Inmovilización de TiO2 sobre polímeros transparentes en el UV-A para la eliminación fotocatalítica de tricloroetileno en aire

El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

Avaliação da radioatividade natural em tintas de uso comercial no Brasil

A radioatividade natural presente em solos, rochas e materiais de construção, devida ao 40K e às séries radioativas do 232Th e 238U é a principal contribuição à exposição externa aos seres humanos. Neste trabalho, determinou-se as concentrações de atividade de 226Ra (da série do 238U), 232Th e 40K presentes em 50 amostras de tintas látex de cor branca comercializadas no Brasil, especificamente, 15 do tipo econômico, 15 do tipo standard, 20 do tipo premium e em uma amostra de dióxido de titânio. As amostras foram seladas e armazenadas por um período mínimo de 30 dias para se alcançar o equilíbrio radioativo secular nas séries do 238U e do 232Th e medidas pela técnica analítica de espectrometria gama de alta resolução. As concentrações de atividade foram calculadas utilizando-se as médias ponderadas pelas incertezas do 214Pb e 214Bi para o 226Ra e médias ponderadas pelas incertezas do 228Ac, 212Pb e 212Bi para o 232Th. A concentração de atividade do 40K foi determinada pela sua transição única de 1460,8 keV. Fatores de autoatenuação gama foram calculados e utilizados para correção da concentração de atividade das amostras com densidade maior que 1,0 g.cm-3. Os índices radiológicos equivalente em rádio (Raeq), índice de concentração de atividade (Iγ), índice de risco à exposição gama interna (Hin), o índice de risco à exposição gama externa (Hex) e a taxa de dose (D) e dose efetiva anual (Def) foram calculados a partir das concentrações de atividade do 226Ra, 232Th e 40K. As concentrações de atividade de 226Ra das tintas variaram entre valores abaixo da atividade mínima detectável e 38,7 Bq.kg-1, as de 232Th variaram entre valores abaixo da atividade mínima detectável e 101,2 Bq.kg-1 e as de 40K variaram entre valores abaixo da atividade mínima detectável e 256 Bq.kg-1. O Raeq variou entre 1,41 Bq.kg-1 e 203 Bq.kg-1, o Iγ variou entre 0,0047 e 0,720, o Hin variou entre 0,0076 e 0,653 e o Hex variou entre 0,0038 e 0,549. A taxa de dose variou de 0,170 nGy.h-1 a 21,3 nGy.h-1 e a dose efetiva anual variou entre 0,83 μSv.a-1 e 104,2 μSv.a-1. Estes resultados mostram que as concentrações de atividades das tintas utilizadas neste estudo estão abaixo dos limites recomendados por Hassan et al. para Raeq (370 Bq.kg-1), pela Comissão Européia para o Iγ (limite de 2 para materiais superficiais) e pela Organização para Cooperação Econômica e Desenvolvimento para Hin e para Hex (ambos com limite de 1), para todas as 50 amostras estudadas, mostrando assim a segurança destas tintas com relação a proteção radiológica.

Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Spherical activated carbon as an enhanced support for TiO2/AC photocatalysts

Titanium dioxide nanoparticles prepared in situ by sol–gel method were supported on a spherical activated carbon to prepare TiO2/AC hybrid photocatalysts for the oxidation of gaseous organic compounds. Additionally, a granular activated carbon was studied for comparison purposes. In both types of TiO2/AC composites the effect of different variables (i.e., the thermal treatment conditions used during the preparation of these materials) and the UV-light wavelength used during photocatalytic oxidation were analyzed. The prepared materials were deeply characterized (by gas adsorption, TGA, XRD, SEM and photocatalytic propene oxidation). The obtained results show that the carbon support has an important effect on the properties of the deposited TiO2 and, therefore, on the photocatalytic activity of the resulting TiO2/AC composites. Thus, the hybrid materials prepared over the spherical activated carbon show better results than those prepared over the granular one; a good TiO2 coverage with a high crystallinity of the deposited titanium dioxide, which just needs an air oxidation treatment at low-moderate temperature (350–375 °C) to present high photoactivity, without the need of additional inert atmosphere treatments. Additionally, these materials are more active at 365 nm than at 257.7 nm UV radiation, opening the possibility of using solar light for this application.

