O chorume in natura utilizado foi proveniente do aterro sanitário da cidade de Cachoeira Paulista no interior do estado de São Paulo. Possui baixa razão de biodegradabilidade (DBO/DQO = 0,094) evidenciado principalmente através das análises de caracterização dos parâmetros COT (618,1 mg C/L), DQO (4345,88 mg O2/L) e DBO5 (409,7 mg O2/L) que estão acima do limite permitido pela legislação. Em função disso, os processos oxidativos avançados (POA´s) surgem como alternativa para o seu pré-tratamento. O foco principal desse trabalho foi utilizar a aplicação da fotocatálise homogênea, empregando concomitantemente a luz solar com o reagente Fenton (H2O2 + Fe2+) num reator aberto com volume constante da amostra (3L) em sistema semi-batelada para verificar a eficiência do processo na remoção da carga orgânica. O reator solar possui um suporte de madeira que está direcionado ao Equador com um ângulo de inclinação de 23º, com uma placa metálica sem pigmentação denominada branco, numa vazão constante (13 L / min) em períodos com maior intensidade de radiação UV e monitorados pelo radiômetro. Após o ajuste do chorume de acordo com a planilha experimental, o volume do reagente Ferro (0,82 mol) foi adicionado totalmente no início da reação e o peróxido de hidrogênio (30% m/v) durante 30 min do tempo total de 1 hora, através de uma bureta dosadora, de maneira controlada que o peróxido de hidrogênio fosse consumido integralmente na reação de degradação, aumentando assim sua eficiência. O chorume tratado foi bombeado até a parte superior da placa, percolando-a uniformemente enquanto recebia a radiação solar sobre a placa. O processo fotocatalítico foi otimizado por um planejamento fatorial (23) com duplicata e triplicata no ponto central contendo 19 experimentos com variáveis de entrada: pH (3, 3,5 e 4) , quantidade de [H2O2] ( 73,2 g , 85,4 g e 97,6 g ) e quantidade de [Fe2+ ] (4,0 g , 5,0 g e 6,0 g ). As variáveis respostas do processo utilizadas foram: eficiência de remoção de COT (Carbono Orgânico Total) e DQO (Demanda Química de Oxigênio). As maiores reduções percentuais de DQO e COT, respectivamente, 89,19% e 86,12%, além do aumento de sua biodegradabilidade para 0,55 com um custo de R$ 0,3558 / 3L. Desta forma, o processo fotocatalítico mostrou grande viabilidade técnica e econômica em relação à degradação da carga orgânica de chorume. / The leachate used was fresh from the landfill of the city of Cachoeira Paulista in the state of São Paulo. Has a low ratio of biodegradability (BOD / COD = 0.094) demonstrated mainly through the analysis parameters characterizing the TOC (618,1 mg C / l) COD (mg O2 4345,88 / L) and BOD5 (mg O2 409,7 / L) that are above the limit allowed by law. As a result, the advanced oxidation processes (AOP\'s) are an alternative to their pre-treatment. The main focus of this work was to use the application of photocatalysis homogeneous, employing concurrently sunlight with Fenton\'s reagent (H2O2 + Fe2+) in an open reactor with constant volume of sample (3L) in the semi-batch to verify the efficiency of the process in removal of organic matter. The solar reactor has a wooden support that is directed to the equator with a tilt angle of 23 º, with a metal plate without pigmentation called white, a constant flow rate (13 L / min) in periods with higher UV intensity and monitored by radiometer. After adjusting the leachate according to the experimental sheet, the volume of reagent iron (0,82 mol) was added entirely at the beginning of the reaction and hydrogen peroxide (30% w / v) for 30 min to 1 hour total time through a dosing burette so controlled that the hydrogen peroxide was consumed entirely in the degradation reaction, thus increasing its efficiency. The treated leachate was pumped to the top of the plate evenly percolating while receiving the solar radiation on the plate. The photocatalytic process was optimized by a factorial design (23) with duplicate and triplicate center point experiments containing 19 input variables: pH (3, 3,5 and 4), the amount of [H2O2] (73,2 g, 85,4 g 97,6 g) and the amount of [Fe 2+] (4,0 g, 5,0 g and 6,0 g). The response variables of the process were: removal efficiency of TOC (Total Organic Carbon) and COD (Chemical Oxygen Demand). The largest percentage reductions of COD and TOC, respectively, 89,19% and 86,12%, besides increasing its biodegradability to 0,55 at a cost of R $ 0,3558 / 3L. Thus, the photocatalytic process showed great technical and economic feasibility in relation to the degradation of the organic leachate.

