Due to the environmental problems caused by the steadily increasing usage of fossil fuels, the interest for renewable sources of energy has amplified significantly. Among the several possibilities, hydrogen gas is considered to be one of the most promising fuels forof the future. IfOnce formed from water via photocatalysis it is a desirable, convenient and green improvement in the field of energy. During this work, we have tried to contribute to this important field. 4wt.% Au/TiO2 synthesized by deposition-precipitation with urea was the main photocatalysts used in this project. Other noble metal-loaded (Pt and Ag) titanium dioxide materials were synthesized by deposition precipitation with urea and other methods such as sol gel and sol immobilization. These catalytic systems were studied and their activity compared for hydrogen production from water/methanol mixtures. Sets of monometallic Au, Ag, Pt and bimetallic Au-Pt and Au-Ag supported titanium dioxide were synthesized and tested. Au/TiO2 photocatalysts synthesized by deposition precipitation with urea was were the best in terms of hydrogen production compared to other photocatalysts. In the evaluation of possible sacrificial molecules, isopropanol was less efficient than methanol. Through the formation of bi-metallic Ag-Au/TiO2 and Pt-Au/TiO2 catalysts, the hydrogen production could be further improved. Finally, Ir supported Al2O3 was investigated for the first time as a heterogeneous catalyst for hydrogen production by photocatalytic dehydrogenation of aqueous p-formaldehyde and photoreduction of carbon dioxide.

Photocatalytic degradation of phenol in aqueous solutions was investigated using heterogeneous photocatalysis with titanium dioxide (TiO2) particles immobilized on the inner wall of an annular upflow reactor. The influence of the concentration of phenol (measured as Dissolved Organic Carbon, DOC) at 15, 50, and 100 mgC L -1, the presence of hydrogen peroxide (H202), two different irradiation sources (germicidal and black light lamps), and two different reactor geometries (reactor 1 with 3,3 cm and reactor 2 with 7,0 cm outer diameters) were evaluated. To further investigate the effect of these parameters, the rate of phenol degradation, the quantum yield, and the energy consumption were calculated. According to the results obtained, the solution with an initial DOC concentration of 100 mgC L -1  in the presence of hydrogen peroxide (242 mmol L -1), using reactor 2 with the germicidal lamp as the photon source, gave the best performance, with degradation rates reaching 36,8 mgC h -1 and with one of the lowest energy consumptions (65 kWh m -3 order 1).

"The simultaneous degradation of five organic contaminants: 1,4 dioxane, n-nitrosodimethylamine, tris-2-chloroethyl phosphate, gemfibrozil, and 17β estradiol, was investigated using a 1 L batch water-jacketed UV photoreactor utilizing titanium dioxide (TiO2) nanoparticles (Degussa P-25) as a photocatalyst. The primary objectives of this research were: (1) to experimentally assess the feasibility of heterogeneous photocatalysis as a promising alternative for the degradation of organic compounds in water; and (2) to model the chemical reactions by the application of two different approaches based on adsorption – surface reactions (Langmuir–Hinshelwood) and its simplification to a first order rate reaction. These objectives were motivated by the lack of information regarding simultaneous degradation of organic compounds in different categories as found in real aqueous matrices, and generation of specific intermediates that could eventually represent a potential risk to the environment. Contaminants were chosen based on their occurrence in water sources, their representativeness of individual sub-categories, and their importance as part of the CCL3 as potential contaminants to be regulated. Contaminant degradation was evaluated over time, and the TiO2 concentration and solution pH were varied under constant UV irradiation, oxygen delivery rate, mixing gradient, and temperature. 