Potentiostatic Reversible Photoelectrochromism: An Effect Appearing in Nanoporous TiO2/Ni(OH)2 Thin Films

In the field of energy saving, finding composite materials with the ability of coloring upon both illumination and change of the applied electrode potential keeps on being an important goal. In this context, chemical bath deposition of Ni(OH)2 into nanoporous TiO2 thin films supported on conducting glass leads to electrodes showing both conventional electrochromic behavior (from colorless to dark brown and vice versa) together with photochromism at constant applied potential. The latter phenomenon, reported here for the first time, is characterized by fast and reversible coloration upon UV illumination. The bleaching kinetics shows first order behavior with respect to the NiIII centers in the film, and an order 1.2 with respect to electrons in the TiO2 film. From a more applied point of view, this study opens up the possibility of having two-mode smart windows showing not only conventional electrochromism but also reversible darkening upon illumination.

Argamassas de auto-limpeza : da formulação às aplicações

Atualmente assiste-se a um grave problema de salubridade visual das cidades, designadamente no espaço edificado/ construído. A sujidade é uma ameaça que, junto com os graffitis, tem contribuído para a degradação precoce dos espaços urbanos. A fim de se enfrentar este problema, que tem vindo a proliferar nas cidades, um pouco por todo o mundo, a presente dissertação de mestrado ambiciona contribuir para a sistematização da informação existente sobre a produção e caracterização de argamassas de auto-limpeza. As argamassas de auto-limpeza são produzidas por uma de duas formas: com a adição de nanopartículas de dióxido de titânio (TiO2) na sua matriz ou com a aplicação de um filme fino à base de TiO2 na sua superfície. Esta segunda é apontada como a técnica mais eficaz e económica. Salienta-se o facto do TiO2 ser um dos nanomateriais mais utilizados na construção pelas suas propriedades fotocatalíticas que o capacitam como um dos mais exímios fotocatalisadores, aquando da fotocatálise heterogénea. É graças ao processo de fotodegradação química da fotocatálise, que na presença de luz solar e da ação da água, que o TiO2 é ativado, desencadeando reações químicas que aumentam a eficácia e eficiência fotocatalítica. Analisou-se um conjunto de trabalhos de investigação recentes que comprovam que o uso das argamassas de auto-limpeza é adequado e benéfico em intervenções em edifícios novos como em obras de conservação e reabilitação de edifícios antigos. Além de reduzirem os investimentos em obras de limpeza, manutenção/conservação e reabilitação, prolongam a conservação das fachadas e melhoram os níveis da qualidade do ar. Apesar do crescente número de patentes pedidas e concedidas nesta área, as normas aplicáveis ainda não se encontram uniformizadas. Nesse sentido, a experiência do Japão deve ser tida como exemplo para que os restantes países desenvolvam de forma consensual as suas próprias normas e patentes, permitindo, futuramente, conferir maior credibilidade, segurança no uso dos nanomateriais e uma maior permeabilidade no setor da construção. Elencam-se alguns nano-produtos à base de nano TiO2 comercializados que têm vindo a ser aplicados sobretudo na China, Japão e na Alemanha.

A Two-Step Sol–Gel Method for Synthesis of Nanoporous TiO2

This article reports a study of the effects of synthesis parameters on the preparation and formation of mesoporous titania nanopowders by employing a two-step sol-gel method. These materials displayed crystalline domains characteristic of anatase. The first step of the process involved the hydrolysis of titanium isopropoxide in a basic aqueous solution mediated by neutral surfactant. The solid product obtained from step 1 was then treated in an acidified ethanol solution containing the same titanium precursor to thicken the pore walls. Low pH and higher loading of the Ti precursor in step 2 produced better mesoporosity and crystallinity of titanium dioxide polymorphs. The resultant powder exhibited a high surface area (73.8 m(2)/g) and large pore volume (0.17 cm(3)/g) with uniform mesopores. These materials are envisaged to be used as precursors for mesoporous titania films as a wide band gap semiconductor in dye-sensitized nanocrystalline TiO2 solar cells.

