorreram em pH 8,0 em chapa de ZnO com espessura de 100 micrômetros (?m), utilizando o efluente in natura e o tempo total de reação de 3 h (180min). O efluente tratado pelo POA solar com ZnO foi submetido ao tratamento biológico aerado. O pH ótimo e a concentração de lodo foram de 6,0 e 5,0 mg/L, respectivamente. O percentual de degradação de COT para os tratamentos combinados foi de 75,1 % para o efluente de laticínios utilizado neste estudo. Isto sugere que o tratamento por POA utilizando ZnO seguido de um Tratamento Biológico Aerado seria uma alternativa promissora no tratamento de efluentes de laticínios. / Dairy products are the most perfect type of food for men due to its high nutritive value reflected on its high organic load of wastewater generated. The Advanced Oxidation Processes (AOP) are chemical methods based on the generation of hydroxyls radicals that promote the oxidation of organic compounds. The use of semiconductors in wastewater treatment has been of great interest owing to its high efficiency, photochemical stability, non-toxic nature and lower costs, especially when sunlight is used as source of irradiation. The use of Zinc Oxide (ZnO), for instance, besides being more economic, it also absorbs a greater range of UV spectrum and it has a better performance on neutral pH. This study consisted in evaluating the application and efficiency of solar photocatalytic oxidation (AOP) with ZnO in percentage terms of removal of Total Organic Carbon (TOC) prior to an aerobic biological treatment aiming to improve the conditions of the disposal of this wastewater in order to conserve the water environment and saving natural resources. The AOP system consisted of a working volume of 3 L, a sheet metal 800 x 250 mm covered with a paint formula containing ZnO, a glass vessel, a pump and an open system in order to collect solar UV radiation. The results were obtained and analyzed from design of experiments in terms of percentage of removal of TOC. The maximum percentage was found to be 31.5 % of removal of TOC and at pH 8.0, thickness of the sheet containing ZnO of 100 micrometers (?m), wastewater in natura and total time of reaction of 3 h (180 min). The solar AOP with ZnO treated wastewater was subjected to an aerobic biological treatment. The optimum pH and sludge loading were of 6.0 and 5.0 mg/L, respectively. The combination of both treatments resulted in 75.1 % of removal of TOC from the dairy wastewater used in this study. This suggests that the AOP using ZnO followed by an aerobic biological treatment would be a promising alternative for the treatment of dairy wastewater.

Yip, Ho-yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 181-201). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Contents --- p.vi / List of Figures --- p.x / List of Tables --- p.xvii / Abbreviations --- p.xix / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Polycyclic aromatic hydrocarbons (PAHs) --- p.1 / Chapter 1.1.1 --- Characteristics of PAHs --- p.1 / Chapter 1.1.2 --- Sources of PAHs --- p.2 / Chapter 1.1.3 --- Environmental fates of PAHs --- p.3 / Chapter 1.1.4 --- Effects of PAHs on living organisms --- p.5 / Chapter 1.1.4.1 --- General effects --- p.5 / Chapter 1.1.4.2 --- Effects on plants --- p.6 / Chapter 1.1.4.3 --- Effects on invertebrates --- p.7 / Chapter 1.1.4.4 --- Effects on fishes --- p.7 / Chapter 1.1.4.5 --- Effects on reptiles and amphibians --- p.8 / Chapter 1.1.4.6 --- Effects on birds --- p.9 / Chapter 1.1.4.7 --- Effects on mammals --- p.9 / Chapter 1.2 --- PAH contamination in Hong Kong --- p.10 / Chapter 1.3 --- Treatments of PAH contamination --- p.12 / Chapter 1.3.1 --- Physical treatments --- p.12 / Chapter 1.3.2 --- Chemical treatments --- p.13 / Chapter 1.3.3 --- Biological treatments --- p.14 / Chapter 1.4 --- Advanced oxidation processes (AOPs) --- p.16 / Chapter 1.5 --- Summary --- p.24 / Chapter 2. --- Objectives --- p.27 / Chapter 3. --- Materials and Methods --- p.28 / Chapter 3.1 --- Chemicals --- p.28 / Chapter 3.2 --- Photocatalytic reactor --- p.30 / Chapter 3.3 --- Determination of PAHs concentrations --- p.30 / Chapter 3.3.1 --- Extraction of PAHs --- p.30 / Chapter 3.3.2 --- Quantification of PAHs --- p.32 / Chapter 3.4 --- Optimization of physico-chemical conditions for PCO --- p.37 / Chapter 3.4.1 --- Determination of the reaction time for optimization of PCO --- p.37 / Chapter 3.4.2 --- Effect of titanium dioxide (Ti02) concentration and light intensity --- p.38 / Chapter 3.4.3 --- Effect of initial pH and hydrogen peroxide (H2O2) concentration --- p.38 / Chapter 3.4.4 --- Effect of initial PAHs concentration --- p.39 / Chapter 3.5 --- Toxicity analysis --- p.39 / Chapter 3.5.1 --- Microtox® test for acute toxicity --- p.39 / Chapter 3.5.2 --- Mutatox® test for genotoxicity --- p.42 / Chapter 3.6 --- Determination of total organic carbon (TOC) removal in optimized PCO --- p.43 / Chapter 3.7 --- Determination of degradation pathways --- p.43 / Chapter 3.7.1 --- Extraction of intermediates and/or degradation products --- p.45 / Chapter 3.7.2 --- Identification of intermediates and/or degradation products --- p.45 / Chapter 4. --- Results --- p.49 / Chapter 4.1 --- Determination of PAHs concentrations --- p.49 / Chapter 4.2 --- Optimization of extraction method --- p.49 / Chapter 4.3 --- Optimization of physico-chemical conditions for PCO --- p.49 / Chapter 4.3.1 --- Determination of the reaction time for optimization of PCO --- p.49 / Chapter 4.3.2 --- Effect of Ti02 concentration and light intensity --- p.60 / Chapter 4.3.3 --- Effect of initial pH --- p.88 / Chapter 4.3.4 --- Effect of initial H2O2 concentration --- p.99 / Chapter 4.3.5 --- Effect of initial PAHs concentration --- p.104 / Chapter 4.3.6 --- Improvements on removal efficiency (RE) after optimization --- p.113 / Chapter 4.4 --- Toxicity analysis --- p.122 / Chapter 4.4.1 --- Microtox® test for acute toxicity --- p.122 / Chapter 4.4.2 --- Mutatox® test for genotoxicity --- p.122 / Chapter 4.5 --- Determination of TOC removal in optimized PCO --- p.129 / Chapter 4.6 --- Determination