 Specific accomplishments of this study were: (1) reaction kinetics data were obtained from the UV/TiO2 experiments and showed the potential that this UV/TiO2 process has for effectively removing different types of organic compounds from water; (2) a good fit was obtained between photocatalytic reaction kinetics models and the contaminant data using pseudo first-order and Langmuir-Hinshelwood (L-H) models; (3) results of the analytical methods developed in this study were validated by measurements performed by a certified laboratory; (4) the reaction kinetic parameters obtained in this study were normalized to electrical energy per order, reactor volume and surface area of the photocatalyst in order to provide rate constants with wider applicability for scale-up to more complex systems; and (5) degradation intermediates from the oxidation process and from interaction among compounds were identified and possible pathways for their formation suggested. This research has provided a better understanding of the photocatalytic process for the removal of organic contaminants from complex aqueous matrices."

This century has seen a phenomenal growth in energy demands and environmental pollution, which has given rise to a worldwide awareness for the need to address these issues immediately. / This thesis focuses on the fabrication of high performance electrocatalysts applied in fuel cells and developing appropriate advanced oxidation processes for environmental remediation. It has been shown that ultrasonic irradiation is a promising method of synthesizing nanometre sized metal colloids with specific properties. Sonophotocatalysis has proved to be an effective process for the degradation of organic pollutants / The synthesis of platinum monometallic and platinum-ruthenium bimetallic nanoparticles was successfully achieved by using sonochemical irradiation. A chemical method and a hybrid method were used to reveal and understand the process of Ru(III) reduction by sonochemistry. TEM images of the Pt and PtRu monometallic/bimetallic particles indicate typical diameters of less than 10 nm. An effort was made to investigate the influence of two different methods, namely simultaneous and sequential sonochemical reduction, on the structure and formation of PtRu bimetallic nanoparticles. It has been shown that the sequential reduction method produces a relatively higher yield of core-shell nanoparticles than the simultaneous reduction method. It has been concluded that Pt nanoparticles, which are formed first, play an important role in catalysing the formation of Ru nanoparticles. / A number of methods including chemical, sonochemical and radiolytic synthesis were used to fabricate platinum and platinum-ruthenium monometallic/bimetallic nanoparticles. Furthermore, the evaluation of the electrocatalytic performance of these particles was performed by using cyclic voltammetry. Simultaneous and sequential methods for the synthesis of PtRu were adopted to investigate their influence on the electrocatalytic performance of these bimetallic nanoparticles. thas been shown that simultaneous reduction is an effective means of fabricating high performance electrocatalytic PtRu catalysts. A number of experiments with different ratios of platinum to ruthenium ions in precursor solution were carried out to study the effect of the ruthenium composition in platinum-ruthenium electrodes. It has been found that the methanol oxidation ability of platinum-ruthenium bimetallic nanoparticles can change with the alternation of ratio of Pt(II) to Ru(III) in the precursor solution. Simultaneous radiolytic reduction has the potential to fabricate higher performance electrocatalytic bimetallic nanoparticles. / Although both photo-oxidation and sono-oxidation techniques are fascinating solutions to the environmental problems at hand, the critical limit of these individual processes is their low efficiency of environmental remediation. In my project, sonolysis and photocatalysis (sonophotocatalysis) have been simultaneously employed to degrade selective organic pollutants in aqueous environments, such as methyl orange, p-chlorobenzoic acid, p-aminobenzoic acid and p-hydroxybenzoic acid. Experiments have been carried out in order to improve the efficiency of sonophotocatalytic reactions to ensure that a substantial amount of the electrical energy is utilized in degrading the organic pollutants. / Methyl orange, an azo dye, was selected as the degradation target for sonophotocatalysis. An orthogonal array analysis method was employed to clarify the correlation between the efficiencies of sonolysis, photocatalysis and sonophotocatalysis and the various operation conditions studied. Emphasis was placed on investigating the influence of pH and the ultrasound parameters on these three advanced oxidation processes. It was of interest to find that the degradation of methyl orange originates from hydroxylation and demethylation processes preceding aromatic ring-opening. / Sonophotocatalysis was also applied in the degradation of three aromatic carboxylic acids, p-chlorobenzoic acid, p-hydroxybenzoic acid and p-aminobenzoic acid. Experiments were carried out in order to get a thorough understanding of the synergy effects produced by combining the two oxidation techniques. A number of advanced analytical techniques, such as HPLC and Q-TOF MS/LC, were employed to comprehensively monitor and analyse the sonophotocatalytic degradation process. It has been found that synergistic effects of the combined system have been identified with respect to the parent organic pollutant as well as its degradation products. Additionally, products were quantitatively analysed by a kinetic simulation method in order to understand the reaction mechanism. This method also allowed us to quantify the synergy effects. It was observed that the solution pH played a key role in determining the degradation rate and controlling the direction of the degradation reaction. Based on the analytical data gathered, the sonophotocatalytic degradation pathway of the aromatic carboxylic acids was established. The experimental results suggest that the sonophotocatalytic technique is likely to lead to a complete mineralization of organic pollutants in aqueous solutions.

