Nanotubular titanates were synthesized by a simple methodology using a commercial TiO2 (Degussa P25 containing anatase and rutile phases) and a base (KOH) solution. Prior to the removal of KOH, the samples of TiO2 were aged for three different time intervals (0, 2 days, 61 days). The freshly prepared synthetic samples were characterized for their structural and morphological properties by BET, XRD, Raman, TEM, HRTEM, EDX and SEM. Both TEM and SEM analysis revealed that ageing time influenced the tubular structure and morphology of the new materials. Raman and surface analysis data also showed that ageing time affected both the structural and surface properties of TiO2. The XRD results showed that the crystallinity of the TiO2 decreased with increasing ageing time. Energy dispersive Xray spectroscopy (EDX) showed that the tubes derived from TiO2 are comprised of potassium, titanium and oxygen. Catalysts A, B and C were prepared by the addition of 1 wt% Pd (wet impregnation) to the titanate formed after ageing of the TiO2 in KOH for 0, 2 and 61 days, respectively. The catalysts were tested for the vapour phase hydrogenation of phenol in a fixed-bed micro reactor within the temperature range of 165 to 300oC under atmospheric pressure. Of the three catalysts, catalyst B showed the best activity (conversion 97%) and total selectivity to cyclohexanone (99%). In contrast, catalyst C, which showed a moderate activity favoured selectivity to cyclohexanol. These results are attributed to differences in surface morphologies between the two catalysts B and C, associated with the surface area and a change in the surface acid-base properties. Catalyst B also showed a higher resistance towards deactivation and maintained a higher total selectivity to cyclohexanone than did catalyst C. A hydrothermal treatment of NaOH and TiO2 was employed to prepare two materials, TiO2-B and TiO2-C with relatively small crystallite size and large specific surface area. The hydrogenation of phenol was used to evaluate the activity of the catalysts Pd/TiO2-B and Pd/TiO2-C. The reaction proceeds in a single step and involves the formation of a partially hydrogenated product, namely cyclohexanone. The larger surface area catalyst (Pd/TiO2-C, 89 m2/g) showed better activity and selectivity to cyclohexanone than its counterpart (Pd/TiO2-B, 45 m2/g). The catalyst activity showed significant dependency on the surface area whereas the selectivity was greatly influenced by surface basicity. Titania derived nanotubes synthesized by treating P25 Degussa TiO2 with a concentrated KOH solution and aged for 2 days was used as a catalyst support for the hydrogenation of o-chloronitrobenzene (O-CNB) with Pd as the active phase. The vapour-phase hydrogenation of O-CNB was carried out in ethanol at 250 oC and atmospheric pressure over a Pd/TiO2 derived nanotube catalyst (Pd/TiO2-M). Pd/TiO2-M gave complete conversion (100%) of O-CNB with a selectivity to orthochloroaniline (O-CAN) of 86 %. The stability of the Pd/TiO2 catalyst was tested over 5 hours during which time the conversion slowly dropped to 80 % (selectivity 93 %) due to poisoning. TPR analysis revealed the existence of a strong palladium-support interaction and this was found to be crucial to the overall activity of the catalyst. It has been found that gold supported on potassium titanate, KTiO2(OH) can, under some circumstances, exhibit a superior performance for the oxidation of carbon monoxide, relative to that obtained with titania as a support. It appears that the dispersions of gold on the two types of support are sufficiently similar that other factors are responsible for the improved activity noted. It may be that the higher basic character and detailed structural features of the titanate surface play a role. The effect of the addition of alkali metal ions on the anatase to rutile transformation of titanium dioxide (P25 Degussa) was investigated using X-ray diffraction, Raman spectroscopy, and surface area measurements. Both Li and Cs ions accelerated the anatase to rutile transformation whereas Na and K ions did not show any effect. Furthermore, the effect was more pronounced after addition of the Li ions so that the transformation temperature dramatically decreased from ~800 oC for commercial TiO2 to ~600 oC. The surface area of the TiO2 material decreased with sintering due to the increase in crystalline size. Moreover, the acceleration of the transformation occurred at lower temperatures and at higher Li content. Mesoporous nanocrystalline TiO2 (HSA TiO2) was prepared by hydrothermal treatment of TiO2 with NaOH. The material was very amorphous and underwent the phase transformation from amorphous to anatase phase and subsequently from anatase to rutile phase with sintering. The anatase to rutile transformation was delayed after doping and grain growth was inhibited. After sintering at 800 oC the material (HSA TiO2) still contained a significant amount of the anatase phase. The complete transformation only occurred at ~1000 oC. The esterification of benzoic acid and butyric acid with propanol over alkali metal ions supported on TiO2 was investigated. K/TiO2-D showed the highest conversion for both benzoic acid and butyric acid. The selectivity to propylbenzoate and propylbutyrate was influenced by the basic nature of the catalysts. Butyric acid was found to be more reactive than benzoic acid. The difference in reactivity was explained in terms of steric and inductive effects. The differences in boiling points and pH values were also considered.