of degradation pathways --- p.129 / Chapter 5. --- Discussion --- p.150 / Chapter 5.1 --- Determination of PAHs concentrations --- p.150 / Chapter 5.2 --- Optimization of extraction method --- p.150 / Chapter 5.3 --- Optimization of physico-chemical conditions for PCO --- p.151 / Chapter 5.3.1 --- Determination of the reaction time for optimization of PCO --- p.151 / Chapter 5.3.2 --- Effects of Ti02 concentration and light intensity --- p.152 / Chapter 5.3.3 --- Effects of initial pH --- p.160 / Chapter 5.3.4 --- Effects of initial H202 concentration --- p.163 / Chapter 5.3.5 --- Effects of initial PAHs concentration --- p.165 / Chapter 5.3.6 --- Improvements on RE after optimization --- p.167 / Chapter 5.4 --- Toxicity analysis --- p.169 / Chapter 5.4.1 --- Microtox® test for acute toxicity --- p.169 / Chapter 5.4.2 --- Mutatox® test for genotoxicity --- p.170 / Chapter 5.5 --- Determination of TOC removal in optimized PCO --- p.171 / Chapter 5.6 --- Determination of detoxification pathways --- p.172 / Chapter 6. --- Conclusion --- p.177 / Chapter 7. --- References --- p.181 / Chapter 8. --- Appendix I --- p.202

Submitted by Eunice Novais (enovais@uepg.br) on 2018-06-25T18:19:59Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Angélica de Sousa Hrysyk.pdf: 2633413 bytes, checksum: 814955f505551d7d05e203f53483d1c3 (MD5) / Made available in DSpace on 2018-06-25T18:19:59Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Angélica de Sousa Hrysyk.pdf: 2633413 bytes, checksum: 814955f505551d7d05e203f53483d1c3 (MD5) Previous issue date: 2018-04-06 / Por muito tempo os estudos sobre os tratamentos de resíduos estavam voltados a determinados grupos de poluentes considerados resistentes e tóxicos. Nos últimos anos espécies consideradas micropoluentes, com concentrações da ordem de μg L-1, têm recebido atenção, pois muitos destas possuem atividade farmacológica e devido ao seu grande uso e da baixa eficiência de remoção apresentada pelos sistemas de tratamento de esgoto podem contaminar águas superficiais e subterrâneas. Dessa forma, diversas pesquisas têm sido desenvolvidas na busca de novas formas de tratamento, com capacidade para a remoção de antibióticos, analgésicos, antiinflamatórios, entre outros. Os Processos Oxidativos Avançados (POA’s) têm apresentado reconhecida importância, pois mostram eficiente degradação desses micropoluentes que, em alguns casos, permitem a sua completa mineralização, ou seja, sua conversão em dióxido de carbono, água e íons inorgânicos. Em função de seu elevado uso pela população e potenciais problemas atribuídos a sua presença no ambiente existe a necessidade de investigação sobre metodologias de remediação para os fármacos amoxicilina (AMX), fluoxetina (FLU) e sinvastatina (SIN). Por isso, neste trabalho, foi estudada a potencialidade da fotocatálise heterogênea empregando dióxido de titânio imobilizado em acetato de celulose (TiO2/AC) assistido sob radiação ultravioleta (UV) em relação à remediação de matrizes aquosas contendo os fármacos AMX, FLU e SIN. O fotocatalisador sintetizado foi caracterizado por termogravimetria (TG) e análise térmica diferencial (DTA), Microanálise Quantitativa com mapeamento químico por Espectroscopia de Energia Dispersiva de Raios X (EDS), Difratometria de Raios X (DRX) e Espectroscopia no Infravermelho (FTIR). Os ensaios de degradação dos fármacos foram conduzidos em reator fotoquímico e as frações provenientes foram analisadas por cromatografia líquida de alta eficiência no comprimento de onda de máxima absorção para cada fármaco. Obtiveram-se degradações de 99,1% (SIN em 30 minutos), 85% (FLU em 180 minutos) e 99,0% (AMX em 240 minutos). Ensaios de fotólise foram realizados comprovando a baixa fotossensibilidade dos fármacos, sendo assim, atribui-se a degradação como resultante da interação entre o fotocatalisador TiO2/AC e a radiação ultravioleta. Análises de Cromatografia Gasosa acoplado ao detector de massas (CG/EM) permitiram quantificar e identificar os produtos de degradação, com resultados de Carbono Orgânico Total (COT) foi possível determinar a taxa de mineralização de 70, 43 e 15%, para AMX, FLU e SIN, respectivamente. Ensaios ecotoxicológicos realizados com a planta aquática Lemna aequinoctials Welw mostraram-se eficientes para se compreender como os fármacos e seus produtos de degradação podem afetar os organismos aquáticos. / For a long time the studies on the treatment of residues were directed at certain groups of pollutants considered resistant and toxic. In recent years, species considered micropollutants, with concentrations of the order of μg L-1, have received attention, since many of them have pharmacological activity and due to their great use and the low removal efficiency presented by sewage treatment systems can contaminate surface waters and underground. In this way, several researches have been developed in search of new forms of treatment, with capacity for the removal of antibiotics, analgesics, anti-inflammatories, among others. The Advanced Oxidative Processes (POAs) have been recognized as important because they show an efficient degradation of these micropollutants, which in some cases allow their complete mineralization, that is, their conversion into carbon dioxide, water and inorganic ions. Due to its high use by the population and potential problems attributed to its presence in the environment there is a need for research on remediation methodologies for the drugs amoxicillin (AMX), fluoxetine (FLU) and simvastatin (SIN). Therefore, the potential of heterogeneous photocatalysis using titanium dioxide immobilized in cellulose acetate (TiO2/AC) assisted under ultraviolet (UV) radiation in relation to the remediation of aqueous matrices containing the AMX, FLU and SIN drugs was studied. The photocatalyst was characterized by thermogravimetry (TG) and differential thermal analysis (DTA), Quantitative Microanalysis with chemical mapping by X-ray Dispersive Energy Spectroscopy (EDS), X-ray Diffraction (XRD) and Infrared Spectroscopy (FTIR). The drug degradation assays were conducted