Orientadores: Anne Helene Fostier, Susanne Rath / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-06T03:46:22Z (GMT). No. of bitstreams: 1 Pereira_MariadoSocorroSilva_D.pdf: 916851 bytes, checksum: 669cced4ecf66125f019f5d502b3de80 (MD5) Previous issue date: 2005 / Doutorado / Quimica Analitica / Doutor em Ciências

Orientadores: Elizabete Jordão, Carlos Augusto de Moraes Pires / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T09:13:33Z (GMT). No. of bitstreams: 1 Paschoalino_FlaviaCristinaSertori_M.pdf: 5135552 bytes, checksum: e4bb125b1c8aa2e74689b42ad19d43bb (MD5) Previous issue date: 2008 / Resumo: O fenol e seus derivados estão presentes em efluentes de diversos processos industriais como refino de petróleo e indústria farmacêutica. Devido à sua característica recalcitrante e sua toxicidade, são poucos os processos biológicos capazes de degradá-lo adequadamente sem que uma grande diluição seja realizada, o que o direciona muitas vezes a tecnologias mais caras como a incineração ou o uso de reagentes oxidantes. Uma alternativa a estes métodos é a fotocatálise heterogênea, que é baseada na irradiação (UV) de um catalisador, promovendo a geração de radicais hidroxila ( OH) altamente reativos. Neste trabalho desenvolveu-se um fotoreator confeccionado em vidro PyrexTM, utilizando-se uma lâmpada de vapor de Hg de 250 W em seu centro, o qual era resfriado por uma camisa de vidro concêntrica a uma câmara externa de 290 mL reservada à passagem do efluente a ser tratado. O fotoreator foi acoplado a um recipiente de 500 mL, utilizando-se uma bomba para recirculação do efluente, tornando-o um reator em batelada com recirculação. A eficiência do reator foi avaliada utilizando-se TiO2 e ZnO como fotocatalisadores em suspensão aquosa de 0,5 ou 1,0 g L-1, e fenol a 100 ou 200 mg L-1 como solução-teste. A concentração de fenol foi medida em intervalos de tempo pré-determinados utilizando-se cromatógrafo a gás com detector por ionização em chama. O sistema demonstrou-se muito eficiente, pois atingiu em pouco tempo (135 min), independentemente do catalisador utilizado, a degradação quase que total de fenol para a solução-teste de 100 mg L-1, que é superior às concentrações normalmente utilizadas em trabalhos similares. Para as soluções de 200 mg L-1 a cinética foi mais lenta, mas o processo fotocatalítico foi mais eficiente do que os controles de fotólise e adsorção em todas as combinações testadas. / Abstract: Phenol and its derivatives are present in effluents from various industrial processes like oil refining and pharmaceutical industry. Due its recalcitrant character and toxicity, few biological processes are capable to degrade it properly, requiring expensive technologies such incineration or the use of oxidants. An alternative to these methods is the heterogeneous photocatalysis, which is based on irradiation (UV) of a catalyst, promoting the generation of hydroxyl radicals ( OH) highly reactive. In this work it was developed a photoreactor made in a PyrexTM glass, using a 250 W Hg vapor lamp at its center, which was cooled by a water flux that was concentric to a 290 mL irradiated chamber glass. The photoreactor was attached to a container of 500 mL, using a recirculation pump, making it in a batch reactor with recirculation. The efficiency of the reactor was evaluated by using TiO2 and ZnO as photocatalysis in 0,5 or 1,0 g L-1 slurries, and phenol at 100 or 200 mg L-1 as a solution-test. The concentration of phenol was measured at pre-determined time intervals by using a gas chromatograph with a flame ionization detector. The system proved to be very efficient, because reached in a short time (135 minutes), regardless of