Un nanotube de dioxyde de titane autoporteur (TiO2 nts) est exploré en tant qu’électrode négative potentielle pour les microbatteries Li-ion 3D. Différentes modifications chimiques du TiO2 ont été explorées et étudiées, comme le TiO2 allié au Nb, le TiO2 revêtu d'ALD-Al2O3, le titanate de lithium-TiO2 et le TiO2 sulfuré. Le dépôt d'électrolyte polymère à base de PEO (oxyde d'éthylène) (PMMA-PEG) portant le sel de LiTFSI dans du TiO2 a été obtenu par la réaction d'électropolymérisation sur l'anode TiO2 et la cathode Lithum nickel oxyde de manganèse (LNMO). L'objectif principal ici était d'exploiter la surface active des électrodes par électrodéposition et d'améliorer ainsi l'interface électrode-électrolyte. Une telle micro-batterie contenant des électrodes revêtues de polymère révèle que les valeurs de capacité obtenues à différents taux de C sont doublées lorsque les électrodes sont complètement remplies par l'électrolyte polymère par rapport à la micro-batterie à électrodes brutes. Les excellentes performances électrochimiques sont attribuées aux interfaces électrode-électrolyte améliorées dans les deux électrodes / Self-supported titanium dioxide nanotube (TiO2 nts) is explored as a potential negative electrode for 3D Li-ion microbatteries. Different chemical modifications on the TiO2 nts have been explored and studied like Nb-alloyed TiO2 nts, ALD-Al2O3 coated TiO2 nts, Lithium titanate-TiO2 nts and sulphurized TiO2 nts. The deposition of PEO (polyethylene oxide) based polymer electrolyte (PMMA-PEG) carrying LiTFSI salt into TiO2 nts has been achieved by the electropolymerization reaction on the TiO2 nts anode and the Lithum nickel manganese oxide (LNMO) cathode. The main aim here was to exploit the active surface area of the electrodes using electrodeposition and there by enhance the electrode-electrolyte interface. Such a microbattery containing polymer-coated electrodes reveal that the capacity values obtained at different C-rates are doubled when the electrodes are completely filled by the polymer electrolyte compared with the microbattery with the raw electrodes. The excellent electrochemical performance is attributed to the improved electrode-electrolyte interfaces in both the electrodes

Bone implants procedures involve millions of people every year worldwide. One of the main factors determining implant success is related to the ability of the prostheses to osseointegrate, i.e. to create a structural and functional connection with the living bone. Titanium and titanium alloys are widely used biomaterials for bone implants, due to their superior biocompatibility and corrosion resistance, suitable mechanical properties, and natural ability to osseointegrate. To further enhance the inherent tendency of this class of materials to bond with the host bone tissue, the surface of Ti-based implant is often modified to improve cell responses in terms of adhesion, proliferation and differentiation, all factors contributing to successful osseointegration. In particular, surface topography, both at the micro- and nanoscale, can enhance the implant-living bone interaction. Herein, a possible surface modification strategy aimed at the creation of a dual-scale topography on two different titanium alloys, Ti-6Al-4V and Ti-5Al-5Mo-5V-3Cr, is presented. Dual-scale topography was obtained by electrochemically anodizing samples manufactured by selective laser melting to combine their intrinsic microtopography with the nanotopography offered by titanium dioxide nanotubes (TNTs) generated by anodization. Characterization of the as-printed and as-anodized samples was performed to evaluate parameters of significance in the context of osseointegration. Concerning wettability, it was observed that surfaces with TNTs exhibited high hydrophilicity. The influence of the anodization process parameters on TNTs morphology was examined, and linear dependence of the nanotube diameter on the voltage was identified. Annealing of the as-anodized samples showed that anatase was produced, while preserving the nanotube integrity. Preliminary studies to assess the bioactive properties of the samples showed the spreading of bone-like cells on these substrates and the deposition of mineral during simulated body fluid testing. Therefore, both studies provided promising results to corroborate the hypothesis that dual-scale topography could potentially improve osseointegration. / Thesis / Master of Applied Science (MASc) / Bone implants are often made of titanium-based materials, which, despite their suitable properties, may not sufficiently bond with the living bone tissue. This can lead to implant loosening and failure. To produce customized implants, additive manufacturing, or 3D-printing, can be employed. However, these surfaces require substantial post-processing to produce features capable of promoting bone integration. In this work, a dual-scale surface topography to combine the advantages of both micro- and nanoscale roughness was created using electrochemical anodization on 3D-printed titanium alloy substrates. Preliminary physical, chemical, and biological characterizations suggest that the creation of titania nanotubes on the 3D-printed surfaces of Ti-6Al-4V and Ti-5Al-5Mo-5V-3Cr could improve their ability to bond with bone.