Semiconductor metal oxides can be induced by light with proper wavelength resulting in oxidation and reduction reactions for the transformation of water and oxygen molecules into active radicals. With this method, it is possible to obtain self-cleaning surfaces and products having antimicrobial properties. The aim of this study is to develop semiconductor metal oxide thin films for multifunctional glass products and the characterization of photocatalytic self cleaning and antimicrobial properties. As semiconductor metal oxides / titanium dioxide (TiO2), tin oxide (SnO2) and their binary mixtures (TiO2-SnO2) are selected because of their abundancy, non toxic properties, stability and the ability of absorbing light close to visible range. Also the effect of metal dopants such as praseodymium (Pr), palladium (Pd), silver (Ag) and iron (Fe) was examined with these metal oxides. The colloidal solutions were synthesized by using sol-gel method in order to apply the developed method to industrial usage as applying on large surfaces. The glass substrates were coated with the colloidal solutions by dip coating and the dried samples were calcined under air flow. The best calcination condition for pure TiO2 coated thin film was determined as 400oC for 45 minutes. Surface characterization studies were performed by using UV-Visible Spectrophotometer for band gap measurement, CAM for contact angle measurement, SEM for surface morphology and tophology. The methylene blue adsorption tests were carried out and the effective surface area of the samples were predicted by the Langmuir adsorption isotherm of samples. The photocatalytic activities of the coated thin films were measured with the degradation of organic materials as red wine and methylene blue, and with the antimicrobial activity tests as counting the number of viable E.coli cells. 61.2% deactivation of methylene blue stain was achieved over SnO2 coated thin films while this was 22.1% over TiO2 coated thin films after irradiation for 180 minutes. The superior photocatalytic activity was observed with TiO2 samples doped with Pd and Ag ions. The TiO2-SnO2 coated samples performed limited photocatalytic activity which is less than the activity of SnO2 coated samples which was confirmed with surface area measurements as SnO2 coated samples had higher surface area (9.81 cm2/cm2) than TiO2-SnO2 coated samples. Surface area increased with increasing the amount of SnO2 and it was in the following order: SnO2 &gt / 80% SnO2 + 20% TiO2 &gt / 50% SnO2 + 50%TiO2 &gt / 35% SnO2 + 65%TiO2 &gt / 20% SnO2 + 80% TiO2 &gt / TiO2.

This study combined photocatalytic technology with activated carbon cellulose-paper filter (ACCF) adsorption to decompose gaseous pollutants. Gaseous pollutants were initially adsorbed by activated carbon and could be further decomposed by photocatalytic technology. This study selected acetone (CH3COCH3) as gaseous pollutants. Two market available photocatalysts (photocatalysts¢¹and¢º) were coated on ACCF by impregnation to decompose acetone in a batch photocatlytic reactor. Operating parameters investigated in this study included initial acetone concentration (4.1~10.2 £gM), reaction temperature (40~70¢J), and water vapor (0~20 %). The incident UV light of 365 nm was irradiated by a 20-watt low-pressure mercury lamp placing above the batch photocatalytic reactor. The ACCF coated with TiO2 was placed at the center of the photocatalytic reactor. Acetone was injected into the reactor by a gasket syringe to conduct the photocatalytic tests. Reactants and products were analyzed quantitatively by a gas chromatography with an electron capture detector (GC/DCD) and a flame ionization detector followed by a methaneizer (GC/FID-Methaneizer). Finally, a Langmiur-Hinshewood (L-H) kinetic model was proposed to describe the rate of photocatalytic reaction. Results obtained from the photocatalytic tests indicated that photocatalyst¢º was better than photocatalyst¢¹ for the decomposition of acetone. Experimental results indicated that the size range of self-produced TiO2 photocatalyst by sol-gel was 20~70 nm. The end products were mainly CO and CO2, which resulted in the mineralization ratio up to 98%. Results obtained from the operating parameter tests revealed that the increase of initial acetone concentration enhanced the amount of acetone adsorbed on ACCF, which however did not increase the reaction rate of acetone. Although the increase of reaction temperature could reduce the amount of acetone adsorbed on ACCF, the decomposition rate of acetone could be promoted, so as the yield rate and mineralization ratio of products (CO and CO2). The increase of water vapor could slightly decrease the amount of acetone adsorbed on ACCF. The competitive adsorption phenomenon between acetone and water molecules on active sites could decelerate the decomposion of acetone. Moreover, the ACCF would not be saturated since the adsorbed acetone could be further decomposed quickly by the photocatalysts, which made the TiO2/ACCF more effective on removing acetone and lasted longer than the conventional ACCF. Finally, a modified bimolecular Langmuir-Hinshelwood kinetic model was developed to investigate the influences of initial acetone concentration reaction, temperature, and relative humidity on the promotion and inhibition for the photocatalytic oxidation of acetone. The modified L-H kinetic model could successfully simulate the photocatalytic reaction rate of acetone. Thus, the reaction rate of acetone over TiO2/ACCF could be described by the modified L-H kinetic model.