the catalyst used, the almost total degradation to the solution of phenol-test of 100 mg L-1, which is higher than the concentrations usually used in similar work. For solutions of 200 mg L-1 the kinetics was slower, but the photocatalytic process was more efficient than the controls of photolysis and adsorption in all combinations tested. / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Orientador: Carlos Kenichi Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-19T01:50:40Z (GMT). No. of bitstreams: 1 Boery_MirellaNagibdeOliveira_M.pdf: 2280722 bytes, checksum: de44802a3f6daef5829060dbc3396bce (MD5) Previous issue date: 2011 / Resumo: Este estudo acerca da obtenção controlada das nanopartículas e das fases cristalinas do dióxido de titânio investiga os parâmetros de deposição: fluxo de hidrogênio e oxigênio e, consequentemente, a razão dos gases H2/O2 na deposição pelo método aerossol em chamas. O objetivo é verificar a influência desses parâmetros no tamanho do cristalito, das nanopartículas e nas proporções das fases cristalinas (anatásio e rutilo) do dióxido de titânio (TiO2). Nas amostras caracterizadas são utilizadas as técnicas de difração de raios-X (DRX) e microscopia eletrônica de varredura (MEV). Atualmente o semicondutor TiO2 é um material muito utilizado na fotocatálise heterogênea, por isso muitos pesquisadores tentam otimizar as suas características a fim de obter um máximo de atividade fotocatalítica desse nanomaterial. Através do método aerossol em chamas, nanopartículas de TiO2 foram produzidas pela hidrólise e oxidação do tetracloreto de titânio (TiCl4), com a razão H2/O2 variando entre 0,17 e 3,00, possibilitando estabelecer as condições ideais para se produzir anatásio ou rutilo como única fase, ou a associação de anatásio mais rutilo. Observou-se que a razão H2/O2 possui uma relação direta com as fases cristalinas do dióxido de titânio e com o crescimento dos cristalitos das nanopartículas de TiO2, sendo possível neste trabalho produzir nanopartículas de TiO2 com fase cristalina e tamanho das nanopartículas controladas sem tratamento térmico. Após o tratamento térmico os cristalitos de TiO2 não tiveram grande aumento, mas como esperado, a fase cristalina predominou o rutilo / Abstract: This study aimed to investigated the deposition parameters: flow of hydrogen and oxygen, and consequently the ratio of gases H2/O2 on deposition by flame aerosol method in order to check the influence of these parameters on the crystallite size, and proportions of nanoparticles crystalline phases (anatase and rutile) of titanium dioxide (TiO2), and the samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Nowadays semiconductor TiO2 is a material widely used in photocatalysis, because of this, many researchers try to optimize their characteristics in order to achieve maximum photocatalytic activity of this nanomaterial. Through the flame aerosol method, nanoparticles of TiO2 were produced by hydrolysis and oxidation of titanium tetrachloride (TiCl4), with reason H2/O2 ranging between 0.17 and 3.00, making it possible to establish the ideal conditions to produce pure anatase , pure rutile or association of anatase more rutile. It was observed that the reason H2/O2 has a direct relationship with the crystalline phases of titanium dioxide and the growth of crystallites of TiO2 nanoparticles, it was possible to produce nanoparticles of TiO2 with controlled crystalline phase and size of nanoparticles without heat treatment. After heat treatment, the crystallites of TiO2 have no significant increase, but as expected, the rutile crystalline phase predominated / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Vários