Development of a co-culture model of the human lungs for toxicity testing and identification of biomarkers of inhalation toxicity

The airway epithelium is the first point of contact in the lung for inhaled material, including infectious pathogens and particulate matter, and protects against toxicity from these substances by trapping and clearance via the mucociliary escalator, presence of a protective barrier with tight junctions and initiation of a local inflammatory response. The inflammatory response involves recruitment of phagocytic cells to neutralise and remove and invading materials and is oftern modelled using rodents. However, development of valid in vitro airway epithelial models is of great importance due to the restrictions on animal studies for cosmetic compound testing implicit in the 7th amendment to the European Union Cosmetics Directive. Further, rodent innate immune responses have fundamental differences to human. Pulmonary endothelial cells and leukocytes are also involved in the innate response initiated during pulmonary inflammation. Co-culture models of the airways, in particular where epithelial cells are cultured at air liquid interface with the presence of tight junctions and differentiated mucociliary cells, offer a solution to this problem. Ideally validated models will allow for detection of early biomarkers of response to exposure and investigation into inflammatory response during exposure. This thesis describes the approaches taken towards developing an in vitro epithelial/endothelial cell model of the human airways and identification biomarkers of response to exposure to xenobiotics. The model comprised normal human primary microvascular endothelial cells and the bronchial epithelial cell line BEAS-2B or normal human bronchial epithelial cells. BEAS-2B were chosen as their characterisation at air liquid interface is limited but they are robust in culture, thereby predicted to provide a more reliable test system. Proteomics analysis was undertaken on challenged cells to investigate biomarkers of exposure. BEAS-2B morphology was characterised at air liquid interface compared with normal human bronchial epithelial cells. The results indicate that BEAS-2B cells at an air liquid interface form tight junctions as shown by expression of the tight junction protein zonula occludens-1. To this author’s knowledge this is the first time this result has been reported. The inflammatory response of BEAS-2B (measured as secretion of the inflammatory mediators interleukin-8 and -6) air liquid interface mono-cultures to Escherichia coli lipopolysaccharide or particulate matter (fine and ultrafine titanium dioxide) was comparable to published data for epithelial cells. Cells were also exposed to polymers of “commercial interest” which were in the nanoparticle range (and referred to particles hereafter). BEAS-2B mono-cultures showed an increased secretion of inflammatory mediators after challenge. Inclusion of microvascular endothelial cells resulted in protection against LPS- and particle- induced epithelial toxicity, measured as cell viability and inflammatory response, indicating the importance of co-cultures for investigations into toxicity. Two-dimensional proteomic analysis of lysates from particle-challenged cells failed to identify biomarkers of toxicity due to assay interference and experimental variability. Separately, decreased plasma concentrations of serine protease inhibitors, and the negative acute phase proteins transthyretin, histidine-rich glycoprotein and alpha2-HS glycoprotein were identified as potential biomarkers of methyl methacrylate/ethyl methacrylate/butylacrylate treatment in rats.

Synthesis and evaluation of nanoparticle-polymer composites

This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

Toxicity evaluation of TiO2 Nanoparticles embedded in consumer products

Lo studio è orientato alla determinazione dei rischi tossici posti dalle nanoparticelle di diossido di titanio rilasciate in ambiente marino. L’organismo modello utilizzato per questo studio è la diatomea Thalassiosira pseudonana, la quale è stata scelta per la sua semplicità biologica unita alla fondamentale rilevanza nella catena alimentare e nell’ecosistema marino. Oltre alle nanoparticelle prodotte industrialmente, questo studio ha lo scopo di determinare e confrontare la tossicità delle nanoparticelle utilizzate in alcuni prodotti di cura personale (in particolare crema solare e dentifricio), estraendole direttamente da essi. I nostri risultati mostrano una notevole ridondanza nel legame tra la natura (il tipo) delle nanoparticelle e l’inibizione della normale crescita delle diatomee, che supera la correlazione con tutti gli altri parametri monitorati (concentrazione di nanoparticelle, tempo di esposizione, pH, carica superficiale e dimensione delle particelle stesse), sebbene gli altri parametri risultino direttamente legati agli effetti inibitori. Tali risultati suggeriscono un’intensificazione della ricerca nell’ambito delle nanotecnologie, orientata allo sviluppo di nanomateriali “sostenibili”, ovvero dei quali sono note le potenzialità di impiego, ma anche gli aspetti negativi, che possono di conseguenza essere monitorati con maggiore consapevolezza.