This thesis consists of two research problems in the water decontamination area. In the first work, the main focus is to understand the structure and photocatalytic activity of titanium dioxide with graphene (G-TiO2) which is synthesized by using sol-gel method. The photocatalytic activity of TiO2 is limited by the short electron hole pair recombination time. Graphene, with high specific surface area and unique electronic properties, can be used as a good support for TiO2 to enhance the photocatalytic activity. The obtained G-TiO2 photocatalysts has been characterized by X-Ray Diffraction (XRD), Raman Spectroscopy, Transmission Electron Microscopy (TEM), FTIR Spectroscopy and Ultraviolet visible (UV-vis) Spectroscopy. This prepared G-TiO2 nanocomposite exhibited excellent photocatalysis degradation on methyl orange (MO) under irradiation of simulated sunlight. Such enthralling photocatalyst may find substantial applications in various fields. The primary objective of the second work is to understand the nanocomposite structure of SiO2 coated over graphene (G) nanoplatelets. An attempt has been made to synthesize G-SiO2 nanocomposite using sol-gel technique. The G-SiO2 nanocomposite is characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Raman spectroscopy, FTIR spectroscopy, and Electrochemical and Electrical measurement technique, respectively. In this work, G-SiO2 nanoparticles with the water containing salts of zinc is added, and allowed to settle in water. The ZnCl2 ix concentration displays a whitish color solution which has turned to colorless within one or two hours of treatment with G-SiO2 nanocomposites. The presence of heavy metal is tested using electrochemical cyclic voltammetry (CV) technique. The CV measurement on the water treated with G-SiO2 has been tested for several days to understand the presence of heavy metals in water. Interestingly, the near complete separation has been observed by treating the heavy metal contaminated water sample for one to two days in presence of G-SiO2 nanoparticles. The redox potential observed for the heavy metal has been found to diminish as a function of treatment with respect to time, and no redox peak is observed after the treatment for four to five days. Further test using EDS measurement indicates that the heavy metal ions are observed within the G-SiO2 nanocomposite. The recovery of G-SiO2 nanocomposite is obtained by washing using deionized water. Our experimental finding indicates that the G-SiO2 nanocomposite could be exploited for potential heavy metals cleaning from waste or drinking water.

Η φωτοκαταλυτική παραγωγή H2 μέσω διεργασιών φωτοκαταλυτικής αναμόρφωσης, μελετήθηκε με χρήση νανοκρυσταλλικών υμενίων TiO2 εμπλουτισμένων με εναποτεθειμένα μέταλλα στην επιφάνειά τους. Το TiO2 παρασκευάστηκε με τη μέθοδο sol-gel παρουσία οξικού οξέος και ενός επιφανειακώς δραστικού μορίου, του Triton X-100. Τα υμένια που παρασκευάστηκαν ήταν κρυσταλλικής μορφής ανατάση, με μέσο μέγεθος των σωματιδίων 12 nm, αρκετά σημαντικές υδροφιλικές ιδιότητες και υψηλή προσροφητική ικανότητα, ενώ είναι και πολύ ικανοί φωτοκαταλύτες για την αντίδραση διάσπασης των προσροφημένων χρωστικών στην επιφάνειά τους. Η μελέτη της αντίδρασης παραγωγής H2 πραγματοποιήθηκε με χρήση του φωτοκαταλύτη Pt/TiO2, αφού ο Pt αύξησε τη φωτοκαταλυτική ενεργότητα του υλικού και τη φωτοκαταλυτική απόδοση της αντίδρασης περισσότερο από τα υπόλοιπα μέταλλα. Οι βέλτιστες συνθήκες εναπόθεσης του Pt, ήταν η προσρόφησή του για 30 min από υδατικά διαλύματα Na2PtCl4 συγκέντρωσης 5*10-4 Μ και φωτοβόληση του υλικού για 15 min ώστε να πραγματοποιηθεί η αναγωγή. Η χρήση αυτού του φωτοκαταλύτη έδωσε σημαντικά αποτελέσματα φωτοκαταλυτικής αποικοδόμησης αλκοολών και άλλων προϊόντων βιομάζας