compostos utilizados ou produzidos pelo homem quando lançados no meio ambiente, ou mesmo em estações de tratamento de esgoto, não são facilmente degradados ou removidos. Desse modo, acabam voltando às estações de tratamento de água, que em sua maioria utilizam métodos que não são capazes de remover tais compostos, podendo até aumentar o efeito biológico destes. A detecção destes compostos é um desafio para a Química Analítica, já que ocorrem em baixas concentrações. Degradou-se uma mistura de quatro hormônios ¾ três naturais, 17 β-estradiol (E2), estrona (E1) e estriol (E3), e um sintético, 17 α-etinilestradiol (EE2) ¾ em água de abastecimento público pela fotocatálise heterogênea solar, utilizando-se o fotocatalisador dióxido de titânio suportado em um reator de placa plana operado com reciclo. Foi também desenvolvido e validado um método analítico totalmente automatizado que possibilitou detectar e quantificar baixas concentrações dos quatro hormônios. Foram obtidos limites de quantificação de 10 μg L-1, com a extração de 125 μL de amostra, com coeficiente de variação (< 20%) e exatidão (todos entre 80 a 120%) dentro dos limites aceitáveis para este tipo de análise. Foi possível verificar que a eficiência de degradação atingiu mais de 90% em menos de 4 horas para todos os hormônios. Mesmo com esse nível de degradação não foi possível a remoção da atividade estrogênica. Só houve uma redução significativa após 9 h de degradação. Possivelmente, a atividade estrogênica foi mantida pela concentração restante dos hormônios e/ou pela formação de produtos de degradação que também apresentavam atividade biológica. Alguns desses compostos foram propostos, sendo alguns conhecidos na literatura. No entanto, com as análises realizadas, não foi possível se ter certeza de que os compostos gerados no tratamento são realmente os sugeridos. / Several compounds used or produced by man, when released into the environment, or even in sewage treatment plants, are not easily degraded or removed. Thus, these compounds eventually return to water treatment plants, which mostly use methods incapable of removing them, and may even enhance their biological effect. The detection of these compounds is a challenge to Analytical Chemistry, as they occur at low concentrations. A mixture of four hormones were degraded ¾ three of them of natural origin, 17β-estradiol (E2), estrone (E1), and estriol (E3) and a synthetic one, 17α-ethinyl estradiol (EE2) ¾ in public water supply by solar heterogeneous photocatalysis, using supported titanium dioxide as the photocatalyst in a flat-plate reactor in recycling mode. A fully automated analytical method was developed and validated making it possible to detect and quantify low concentrations of the four hormones. Quantification limits of 10 μg L-1 were achieved with the extraction of a 125 μL-sample, with coefficients of variation (< 20%) and accuracy (all between 80 and 120%) were acceptable limits for this type of analysis. It was possible to observe that the degradation performance reached more than 90% in less than 4 hours for all hormones. Even with this level of degradation it was not possible to remove the estrogenic activity. There was only a significant reduction after 9 h of degradation. Possibly, the estrogenic activity was maintained by the remaining concentration of the hormones and/or by degradation by-products which still present biological activity. Some of these compounds were proposed, some of which have been already published in the literature. However, with the performed analyses, it was not possible to ascertain that the generated compounds during treatment are actually the ones here suggested.