The main objective of this work was to study the applicability of Nano porous/Nanocrystalline TiO2 films for serving the growing demand for fast accurate and low cost air quality analysis techniques. The sensitivity of response to variations in microstructure pointed the way to obtain controlled, reproducible and regular microstructures with critical dimensions proportionate with the Debye- length of the oxide. This work aimed to study the sensor properties of thin films of Nanocrystalline Titania and Titania nanotubes at room temperature. Nano porous/Nanocrystalline TiO2 films were fabricated through evaporation driven convection/sol-gel method by controlling the process conditions. We also fabricated ordered TiO2 nanotube arrays by carefully controlling the anodization conditions. TiO2 nanotube arrays were fabricated through potentiostatic anodization of a Ti metal sheet in various electrolyte mediums. The electrolyte mediums consisted of mixtures of acids ranging from HF, HCl, HNO3, H2SO4, H3PO4 and CH3COOH and polar organic solvents like C2H6OS(DMSO) and C2H4(OH)2(Ethylene Glycol) . Well ordered films consisting of TiO2 nanotube arrays (25 μm to 250 μm in length) were obtained. Contacts were deposited on to the annealed samples. Capacitive gas sensors were fabricated and their response to ammonia gas was evaluated.

Este trabalho apresenta o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com nitrogênio, visando melhorar sua atividade fotocatalítica sob radiação visível. Os nanotubos de TiO2 foram preparados pelo método hidrotérmico, onde partículas de TiO2 reagem com NaOH a temperatura e pressão elevadas. Em seguida o material é tratado, através de uma lavagem ácida e calcinação, de modo a apresentar as características desejáveis para a aplicação como fotocatalisador. Foram determinadas as melhores condições de obtenção dos nanotubos avaliando-se sua atividade fotocatalítica, variando-se o pH da solução de lavagem e temperatura de calcinação. Determinadas essas condições, buscou-se em três compostos nitrogenados o melhor desempenho para dopagem de nanotubos. Foram eles: amônia, uréia e tiouréia. A reação de degradação do corante rodamina B foi utilizada para avaliar a atividade fotocatalítica dos catalisadores. Os experimentos foram realizados em um reator batelada agitado, com o catalisador em suspensão e na presença de aeração, sob radiação UV e visível. Avaliaram-se inicialmente as condições de reação, como concentração de catalisador e de corante, com o catalisador comercial e precursor de Ti, P25 Degussa. Além da determinação da atividade fotocatalítica, foram feitas as seguintes análises para caracterização dos materiais: difração de raios X (DRX), espectroscopia de refletância difusa (ERD), microscopia eletrônica de transmissão (MET) e determinação da área específica e volume de poros. A partir dos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV nenhum catalisador foi mais ativo que o P 25. Sob radiação visível, as amostras dopadas com tiouréia (NTT-4-500/TiouréiaI) e amônia (NTT-7-600/NH3I) apresentaram os melhores resultados, com um aumento na fotodegradação de 16 e 30 % em relação às amostras não dopadas, respectivamente. / This work presents the study of the catalytic performance of nanostructured titanium oxide, TiO2, doped with nitrogen in order to improve its photocatalytic activity under visible light. TiO2 nanotubes were prepared by hydrothermal method, where TiO2 particles react with NaOH at high temperature and pressure. Then the material was handled through an acid wash and calcination, in order to produce desirable characteristics for the photocatalyst applications. The best conditions for titania nanotubes preparation were determined by varying the pH of the wash water and calcination temperature. Established these conditions, the research focused on obtaining among three nitrogen doping the one that provided best performance of nanotubes. They were: ammonium hydroxide, urea and thiourea. The degradation reaction of rhodamine B dye was used to evaluate the photocatalytic activity of catalyst. The experiments were performed in a stirred batch reactor, with the catalyst in suspension and in the presence of aeration, in