in a photochemical reactor and the fractions obtained were analyzed by high performance liquid chromatography at the maximum absorption wavelength for each drug. Degradations of 99.1% (SIN in 30 minutes), 85% (FLU in 180 minutes) and 99.0% (AMX in 240 minutes) were obtained. Photolysis assays were performed proving the low photosensitivity of the drugs, thus, degradation is attributed as a result of the interaction between the TiO2 / AC photocatalyst and ultraviolet radiation. Analysis of Gas Chromatography coupled to the mass detector (GC / MS) allowed to quantify and identify the degradation products, with results of Total Organic Carbon (TOC), it was possible to determine the mineralization rate of 70, 43 and 15% for AMX, FLU and SIN, respectively. Ecotoxicological assays performed with the aquatic plant Lemna aequinoctials Welw have been shown to be effective in understanding how drugs and their degradation products can affect aquatic organisms.

To design an efficient solar energy conversion device, theoretical input is extremely important to provide the basic guideline for experimental scientists, to fabricate the most efficient, cheap, and stable device with less efforts. This desire can be made possible if computational scientist use a proper theoretical protocol, design an energy material, then the experimentalist will only invest weeks or months on the synthetic effort. This thesis highlights my recent efforts in this direction. Monoclinic BiVO4 is has been using as a photocatalyst due to its stability, cheap, easily synthesizable, narrow band gap and ideal VB (-6.80 eV vs vacuum) but inappropriate CB (-4.56 eV vs vacuum) edge position, responsible for its low efficiency. We have carried out a comprehensive experimental and periodic density functional theory (DFT) simulations of the pristine, Oxygen defective (Ov), Se doped monoclinic BiVO4 and heterojunction with Selenium (Se-BiVO4), to improve not only its CB edge position but photocatalytic and charge carrier properties. It is found that Ov (1% Oxygen vacancy) and mild doped BiVO4 (1 to 2% Se) are thermodynamically stable, have ideal band edges ~ -4.30 eV), band gaps (~1.96 eV), and small effective masses of electrons and holes. We have also investigated the contribution of Se to higher performance by effecting morphology, light absorption and charge transfer properties in heterojunction. Finally, it is found that Se makes a direct Z-scheme (band alignments) with BiVO4 where the photoexcited electron of BiVO4 recombine with the VB of Se, consequences electron-hole separation at Se and BiVO4, respectively, as a result, enhanced photocurrent is obtained. Theoretical study of β-TaON in the form of primitive unit cell, supercell and its N, Ta, and O terminated surfaces are carried out with the help of periodic DFT. Optical and electronic properties of all these different species are simulated, which predict TaON as the best candidate for photocatalytic water splitting contrast to their Ta2O5 and Ta3N5 counterparts. The calculated bandgap, valence band, and conduction band edge positions predict that β-TaON should be an efficient photoanodic material. The valence band is made up of N 2p orbitals with a minor contribution from O 2p, while the conduction band is made up of Ta 5d. Turning to thin films, the valence band maximum; VBM (−6.4 eV vs. vacuum) and the conduction band minimum; CBM (−3.3 eV vs. vacuum) of (010)-O terminated surface are respectively well below and above the redox potentials of water as required for photocatalysis. Charge carriers have smaller effective masses than in the (001)-N terminated film (VBM −5.8 and CBM −3.7 eV vs. vacuum). However, due to wide band gap (3.0 eV) of (010)-O terminated surface, it cannot absorb visible wavelengths. On the other hand, the (001)-N terminated TaON thin film has a smaller band gap in the visible region (2.1 eV) but the bands are not aligned to the redox potential of water. Possibly a mixed phase material would produce an efficient photoanode for solar water splitting, where one phase performs the oxidation and the other reduction. Computational study of an optically transparent, near-infrared-absorbing low energy gap conjugated polymer, donor−acceptor−donor (D-A-D) with promising attributes for photovoltaic application is reported herein. The D and A moiety on the polymeric backbone have been found to be responsible for tuning the band gap, optical gap, open circuit (Voc) and short-circuit current density (Jsc) in the polymers solar cells (PSC). Reduction in the band gap, high charge transformation, and enhanced visible light absorption in the D-A-D system is because of strong overlapping of molecular orbitals of D and A. In addition, the enhanced planarity and weak steric hindrance between adjacent units of D-A-D, resulted in red-shifting of its onset of absorption. Finally, PSC properties of the designed D-A-D was modeled in the bulk heterojunction solar cell, which gives theoretical Voc of about 1.02 eV. DFT study has been carried out to design a new All-Solid-State dye-sensitized solar cell (SDSC), by applying a donor-acceptor conjugated polymer instead of liquid electrolyte. The typical redox mediator (I1−/I3−) is replaced with a narrow band gap, hole transporting material (HTM). A unique “upstairs” like band energy diagram is created by packing N3 between HTM and TiO2. Our theoretical simulations prove that the proposed configuration will be highly efficient as the HOMO level of HTM is 1.19 eV above the HOMO of sanitizer (dye); providing an efficient pathway for charge transfer. High short-circuit current density and power conversion efficiency is promised from the strong overlapping of molecular orbitals of HTM and sensitizer. A low reorganization energy of 0.21 eV and exciton binding energy of 0.55 eV, confirm the high efficiency of HTM. Theoretical and experimental studies of a series of four porphyrin-furan dyads were designed and synthesized, having anchoring groups, either at meso-phenyl or pyrrole-β position of a zinc porphyrin based on donor–π–acceptor (D–π–A) approach. The porphyrin macrocycle acts as donor, furan hetero cycle acts as π-spacer and either cyanoacetic acid or malonic acid group acts as acceptor. Optical bandgap, natural bonding, and molecular bonding orbital (HOMO–LUMO) analysis confirm the high efficiency pyrrole-β substituted zinc porphyrins contrast to meso-phenyl dyads. DFT study of polypyrrole-TiO2 composites has been carried out to explore their optical, electronic and charge transfer properties for the development of an efficient photocatalyst. Titanium dioxide (Ti16O32) was interacted with a range of pyrrole (Py) oligomers to predict the optimum composition of nPy-TiO2 composite with suitable band structure for efficient photocatalytic properties. The study has revealed that Py-Ti16O32 composites have narrow band gap and better visible light absorption capability compared to individual constituents. A red-shifting in λmax, narrowing band gap, and strong intermolecular interaction energy (-41 to −72 kcal/mol) of nPy-Ti16O32 composites confirm the existence of strong covalent type interactions. Electron−hole transferring phenomena are simulated with natural bonding orbital analysis where Py oligomers found as donor and Ti16O32 as an acceptor in nPy-Ti16O32 composites. Sensitivity and selectivity of polypyrrole (PPy) towards NH3, CO2 and CO have been studied at DFT. PPy oligomers are used both, in the doped (PPy+) and neutral (PPy) form, for their sensing abilities to realize the best state for gas sensing. Interaction energies and amount of charges (NBO and Mulliken charge analysis) are simulated which reveal the sensing ability of PPy towards these gases. PPy, both in doped and neutral state, is more sensitive to NH3 compared to CO2 and CO. More interestingly, NH3 causes doping of PPy and de-doping of PPy+, providing evidence that PPy/PPy+ is an excellent sensor for NH3 gas. UV-vis and UV-vis-near-IR spectra of nPy, nPy+, and nPy/nPy+-X complexes demonstrate strong interaction of PPy/PPy+ with these atmospheric gases. The applications of graphene (GR) and its derivatives in the field of composite materials for solar energy conversion, energy storage, environment purification and biosensor applications have been reviewed. The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing and removal of heavy metal ions is presented. Additionally, the presences of graphene composites in the bio-sensing field have been also discussed in this review.

Com o crescimento industrial e urbanização, diversos tipos de poluentes estão sendo encontrados com maior frequência e concentração em corpos hídricos. Um exemplo, são os corantes utilizados pelas indústrias têxteis. Grande parte desses poluentes, não é eliminada pelos processos atuais comumente empregados em estações de tratamento de águas residuais e plantas de tratamento de água potável. Devido a este fato, novas tecnologias para o tratamento da água estão sendo desenvolvidas, como os Processos Oxidativos Avançados (POAs). O objetivo do trabalho foi avaliar os fatores (físicos, químicos e estruturais) de um fotocatalisador (dióxido de titânio - TiO2), bem como as variáveis de um reator fotocatalítico que interferem na fotocatálise heterogênea (um tipo de POA). Para isso, sintetizou-se partindo do TiCl4, compostos de TiO2 com diferentes: morfologias (microesferas e nanotubos), características físicas e químicas, de modo a avaliar suas propriedades fotocatalíticas na degradação de corantes (azul de metileno e rodamina B), comparando os resultados aos obtidos com o nanopó comercial TiO2-P25. O reator fotocatalítico foi construído permitindo variar a potência, o comprimento de onda e a distância das lâmpadas para o sistema de reação. As microesferas sintetizadas a 550° (MT550) e nanotubos de titânia (NTT) apresentaram propriedades fotocatalíticas equivalentes ou superiores às do P25. O reator otimizado operou com quatro lâmpadas UVA próximas. O pH do meio foi determinante nos ensaios de fotocatálise. Sob pH neutro, as microesferas atuaram como adsorventes e fotocatalisadoras da rodamina B e adsorventes do azul de metileno. O P25 apresentou alta capacidade catalítica, em particular para meios neutro e básico. NTT demonstrou alta capacidade de adsorção do azul de metileno, porém baixo rendimento na adsorção e fotocatálise da rodamina B. / With industrial growth and urbanization, several types of pollutants are being found with greater frequency and concentration in water bodies. An example, are the dyes used by the textile industries. Most of these pollutants are not eliminated by current processes commonly used in sewage treatment plants and drinking water treatment plants. Due to this fact, new technologies for water treatment are being developed, such as Advanced Oxidative Processes (POAs). The aim of this work was to evaluate the physical, chemical and structural properties of a photocatalyst (titanium dioxide - TiO2), as well as the variables of a photocatalytic reactor that interfere with heterogeneous photocatalysis (a type of POA). For this, TiO2 compounds with different morphologies (microspheres and nanotubes), physical and chemical characteristics were synthesized from TiCl4, in order to evaluate their photocatalytic properties in the degradation of dyes (methylene blue and rhodamine B), comparing the results obtained with the commercial nanopowder TiO2-P25. The photocatalytic reactor was constructed allowing to vary the power, wavelength and distance of the lamps to the reaction system. The microspheres synthesized at 550°C (MT550) and titania nanotubes (NTT) showed photocatalytic properties similar to or superior to those of P25. The optimized reactor operated with four nearby UVA lamps. The pH of the medium was determinant in the photocatalysis experiments. At neutral pH, the microspheres acted as adsorbents and photocatalysts of rhodamine B and adsorbents of methylene blue. P25 showed high catalytic capacity, in particular for neutral and basic media. NTT showed high adsorption capacity of methylene blue, but low yields in adsorption and photocatalysis of rhodamine B.