Entre os processos oxidativos avançados, a fotocatálise heterogênea tem se destacado na degradação de poluentes recalcitrantes aos tratamentos convencionais. Neste processo, a geração de espécies radicalares ocorre a partir de uma fotoreação catalisada por materiais semicondutores, sendo o dióxido de titânio um dos mais utilizados, principalmente, devido a sua estabilidade química e baixo custo. A estrutura do TiO2 possui grande influência no processo fotocatalítico. Neste trabalho buscou-se preparar, a partir do TiO2 comercial e do TiO2 sintetizado pelo método sol gel, diferentes nanoestruturas do dióxido de titânio e avaliar o desempenho fotocatalítico destes materiais na degradação de fenol. Utilizando o tratamento hidrotérmico em meio fortemente alcalino, foi possível obter materiais nanoestruturados com maior área superficial, de até 308 m2 g-1. O tratamento foi aplicado em três diferentes precursores, com diferentes morfologias inicias. Avaliou-se o efeito de diferentes temperaturas (120 e 200 ºC) e tempos de tratamento (12, 24 e 48 horas), a fim de avaliar a influência das condições de tratamento e da morfologia inicial nos materiais obtidos. As amostras obtidas foram empregadas como catalisadores na degradação do poluente fenol por fotocatalise heterogênea. Em dois dos precursores estudados foram obtidas estruturas nanotubulares quando empregou-se condições mais brandas de tratamento. Em temperaturas mais severas, observou-se a formação de nanobastões. As amostras nanotubulares derivadas do TiO2 comercial anatásio, quando aplicadas na degradação do fenol, permitiram porcentagens de degradação superiores ao do precursor. Quando calcinadas, as amostras apresentaram resultados ainda melhores. O material tratado por 48 horas à 120 ºC possibilitou uma degradação de cerca de 100% do poluente, após 3 horas de irradiação. Utilizando três precursores com morfologias iniciais distintos foram observados resultados diferentes quanto a formação de nanoestruturas e atividade fotocatalítica, sendo o material obtido utilizando o TiO2 comercial anatásio, o que apresentou melhores resultados na degradação do fenol. / Among the advanced oxidation processes, heterogeneous photocatalysis has attracted great attention due the degradation of pollutants recalcitrant to conventional treatments. In this process, the generation of radical species takes place from a photoreaction catalyzed by semiconductor materials. Titanium dioxide is the most used catalyst mainly because of its chemical stability and low cost. The TiO2 structure has great influence on the photocatalytic process. In this study, different nanostructures of titanium dioxide were prepared from commercial TiO2 and TiO2 synthesized by sol gel method. The performance of these materials was evaluated the on the photocatalytic degradation of phenol. Using the hydrothermal treatment in strongly alkaline media, it was possible to obtain nanostructured materials with higher surface area, up to 308 m2 g-1. The treatment was employed in three different precursors with different initial morphology. It was evaluated the effect of different temperatures (120 and 200 °C) and treatment times (12, 24 and 48 hours) to assess the influence of processing conditions and of the initial morphology. The different materials were employed as catalysts in the phenol degradation by heterogeneous photocatalysis. In two precursors studied, nanotubular structures were obtained when it was used milder conditions of treatment. In more severe temperatures, it was observed nanorods formation. Nanotubular samples were obtained from commercial TiO2 anatase. When applied to the degradation of phenol, this material allowed degradation percentages higher than the precursor. When calcined, these samples showed even better results. The material treated for 48 hours at 120 °C allowed a phenol degradation of almost 100% after 3 hours of irradiation. Using three precursors with different initial morphologies it was observed different results regarding the formation of nanostructures and photocatalytic activity. The material obtained from the commercial anatase TiO2 it was the sample which presented the best result in the degradation of phenol