the presence of UV and visible radiations. Initially the reaction conditions, such as catalyst and dye concentrations, were determined with the commercial catalyst and Ti precursor, P25 Degussa. In addition to determining the photocatalytic activity, the material characterization was made by X-ray diffraction (XRD), diffusive reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determination of specific area and pore volume by N2 absorption isotherms. The photocatalytic tests showed that the acid washed and calcination had a strong influence on its photocatalytic activity. No synthesized catalyst presented a larger photodegradation activity under UV light than P25. Under visible light, the samples doped with thiourea (NTT-4-500/TiouréiaI), and ammonia (NTT-7-600/NH3I) showed the best results with an increase in the photodegradation activity of 16 and 30% compared to the undoped samples, respectively.

No presente trabalho foi realizado o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com diferentes metais (prata, ouro, cobre, paládio e zinco), a fim de promover um aumento da atividade fotocatalítica sob radiação visível. Os experimentos foram realizados em um reator batelada de vidro, com controle de temperatura e catalisador em suspensão, sob radiação UV e visível, usando-se rodamina B (RhB) como molécula teste. Além disso, foram avaliadas as condições de reação, como as concentrações de catalisador e de corante, e do catalisador comercial P-25 Degussa. Para síntese dos nanotubos de TiO2 utilizou-se o método hidrotérmico, que consiste na reação de partículas de TiO2 com uma solução aquosa de NaOH sob temperatura e pressão elevadas, seguida de lavagem ácida e calcinação. Foram determinadas as melhores condições de obtenção dos nanotubos, variando-se o pH da solução de lavagem e temperatura de calcinação, antes da dopagem com metais. Além da avaliação da atividade fotocatalítica, a difração de raios X (DRX), espectroscopia de reflectância difusa (ERD), microscopia eletrônica de transmissão (MET) e a determinação da área específica e volume de poros foram utilizadas para caracterização dos fotocatalisadores dopados e dos nanotubos de TiO2 (NTTs). Pelos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV apenas o catalisador dopado com paládio foi mais ativo que o P 25, com uma degradação de 93%. Sob radiação visível, as amostras dopadas com prata (NTT-4-600/Ag+UV e NTT-4-600/Ag+escuro), paládio (NTT-4-500/Pd) e ouro (NTT-4-500/AuI) apresentaram os melhores resultados, em relação às amostras não dopadas, com degradação de 19%, 11%, 17% e 16% respectivamente. / The performance of nanostructured titanium dioxide catalysts doped with different metals was studied (silver, gold, copper, palladium and zinc), in order to promote an increase in the photocatalytic activity under visible light. The experiments were performed in a glass batch reactor with controlled temperature and catalyst in suspension under UV and visible radiation for rhodamine B (RhB) degradation. In addition, was evaluated the reaction conditions such as catalyst and dye concentration, and the performance of the commercial catalyst TiO2 Degussa P-25. TiO2 nanotubes were synthesized by hydrothermal method, which consists of the reaction of TiO2 particles with aqueous NaOH solution under elevated temperature and pressure, followed by acid washing and calcining. Before the doping metals were determined the best conditions for to obtain nanotubes, by varying the pH of the wash and calcination temperature. In addition to the evaluation of photocatalytic activity, the X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determine the specific area and pore volume were the techniques used for characterization of doped photocatalysts and TiO2 nanotubes (NTTs). The photocatalytic tests showed that the treatments had a great influence on its catalytic activity. Under UV radiation only doped with palladium catalyst was more active than the P 25, with a 93% degradation. Under visible light, the samples doped with silver (NTT-4-600/Ag+UV e NTT-4-600/Ag+dark), palladium (NTT-4-500/Pd) and gold (NTT-4-500/ AuI) showed the best results, with a degradation 19%, 11%, 17% e 16% respectively.