Ce travail de thèse porte sur l’effet de la fluoration sur la réactivité du dioxyde de titane. Dans ce travail, trois familles de TiO2, dont l’anatase pure, le rutile pure et le TiO2 de la phase mixte anatase/rutile ont été fluorées par la méthode dite du choc thermique à différentes températures, de 400 – 950°C. Les influences de la fluoration sur les propriétés et la composition élémentaire de leur surface ont été étudiées par spectroscopie photoélectronique à rayonnements X (XPS). L’évolution de la structure cristalline, la morphologie et les propriétés optiques de ces catalyseurs en fonction de la fluoration a été également étudiée en détail par diffraction des rayons X, nanosonde Auger et spectroscopie de réflectance diffuse UV - Visible. Leur activité photocatalytique a été évaluée par la dégradation du bleu de méthylène en solution. Jusqu’à 500°C, la fluoration est uniquement surfacique et ne modifie ni la structure ni la morphologie des particules TiO2. Cependant la fluoration augmente la teneur en groupement OH de surface, ce qui contribue à l’augmentation de l’activité photocatalytique. Par contre, au-delà de 500°C, la méthode de fluoration forme une phase parasite anisotrope, K2Ti6O13 qui réduit les performances photocatalytiques. La réactivité de surface des catalyseurs fluorés a été également évaluée par l’adsorption de sondes gazeuses acide SO2 et basique NH3, couplée à l’analyse XPS. Les résultats montrent que tous les catalyseurs possèdent des surfaces amphotères dont l’acidité et la basicité sont significativement influencées par la fluoration. / The thesis aimed to investigate the influences of fluorination on the reactivity of titanium dioxide. In this work, three crystallographic families of TiO2: pure anatase, pure rutile and TiO2 P25 (mixed phase anatase/rutile), were fluorinated by thermal shock method at different temperatures, from 400 to 950°C. The influence of fluorination on the properties and elementary composition of their surface was studied by X ray photoelectron spectroscopy (XPS). The evolution of crystal structure, morphology and optic properties of these catalysts versus the fluorination was also studied in detail by X ray diffraction, Auger nanoprobe and diffuse reflectance UV – Visible spectroscopy. Their photocatalytic activity was evaluated by the degradation of methylene blue in solution. According to the results, the fluorination below 600°C only occurs on the surface and does not modify the structure and the particle size of TiO2. However, the fluorination enhances the surface hydroxyl groups, which are assigned to the improvement of photocatalytic activity. For the fluorination over 600°C, the parasite anisotropic K2Ti6O13 phase is formed, resulting in the reduction of photocatalytic performances.The surface reactivity of our catalysts was also evaluated by the adsorption of probe molecules acid SO2 and basic NH3, coupled with XPS analysis. The results show that the surface of all catalysts is amphoteric with the acidity and basicity significantly affected by fluorination.

Cheng Yee Wan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 95-112). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vi / List of Figures --- p.xi / List of Plates --- p.xiv / List of Tables --- p.xvi / Abbreviations --- p.xviii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Legionella pneumophila --- p.1 / Chapter 1.1.1 --- Bacterial morphology and ultrastructure --- p.2 / Chapter 1.1.2 --- Microbial ecology and natural habitats --- p.4 / Chapter 1.1.2.1 --- Association with amoeba --- p.5 / Chapter 1.1.2.2 --- Association with biofilm --- p.5 / Chapter 1.2 --- Legionnaires' disease and clinical significance --- p.6 / Chapter 1.2.1 --- Epidemiology --- p.6 / Chapter 1.2.1.1 --- Worldwide distribution --- p.6 / Chapter 1.2.1.2 --- Local situation --- p.7 / Chapter 1.2.2 --- Clinical presentation --- p.7 / Chapter 1.2.3 --- Route of infection and pathogenesis --- p.8 / Chapter 1.2.4 --- Diagnosis --- p.10 / Chapter 1.2.4.1 --- Culture of Legionella --- p.10 / Chapter 1.2.4.2 --- Direct fluorescent antibody (DFA) staining --- p.13 / Chapter 1.2.4.3 --- Serologic tests --- p.13 / Chapter 1.2.4.4 --- Urine antigen testing --- p.14 / Chapter 1.2.4.5 --- Detection of Legionella nucleic acid --- p.15 / Chapter 1.2.5 --- Risk factors --- p.15 / Chapter 1.2.6 --- Treatment for Legionella infection --- p.16 / Chapter 1.3 --- Detection of Legionella in environment --- p.16 / Chapter 1.4 --- Disinfection methods --- p.17 / Chapter 1.4.1 --- Physical methods --- p.19 / Chapter 1.4.1.1 --- Filtration --- p.19 / Chapter 1.4.1.2 --- UV-C irradiation --- p.20 / Chapter 1.4.1.3 --- Thermal eradication (superheat-and-flush) --- p.21 / Chapter 1.4.2 --- Chemical methods --- p.21 / Chapter 1.4.2.1 --- Chlorination --- p.21 / Chapter 1.4.2.2 --- Copper-silver ionization --- p.22 / Chapter 1.4.3 --- Effect of biofilm and other factors on disinfection --- p.23 / Chapter 1.5 --- Photocatalytic oxidation (PCO) --- p.24 / Chapter 1.5.1 --- Generation of strong oxidants --- p.24 / Chapter 1.5.2 --- Disinfection mechanism(s) --- p.27 / Chapter 1.5.3 --- Major factors affecting the process --- p.28 / Chapter 2. --- Objectives --- p.30 / Chapter 3. --- Materials and Methods --- p.31 / Chapter 3.1 --- Chemicals --- p.31 / Chapter 3.2 --- Bacterial strains and culture --- p.31 / Chapter 3.3 --- Photocatalytic reactor --- p.33 / Chapter 3.4 --- PCO efficacy tests --- p.33 / Chapter 3.5 --- PCO sensitivity tests --- p.35 / Chapter 3.6 --- Optimisation of PCO conditions --- p.35 / Chapter 3.6.1 --- Optimization of TiO2 concentration --- p.36 / Chapter 3.6.2 --- Optimization of UV intensity --- p.36 / Chapter 3.6.3 --- Optimization of depth of reaction mixture --- p.36 / Chapter 3.6.4 --- Optimization of stirring rate --- p.37 / Chapter 3.6.5 --- Optimization of initial pH --- p.37 / Chapter 3.6.6 --- Optimization of treatment time and initial cell concentration --- p.37 / Chapter 3.6.7 --- Combinational optimization --- p.37 / Chapter 3.7 --- Transmission electron microscopy (TEM) --- p.38 / Chapter 3.8 --- Fatty acid profile analysis --- p.40 / Chapter 3.9 --- Total organic carbon (TOC) analysis --- p.42 / Chapter 3.10 --- UV-C irradiation --- p.44 / Chapter 3.11 --- Hyperchlorination --- p.44 / Chapter 3.12 --- Statistical analysis and replication --- p.45 / Chapter 3.13 --- Safety precautions --- p.45 / Chapter 4. --- Results --- p.46 / Chapter 4.1 --- Efficacy test --- p.46 / Chapter 4.2 --- PCO sensitivity --- p.47 / Chapter 4.3 --- Optimization of PCO conditions --- p.48 / Chapter 4.3.1 --- TiO2 concentration --- p.48 / Chapter 4.3.2 --- UV intensity --- p.48 / Chapter 4.3.3 --- Depth of reaction mixture --- p.51 / Chapter 4.3.4 --- Stirring rate --- p.56 / Chapter 4.3.5 --- Effect of initial pH --- p.56 / Chapter 4.3.6 --- Effect of treatment time and initial concentrations --- p.56 / Chapter 4.3.7 --- Combinational effects --- p.63 / Chapter 4.4 --- Transmission electron microscopy (TEM) --- p.66 / Chapter 4.4.1 --- Morphological changes induced by PCO --- p.66 / Chapter 4.4.2 --- Comparisons with changes caused by UV-C irradiation and chlorination --- p.67 / Chapter 4.5 --- Fatty acid profile analysis --- p.71 / Chapter 4.6 --- Total organic carbon (TOC) analysis --- p.73 / Chapter 4.7 --- UV-C irradiation --- p.74 / Chapter 4.8 --- Hyperchlorination --- p.74 / Chapter 5. --- Discussion --- p.76 / Chapter 5.1 --- Efficacy test --- p.76 / Chapter 5.2 --- PCO sensitivity --- p.76 / Chapter 5.3 --- Optimization of PCO conditions --- p.77 / Chapter 5.3.1 --- Effect of TiO2 concentration --- p.77 / Chapter 5.3.2 --- Effect of UV intensity --- p.78 / Chapter 5.3.3 --- Effect of depth of reaction mixture --- p.79 / Chapter 5.3.4 --- Effect of stirring rate --- p.79 / Chapter 5.3.5 --- Effect of initial pH --- p.80 / Chapter 5.3.6 --- Effect of treatment time and initial concentrations --- p.81 / Chapter 5.3.7 --- Combinational effect --- p.82 / Chapter 5.4 --- Transmission electron microscopy (TEM) --- p.83 / Chapter 5.4.1 --- Morphological changes induced by PCO --- p.83 / Chapter 5.4.2 --- Comparisons with changes caused by UV-C irradiation and chlorination --- p.85 / Chapter 5.5 --- Fatty acid profile analysis --- p.85 / Chapter 5.6 --- Total organic carbon (TOC) analysis --- p.86 / Chapter 5.7 --- Comparisons of the three disinfection methods --- p.88 / Chapter 6. --- Conclusion --- p.91 / Chapter 7. --- References --- p.95 / Chapter 8. --- Appendix --- p.113

Les biofilms en industries agroalimentaires (IAA) représentent un problème récurrent aux conséquences économiques et de sécurité sanitaire. Le développement de surfaces photoactives aux propriétés antibactériennes pourrait faciliter leur élimination. Une solution serait de déposer une couche mince de dioxyde de titane (TiO2) sur des matériaux rencontrés dans les IAA. Les objectifs de cette thèse ont donc été d’optimiser des couches minces de TiO2 aux propriétés antibactériennes et d’étudier les mécanismes impliqués dans la photocatalyse. Les dépôts sont réalisés par pulvérisation cathodique radiofréquence dans différentes conditions (température, PO2, durée), d’abord sur substrat de verre puis sur acier inoxydable 316La caractérisation des couches minces par microscopie à balayage, diffraction des rayons X, a montré des différences dues au changement de substrat. Les différentes optimisations ont conduit à l’obtention de couches minces possédant une activité photocatalytique et des propriétés antibactériennes sur des souches représentatives de la flore retrouvée dans les IAA de la filière « viande » : L. monocytogenes, Y. enterocolitica et P. fragi. Des diminutions de la population bactérienne entre 1,5Log et 3Log ont été observées. La production d’espèces réactives de l’oxygène (H2O2, ¿OH, O2-¿) a été étudiée par des méthodes spectrocolorimétriques. L’H2O2 à la surface de la couche mince serait converti en ¿OH. L’étude des mécanismes de réponse de L. monocytogenes face à la photocatalyse des couches minces a été initiée par une approche transcriptomique, en suivant l’exp / Biofilms in food industries represent a recurrent problem with economic and health safety implications. The development of photoactive surfaces with antibacterial properties could facilitate their elimination. One solution would be to deposit a thin layer of titanium dioxide (TiO2) on conventional materials used in food plants. The objectives of this thesis were the optimization of thin films of TiO2 with antibacterial properties and to study the mechanisms involved in photocatalysis. Deposits were made by radio-frequency sputtering under