O dióxido de titânio (TiO2) é atualmente um dos catalisadores mais utilizados para remoção de poluentes em efluentes, devido a sua alta estabilidade química, baixo custo, não toxicidade e possibilidade de ativação por radiação solar. O ferricianeto ()63− é um dos complexos cianometálicos mais estáveis gerados nos efluentes da mineração aurífera. Nesta pesquisa se apresenta o estudo de degradação deste complexo por meio de fotolise, fotocatálise com TiO2, e fotocatalise assistida com peróxido (H2O2). Para conferir a degradação do complexo foram analisados ao final do processo, parâmetros químicos como quantificação de cianeto livre, formação de amônia, nitrato, assim como precipitação de ferro metálico. Os ensaios foram feitos no Laboratório de Fotoquímica e Superfícies-LAFOS da Universidade Federal Rio Grande do Sul por meio de uma lâmpada de irradiação UV, o reagente utilizado foi o ferricianeto de potássio [K3Fe(CN)6] grau analítico, preparado como uma solução sintética em condições próximas do pH dos efluentes de mineradoras, a pesquisa foi conduzida em condições de pressão e temperatura ambiente (1 atm e 25°C), testando diferentes concentrações de TiO2 e um analise sob irradiação solar. A partir de uma solução de 100 mg L-1 o efeito da fotólise demostrou que o complexo estudado apresenta uma grande estabilidade uma vez que em condições de irradiação UV (λ>300nm) foi observada uma baixa taxa de degradação após um período de 24 h, abaixo de 20%, enquanto em um sistema de fotocatálise heterogênea com TiO2 em condições alcalinas foram obtidas degradações de até 70%. O melhor resultado se atingiu no sistema de fotocatalise assistida com peroxido, sendo usado 2.5 vezes menos peroxido do que é utilizado na indústria, alcançando 83% degradação para um dos complexos mais estáveis formado pelo cianeto, o ferricianeto. Foram avaliados diferentes parâmetros para analisar o comportamento e degradação do complexo ferricianeto, como por exemplo a adsorção em fase escura do complexo sobre o catalisador; efeito da dosagem de TiO2, ação do H2O2 em baixa concentração, incidência da radiação UV em diferentes fontes com potência de 120 e 200 W e finalmente com radiação solar. Os resultados obtidos mostraram a influência do TiO2 junto com irradiação UV para atingir a degradação do complexo e formação de produtos menos tóxicos. / Titanium dioxide (TiO2) is one of the most frequently used catalysts applied for effluent treatment by pollution removal due to its high chemical stability, low cost, non-toxicity and the solar power is capable to activated it. Ferricyanide ()63− is one of the most stable cyanometallic complexes generated in the gold mining effluents. This research presents the study degradation of this complex by means of photolysis, photocatalysis with TiO2, and photocatalysis assisted with peroxide (H2O2). In order to verify the degradation of the complex, chemical parameters such as quantification of free cyanide, formation of ammonia, nitrate, as well as precipitation of metallic iron were analyzed at the end of the process. The tests were conducted at LAFOS (Surface and Photochemistry Laboratory) at UFRGS (Federal University of Rio Grande do Sul), using a UV irradiation lamp, the reagent used was potassium ferricyanide [K3Fe(CN)6] analytical grade, prepared as a synthetic solution with pH close to what is found at mining companies effluents. The tests were performed at normal temperature and pressure (1 atm e 25°C), testing different concentrations of TiO2 and an analysis under solar irradiation. From a solution of 100 mg L-1 the photolysis effect showed that the complex studied feature a high stability since under UV irradiation conditions (λ> 300 nm) a low degradation rate was observed after a period of 24 h, below 20%, whereas in a heterogeneous photocatalysis system with TiO2 under alkaline conditions degradations of up to 70% were obtained. The best result was obtained in the peroxide assisted photocatalysis system, using 2.5 times less peroxide than is used by the industry, reaching 83% degradation to one of the most stable complexes formed by cyanide, ferricyanide. Different parameters were used to analyze the degradation of ferricyanide complex, such as adsorption in dark stage over the catalyst; low concentration of H2O2, effects from TiO2 dosage, UV radiation incidence from different sources of 120 and 200W and finally solar radiation. The results obtained show the TiO2 influence along with UV irradiation to achieve degradation of the complex and less toxic products.