No presente trabalho foi realizado o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com diferentes metais (prata, ouro, cobre, paládio e zinco), a fim de promover um aumento da atividade fotocatalítica sob radiação visível. Os experimentos foram realizados em um reator batelada de vidro, com controle de temperatura e catalisador em suspensão, sob radiação UV e visível, usando-se rodamina B (RhB) como molécula teste. Além disso, foram avaliadas as condições de reação, como as concentrações de catalisador e de corante, e do catalisador comercial P-25 Degussa. Para síntese dos nanotubos de TiO2 utilizou-se o método hidrotérmico, que consiste na reação de partículas de TiO2 com uma solução aquosa de NaOH sob temperatura e pressão elevadas, seguida de lavagem ácida e calcinação. Foram determinadas as melhores condições de obtenção dos nanotubos, variando-se o pH da solução de lavagem e temperatura de calcinação, antes da dopagem com metais. Além da avaliação da atividade fotocatalítica, a difração de raios X (DRX), espectroscopia de reflectância difusa (ERD), microscopia eletrônica de transmissão (MET) e a determinação da área específica e volume de poros foram utilizadas para caracterização dos fotocatalisadores dopados e dos nanotubos de TiO2 (NTTs). Pelos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV apenas o catalisador dopado com paládio foi mais ativo que o P 25, com uma degradação de 93%. Sob radiação visível, as amostras dopadas com prata (NTT-4-600/Ag+UV e NTT-4-600/Ag+escuro), paládio (NTT-4-500/Pd) e ouro (NTT-4-500/AuI) apresentaram os melhores resultados, em relação às amostras não dopadas, com degradação de 19%, 11%, 17% e 16% respectivamente. / The performance of nanostructured titanium dioxide catalysts doped with different metals was studied (silver, gold, copper, palladium and zinc), in order to promote an increase in the photocatalytic activity under visible light. The experiments were performed in a glass batch reactor with controlled temperature and catalyst in suspension under UV and visible radiation for rhodamine B (RhB) degradation. In addition, was evaluated the reaction conditions such as catalyst and dye concentration, and the performance of the commercial catalyst TiO2 Degussa P-25. TiO2 nanotubes were synthesized by hydrothermal method, which consists of the reaction of TiO2 particles with aqueous NaOH solution under elevated temperature and pressure, followed by acid washing and calcining. Before the doping metals were determined the best conditions for to obtain nanotubes, by varying the pH of the wash and calcination temperature. In addition to the evaluation of photocatalytic activity, the X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determine the specific area and pore volume were the techniques used for characterization of doped photocatalysts and TiO2 nanotubes (NTTs). The photocatalytic tests showed that the treatments had a great influence on its catalytic activity. Under UV radiation only doped with palladium catalyst was more active than the P 25, with a 93% degradation. Under visible light, the samples doped with silver (NTT-4-600/Ag+UV e NTT-4-600/Ag+dark), palladium (NTT-4-500/Pd) and gold (NTT-4-500/ AuI) showed the best results, with a degradation 19%, 11%, 17% e 16% respectively.