different conditions (temperature, oxygen partial pressure, duration), first on a glass substrate and then on 316 stainless steel. Characterization of thin layers by scanning microscopy, diffraction of X-ray, showed differences due to substrate changeTiO2 thin layers obtained either on glass or stainless steel showed photocatalytic and antibacterial properties on representative strains of the flora found in the meat industry: Listeria monocytogenes, Yersinia enterocolitica and Pseudomonas fragi. Decreases in the bacterial population between 1.5Log and 3Log were observed. The production of reactive oxygen species (ROS) was studied by spectrocolorimetric methods. It seems that H2O2 on the surface is converted in another ROS, ¿OH. Finally, the study of the bacterial response mechanisms to photocatalysis, especially for L. monocytogenes, was initiated by a transcriptomic approach by following the expression of genes involved in the response to oxidative stress. However, the method used requires an optimization in order to be used for the bac

Submitted by JÚLIO HEBER SILVA (julioheber@yahoo.com.br) on 2018-03-29T17:08:27Z No. of bitstreams: 2 Dissertação - Nara Lúcia de Oliveira - 2018.pdf: 3506287 bytes, checksum: 7dcae9c4c0620421fdfd1b8117f3408c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-02T12:15:14Z (GMT) No. of bitstreams: 2 Dissertação - Nara Lúcia de Oliveira - 2018.pdf: 3506287 bytes, checksum: 7dcae9c4c0620421fdfd1b8117f3408c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-02T12:15:14Z (GMT). No. of bitstreams: 2 Dissertação - Nara Lúcia de Oliveira - 2018.pdf: 3506287 bytes, checksum: 7dcae9c4c0620421fdfd1b8117f3408c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-02-27 / The development of ceramic materials is important for the advancement of new technologies and the emergence of new economically viable materials. Modifying the synthesis method and relating its physical and chemical characteristics to possible industrial applications is part of the improvement process and offers alternatives to current production in improving the final product. In the present work, the synthesis and structural characterization of strontium and zinc stannates by the co-precipitation method, with and without microwave-assisted hydrothermal treatment, was carried out. The interest in the study with the application of the microwaves is in the sense of reducing the time and temperature of obtaining the main phase, perovskite. From the results of X-ray diffraction (XRD) it was possible to identify the formation of strontium and zinc stannates, monophasic after the addition of polyethylene glycol. The strontium stannate perovskite phase was obtained from the methodology with and without hydrothermal treatment assisted by microwave after calcination at 600 ºC for 2 hours. The zinc stannate with perovskite structure was obtained by the methodology with and without hydrothermal treatment assisted by microwaves without calcination. From the UV-VIS results optical values were obtained using Wood and Tauc theory. These values were all compatible with semiconductor materials, values between 2 and 4 eV. The images of the Electronic Transmission Electron Microscopy (ETM) characterization show the formation of nanotubes for the SrSnO3 samples and the cube morphology for the ZnSnO3 sample. The best performance was presented by the sample of ZnSnO3 calcined at 600 ºC, after hydrothermal treatment, presenting by XRD the formation of secondary phases, such as the spinel and rutile structure. / O desenvolvimento de materiais cerâmicos é importante para o avanço de novas tecnologias e o surgimento de novos materiais economicamente viáveis. Modificar o método de síntese e relacionar as suas características físicas e químicas com possíveis aplicações industriais, faz parte do processo de melhoramento e oferece alternativas à produção atual em melhorar o produto final. No presente trabalho realizou-se o estudo da síntese e a caracterização estrutural de estanatos de estrôncio e de zinco pelo método de coprecipitação, sem e com tratamento hidrotérmico assistido por micro-ondas. O interesse no estudo com a aplicação das micro-ondas é no sentido de reduzir o tempo e a temperatura de obtenção da fase principal, perovskita. Dos resultados de Difração de Raios X (DRX) foi possível identificar a formação de estanato de estrôncio e de zinco, monofásico após a adição de polietilenoglicol. O estanato de estrôncio a fase perovskita foi obtida da metodologia com e sem tratamento hidrotérmico assistido por micro-ondas após calcinação a 600 ºC por 2 horas. O estanato de zinco com estrutura perovskita foi obtido pela metodologia com e sem tratamento hidrotérmico assistido por micro-ondas sem calcinação. Dos resultados de UV-VIS foram obtidos valores de “gap” óptico utilizando teoria de Wood e Tauc. Estes valores foram todos compatíveis com materiais semicondutores, valores entre 2 e 4 eV. As imagens da caracterização por Microscopia Eletrônica de Transmissão (MET), mostram a formação de nano-tubos para as amostras de SrSnO3 e a morfologia de cubos para a amostra de ZnSnO3. O melhor desempenho foi apresentado pela amostra de ZnSnO3 calcinada a 600 ºC, após tratamento hidrotérmico, apresentando por DRX a formação fases secundárias, tais como a estrutura espinélio e rutilo.