Degradação de paracetamol empregando tecnologia oxidativa avançada baseada em fotocatálise heterogênea usando irradiação artificial e solar

In this work, the oxidation and mineralization of paracetamol, based in an advanced oxidative process promoted by heterogeneous photocatalysis, was evaluated. The action of two photocatalysts (titanium dioxide, and a composite based on the association between titanium dioxide and zinc phthalocyanine dye) was studied. First of all, experiments in laboratory scale were performed using as radiation font a 400 W high pressure mercury lamp. The mineralization of paracetamol, promoted by both photocatalysts, was evaluated working with 4L of solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. To find the best experimental conditions, the influence of hydrogen peroxide concentration and pH was evaluated for the reactions. The best results for the reactions in laboratory scale was obtained using 33,00 mg L-1 of hydrogen peroxide in natural pH (6,80). Under these conditions, 100% oxidation was reached in just 40 minutes of reaction using TiO2 P25, while the mineralization was 78%. Using the composite, the mineralization was 63% in 2 hours of reaction and a oxidation of almost 100% was reached after 60 minutes. A CPC reactor (compound parabolic concentrator) was employed in the expanded work scale, using the sun as irradiation source. In this case the experiments were performed using 50 L of aqueous solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. The assays were done at pH 3,00 and natural pH (6,80). The used concentration of hydrogen peroxide was 33,00 mg L-1, adopted after laboratory scale studies. The reaction at pH 3,00 shows to be more advantageous, since under natural pH (6,80), the use of deionized water was necessary to prepare the solutions, probably because the deleterious action of carbonate ions, known hydroxyl radical scavengers. Using solar irradiation, the reaction mediated by the composite was more efficient when compared with the assays under laboratory scale since the composite presents the advantage of promoting a better use of visible radiation. Under these conditions, the mineralization increased from 40% to 56% under pH 3,00. At natural pH the oxidation occurred more slowly and the mineralization decreased from 56% to 50%. Thus, the use of pH 3,00 will be more interesting in real scale applications, even if it is necessary the pH correction before the discard of the treated effluent to the environment.

Caracterização e avaliação da atividade fotocatalítica de catalisadores baseados no TiO2, sintetizados mediante hidrólise em uma mistura de solventes

This study involved the synthesis of photocatalysts based on titanium dioxide (TiO2). The photocatalysts were synthesized by the sol-gel method using three different proportions of acetone (25%, 50% and 75% v/v) in water/acetone mixtures, in order to control the hydrolysis of the precursor of titanium (titanium tetraisopropoxide). Aiming to investigate the structural, morphological and electronic changes provoked by the use of the solvent mixtures, different methodologies were used to characterize the oxides, such as X-ray diffraction (XRD), RAMAN spectroscopy, UV-Vis diffuse reflectance spectroscopy, and measurements of specific surface area (BET). XRD combined to RAMAN analyses revealed that the products are two-phase highly crystalline oxides involving anatase as main phase and brookite. Besides, the refined XRD using the method of Rietveld demonstrated that the presence of acetone during the synthesis influenced in the composition of the crystalline phases, increasing the proportion of the brookite phase between 13 and 22%. The band gap energy of these oxides practically did not suffer changes as function of the synthesis conditions. As shown by the isotherm, these photocatalysts are mesoporous materials with mean diameter of pores of 7 nm and approximately 20% of porosity. The surface area of the oxides prepared by hydrolysis in presence of acetone was 12% higher compared to the bare oxide. After characterized, these oxides had their photocatalytic activities evaluated by photodegradation of the azo dyes Ponceau 4R (P4R), Tartrazine (TTZ) and Reactive Red 120 (RR120), and also by the ability to mediate the photocatalytic production of hydrogen. Using the most efficient photocatalyst, the mineralization achieved for the dyes P4R, RR120 and TTZ was of respectively 83%, 79% and 56% in 120 minutes of reaction, while the discoloration of P4R e RR120 reached 100% and 94% for TTZ. In addition, the same photocatalyst in the presence of 0.5% w/w of Platinum and suspended in a 5:1 v/v water/methanol mixture, produced 56 mmol of gaseous hydrogen in five hours of experiment, corresponding to a specific rate of hydrogen production of 139.5 mmol h-1 g-1.