Este trabalho apresenta o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com nitrogênio, visando melhorar sua atividade fotocatalítica sob radiação visível. Os nanotubos de TiO2 foram preparados pelo método hidrotérmico, onde partículas de TiO2 reagem com NaOH a temperatura e pressão elevadas. Em seguida o material é tratado, através de uma lavagem ácida e calcinação, de modo a apresentar as características desejáveis para a aplicação como fotocatalisador. Foram determinadas as melhores condições de obtenção dos nanotubos avaliando-se sua atividade fotocatalítica, variando-se o pH da solução de lavagem e temperatura de calcinação. Determinadas essas condições, buscou-se em três compostos nitrogenados o melhor desempenho para dopagem de nanotubos. Foram eles: amônia, uréia e tiouréia. A reação de degradação do corante rodamina B foi utilizada para avaliar a atividade fotocatalítica dos catalisadores. Os experimentos foram realizados em um reator batelada agitado, com o catalisador em suspensão e na presença de aeração, sob radiação UV e visível. Avaliaram-se inicialmente as condições de reação, como concentração de catalisador e de corante, com o catalisador comercial e precursor de Ti, P25 Degussa. Além da determinação da atividade fotocatalítica, foram feitas as seguintes análises para caracterização dos materiais: difração de raios X (DRX), espectroscopia de refletância difusa (ERD), microscopia eletrônica de transmissão (MET) e determinação da área específica e volume de poros. A partir dos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV nenhum catalisador foi mais ativo que o P 25. Sob radiação visível, as amostras dopadas com tiouréia (NTT-4-500/TiouréiaI) e amônia (NTT-7-600/NH3I) apresentaram os melhores resultados, com um aumento na fotodegradação de 16 e 30 % em relação às amostras não dopadas, respectivamente. / This work presents the study of the catalytic performance of nanostructured titanium oxide, TiO2, doped with nitrogen in order to improve its photocatalytic activity under visible light. TiO2 nanotubes were prepared by hydrothermal method, where TiO2 particles react with NaOH at high temperature and pressure. Then the material was handled through an acid wash and calcination, in order to produce desirable characteristics for the photocatalyst applications. The best conditions for titania nanotubes preparation were determined by varying the pH of the wash water and calcination temperature. Established these conditions, the research focused on obtaining among three nitrogen doping the one that provided best performance of nanotubes. They were: ammonium hydroxide, urea and thiourea. The degradation reaction of rhodamine B dye was used to evaluate the photocatalytic activity of catalyst. The experiments were performed in a stirred batch reactor, with the catalyst in suspension and in the presence of aeration, in the presence of UV and visible radiations. Initially the reaction conditions, such as catalyst and dye concentrations, were determined with the commercial catalyst and Ti precursor, P25 Degussa. In addition to determining the photocatalytic activity, the material characterization was made by X-ray diffraction (XRD), diffusive reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determination of specific area and pore volume by N2 absorption isotherms. The photocatalytic tests showed that the acid washed and calcination had a strong influence on its photocatalytic activity. No synthesized catalyst presented a larger photodegradation activity under UV light than P25. Under visible light, the samples doped with thiourea (NTT-4-500/TiouréiaI), and ammonia (NTT-7-600/NH3I) showed the best results with an increase in the photodegradation activity of 16 and 30% compared to the undoped samples, respectively.

Este trabalho apresenta o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com nitrogênio, visando melhorar sua atividade fotocatalítica sob radiação visível. Os nanotubos de TiO2 foram preparados pelo método hidrotérmico, onde partículas de TiO2 reagem com NaOH a temperatura e pressão elevadas. Em seguida o material é tratado, através de uma lavagem ácida e calcinação, de modo a apresentar as características desejáveis para a aplicação como fotocatalisador. Foram determinadas as melhores condições de obtenção dos nanotubos avaliando-se sua atividade fotocatalítica, variando-se o pH da solução de lavagem e temperatura de calcinação. Determinadas essas condições, buscou-se em três compostos nitrogenados o melhor desempenho para dopagem de nanotubos. Foram eles: amônia, uréia e tiouréia. A reação de degradação do corante rodamina B foi utilizada para avaliar a atividade fotocatalítica dos catalisadores. Os experimentos foram realizados em um reator batelada agitado, com o catalisador em suspensão e na presença de aeração, sob radiação UV e visível. Avaliaram-se inicialmente as condições de reação, como concentração de catalisador e de corante, com o catalisador comercial e precursor de Ti, P25 Degussa. Além da determinação da atividade fotocatalítica, foram feitas as seguintes análises para caracterização dos materiais: difração de raios X (DRX), espectroscopia de refletância difusa (ERD), microscopia eletrônica de transmissão (MET) e determinação da área específica e volume de poros. A partir dos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV nenhum catalisador foi mais ativo que o P 25. Sob radiação visível, as amostras dopadas com tiouréia (NTT-4-500/TiouréiaI) e amônia (NTT-7-600/NH3I) apresentaram os melhores resultados, com um aumento na fotodegradação de 16 e 30 % em relação às amostras não dopadas, respectivamente. / This work presents the study of the catalytic performance of nanostructured titanium oxide, TiO2, doped with nitrogen in order to improve its photocatalytic activity under visible light. TiO2 nanotubes were prepared by hydrothermal method, where TiO2 particles react with NaOH at high temperature and pressure. Then the material was handled through an acid wash and calcination, in order to produce desirable characteristics for the photocatalyst applications. The best conditions for titania nanotubes preparation were determined by varying the pH of the wash water and calcination temperature. Established these conditions, the research focused on obtaining among three nitrogen doping the one that provided best performance of nanotubes. They were: ammonium hydroxide, urea and thiourea. The degradation reaction of rhodamine B dye was used to evaluate the photocatalytic activity of catalyst. The experiments were performed in a stirred batch reactor, with the catalyst in suspension and in the presence of aeration, in the presence of UV and visible radiations. Initially the reaction conditions, such as catalyst and dye concentrations, were determined with the commercial catalyst and Ti precursor, P25 Degussa. In addition to determining the photocatalytic activity, the material characterization was made by X-ray diffraction (XRD), diffusive reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determination of specific area and pore volume by N2 absorption isotherms. The photocatalytic tests showed that the acid washed and calcination had a strong influence on its photocatalytic activity. No synthesized catalyst presented a larger photodegradation activity under UV light than P25. Under visible light, the samples doped with thiourea (NTT-4-500/TiouréiaI), and ammonia (NTT-7-600/NH3I) showed the best results with an increase in the photodegradation activity of 16 and 30% compared to the undoped samples, respectively.