Made available in DSpace on 2015-09-25T12:23:34Z (GMT). No. of bitstreams: 1 MyrthisVirginiaAlvesDeAlmeidaReinaldo.pdf: 991886 bytes, checksum: b2a23283e6671d15e111f946866efab9 (MD5) Previous issue date: 2006-02-23 / This research was accomplished with the purpose of studying the acting of a process developed for environmental disinfection, contributing for disinfection of wastewaters from anaerobic treatment systems of sanitary sewers. This process used the heterogeneous photocatalysis, that consists of the oxidation of organic pollutants through the generation of radicals hidroxila ( OH), highly oxidizers, which is gotten with the aid of a semiconductor and a UV radiation source. The semiconductor was the titanium dioxide (TiO2) and the source of energy from artificial luminous source (UV lamp) and natural (Sun) of ultraviolet radiation. Two types of reactors were used: a reactor type concentric tubes containing a 15W bactericidal UV lamp inside, treating wastewaters coming of two systems: UASB and Anaerobic Filter of Chicanes, with a flow of recirculation of 72 L.h-1 for 2 hours. In this reactor was made experiments with and without TiO2 in suspension. And a TiO2 impregnated plate reactor, treating wastewater of the anaerobic filter of chicanes, working in four different flow of recirculation: 13,2L.h-1, 25L.h-1, 42L.h-1 and 75L.h-1, for 4 hours of exposed to the sunlight. For both were evaluated the removal efficiencies of the fecal contamination indicative microorganisms - thermotolerants coliforms, and the rate of bacterial inativation through the study of the kinetic constant (k) and analyzed the physical and chemical parameters corresponding to the variation of the temperature, pH, electric conductivity (CE), total alkalinity and to bicarbonate, total nitrogen Kjeldahl (TNK), ammonia (NH3), total phosphor and orthophosphate, solids and your fractions, volatile greasiest acids (AGV) and removal of the organic matter (QDO). The kinetics study of the bacterial inativation (k) it revealed the best acting, in the concentric tubes reactor, for the experiment with photocatalysis using the anaerobic filter of chicanes wastewater. Already in the impregnated plate reactor, the best acting was observed in the 25L.h-1 flow, with 100% thermotolerants coliforms removed. The experiment with impregnated plate reactor it was shown efficient in the removal of the nitrogen compounds TNK and Ammonia. The smallest removal efficiency of thermotolerants coliforms of the UASB wastewater, in the concentric tubes reactor, was due to the high concentration of solids in suspension of the secondary wastewater, what block the uniformity of the UV radiation penetration. High evaporation rates, frequent in the experiments with the impregnated plate reactor, they caused increase in the final concentration of some parameters. The process of the heterogeneous photocatalysis is an efficient alternative method for the disinfection of tertiary wastewater with low concentration of solids in suspension. / Esta pesquisa foi realizada com a finalidade de estudar o desempenho de um processo desenvolvido para descontaminação ambiental, contribuindo para a desinfecção de efluentes de sistemas de tratamento anaeróbio de esgotos sanitários. Este processo foi o da fotocatálise heterogênea, que consiste na oxidação de contaminantes orgânicos através da geração de radicais hidroxila ( OH), altamente oxidantes, e que é conseguido com o auxílio de um fotocatalisador, no caso um semicondutor, e uma fonte de radiação UV. O semicondutor utilizado foi o dióxido de titânio (TiO2) e a fonte de energia luminosa proveniente de fonte artificial (lâmpada UV) e natural (Sol) de radiação ultravioleta. Foram utilizados dois tipos de reatores: um reator do tipo tubos concêntricos contendo uma lâmpada UV germicida 15W em seu interior, tratando efluentes provenientes de dois sistemas: UASB e filtro anaeróbio de chicanas, com uma vazão de recirculação de 72 L.h-1 durante 2 horas, com os quais foram feitos experimentos com e sem a utilização do TiO2 em suspensão; e um reator de placa impregnada com TiO2, tratando efluente do filtro anaeróbio de chicanas, trabalhando em quatro diferentes vazões de recirculação: 13,2 L.h-1, 25 L.h-1, 42 L.h-1 e 75 L.h-1, durante 4 horas de exposição à luz solar. Para ambos os reatores foram avaliadas as eficiências de remoção dos microrganismos indicadores de contaminação fecal os coliformes termotolerantes, como também a taxa de inativação bacteriana através do estudo da constante cinética (k) e analisados os parâmetros físico e químicos correspondentes à variação da temperatura, pH, condutividade elétrica (CE), alcalinidade total e a bicarbonato, nitrogênio total Kjeldahl (NTK), nitrogênio amoniacal (NH3), fósforo total e ortofosfato, sólidos e suas frações, ácidos graxos voláteis (AGV) e remoção de matéria orgânica (DQO). O estudo da constante cinética de inativação bacteriana (k) revelou o melhor desempenho, no reator de tubos concêntricos, para o experimento com fotocatálise utilizando o efluente do filtro anaeróbio de chicanas. Já no reator de placa impregnada, o melhor desempenho foi observado na vazão de 25L.h-1, com 100% dos coliformes termotolerantes removidos. O experimento com o reator de placa impregnada mostrou-se eficiente na remoção dos compostos nitrogenados NTK e N-amoniacal. A menor eficiência de remoção de coliformes termotolerantes do efluente do reator UASB, no reator de tubos concêntricos, deveu-se à alta concentração de sólidos em suspensão do efluente secundário, o que impede a uniformidade da penetração da radiação UV. Elevadas taxas de evaporação, freqüentes nos experimentos com o reator de placa impregnada, provocaram aumento na concentração final de alguns parâmetros. O processo da fotocatálise heterogênea é um método alternativo eficiente para a desinfecção de efluentes terciários com baixa concentração de sólidos em suspensão.