No presente trabalho foi realizado o estudo do desempenho de catalisadores nanoestruturados de dióxido de titânio, TiO2, dopados com diferentes metais (prata, ouro, cobre, paládio e zinco), a fim de promover um aumento da atividade fotocatalítica sob radiação visível. Os experimentos foram realizados em um reator batelada de vidro, com controle de temperatura e catalisador em suspensão, sob radiação UV e visível, usando-se rodamina B (RhB) como molécula teste. Além disso, foram avaliadas as condições de reação, como as concentrações de catalisador e de corante, e do catalisador comercial P-25 Degussa. Para síntese dos nanotubos de TiO2 utilizou-se o método hidrotérmico, que consiste na reação de partículas de TiO2 com uma solução aquosa de NaOH sob temperatura e pressão elevadas, seguida de lavagem ácida e calcinação. Foram determinadas as melhores condições de obtenção dos nanotubos, variando-se o pH da solução de lavagem e temperatura de calcinação, antes da dopagem com metais. Além da avaliação da atividade fotocatalítica, a difração de raios X (DRX), espectroscopia de reflectância difusa (ERD), microscopia eletrônica de transmissão (MET) e a determinação da área específica e volume de poros foram utilizadas para caracterização dos fotocatalisadores dopados e dos nanotubos de TiO2 (NTTs). Pelos ensaios fotocatalíticos observou-se que os tratamentos a que foram submetidos os materiais tiveram grande influência na sua atividade catalítica. Sob radiação UV apenas o catalisador dopado com paládio foi mais ativo que o P 25, com uma degradação de 93%. Sob radiação visível, as amostras dopadas com prata (NTT-4-600/Ag+UV e NTT-4-600/Ag+escuro), paládio (NTT-4-500/Pd) e ouro (NTT-4-500/AuI) apresentaram os melhores resultados, em relação às amostras não dopadas, com degradação de 19%, 11%, 17% e 16% respectivamente. / The performance of nanostructured titanium dioxide catalysts doped with different metals was studied (silver, gold, copper, palladium and zinc), in order to promote an increase in the photocatalytic activity under visible light. The experiments were performed in a glass batch reactor with controlled temperature and catalyst in suspension under UV and visible radiation for rhodamine B (RhB) degradation. In addition, was evaluated the reaction conditions such as catalyst and dye concentration, and the performance of the commercial catalyst TiO2 Degussa P-25. TiO2 nanotubes were synthesized by hydrothermal method, which consists of the reaction of TiO2 particles with aqueous NaOH solution under elevated temperature and pressure, followed by acid washing and calcining. Before the doping metals were determined the best conditions for to obtain nanotubes, by varying the pH of the wash and calcination temperature. In addition to the evaluation of photocatalytic activity, the X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and determine the specific area and pore volume were the techniques used for characterization of doped photocatalysts and TiO2 nanotubes (NTTs). The photocatalytic tests showed that the treatments had a great influence on its catalytic activity. Under UV radiation only doped with palladium catalyst was more active than the P 25, with a 93% degradation. Under visible light, the samples doped with silver (NTT-4-600/Ag+UV e NTT-4-600/Ag+dark), palladium (NTT-4-500/Pd) and gold (NTT-4-500/ AuI) showed the best results, with a degradation 19%, 11%, 17% e 16% respectively.