σε υδατικά διαλύματα. Από τις ενώσεις που μελετήθηκαν, η χρήση της αιθανόλης και της γλυκερόλης οδήγησε στη μεγαλύτερη αύξηση του ρυθμού φωτοκαταλυτικής παραγωγής H2. Η αντίδραση της φωτοκαταλυτικής αναμόρφωσης πραγματοποιήθηκε κυρίως με χρήση υπεριώδους ακτινοβολίας UVA (Black light, ~360 nm), παρουσία ενώσεων με γενικό χημικό τύπο CxHyOz. Κυριότερες κατηγορίες αυτών των ενώσεων είναι οι αλκοόλες, τα σάκχαρα, οι πολυόλες και τα οργανικά οξέα. Επίσης, τα φωτοκαταλυτικά υμένια Pt/TiO2 είναι ικανά να προκαλέσουν την φωτοκαταλυτική παραγωγή H2 μέσα από μικρογαλακτώματα διασποράς ελαίου σε νερό. Η συνολική διεργασία της φωτοκαταλυτικής αναμόρφωσης αποτελεί μια ιδιαίτερα ελκυστική διεργασία, η οποία πραγματοποιείται με αρκετά ικανοποιητική απόδοση, με την κατάλληλη χρήση του φωτοκαταλύτη Pt/TiO2, σε μορφή λεπτών υμενίων. / Nanocrystalline titanium dioxide films, with deposited noble metals on their surface were studied for the photocatalytic production of Η2, through the so-called “photocatalytic reforming” processes. These films were deposited on glass substrates by using sol-gel procedures, carried out in the presence of acetic acid and a surfactant template, Triton X-100. The titania films consist of anatase nanocrystals, of about 12 nm average particle size. They were highly hydrophilic and were strong adsorbers of positively charged organic substances. Photodegradation of adsorbed dyes was very efficient on these titania nanoparticulate films. Photocatalytic hydrogen production was studied by using nanocrystalline films of Pt/TiO2. Pt gave the best results concerning photocatalytic activity of titanium dioxide. The best conditions of platinum deposition, through its adsorption from aqueous solutions, were 30 min of adsorption in the dark from an aqueous solution of Na2PtCl4, having a concentration of 5*10-4 M, followed by the reduction of the adsorbed ions of Pt (II) by UV treatment. Using this type of photocatalyst lead to high efficiency of photodegradation of alcohols and generally products, derived from biomass in aqueous solutions. From all the compounds examined, ethanol and glycerol gave the highest photocatalytic hydrogen production rates. The photocatalytic reforming reaction, was carried out using UVA (black light, ~360 nm) radiation, that comes from low-energy black light sources and was applied on chemical compounds that have the general chemical structure of CxHyOz. Several categories of substances may have this structure, such as alcohols, saccharides, polyols and organic acids. Also, photocatalytic nanocrystalline films Pt/TiO2 led to substantially efficient process of hydrogen production, by using colloidal dispersions of oil-in-water microemulsion. The whole process of photocatalytic reforming of several substances can be a very attractive and very promising process, by employing nanocrystalline titania films, Pt/TiO2.

No description available.

In this thesis, we focused on understanding the synthesis of titanium dioxide (TiO2) films and nitrogen doped TiO2 films using an atmospheric pressure Dielectric Barrier Discharge (DBD). The first part of the work was dedicated to the deposition of TiO2 films by cold plasma DBD with titanium tetraisopropoxide as precursor in a single-step process at room temperature. The deposition rate was about 70 nm·min-1. The photocatalytic degradation rate for the degradation of methylene blue (MB) under ultra violet (UV) irradiation of the TiO2 film after annealing was close to a reference anatase TiO2 spin coated film. Moreover, the TiO2 films showed a good photocatalytic stability. The second part of the study focused on the optimization and the understanding of the effect of the plasma parameters (gas flow rate and power) on the morphology of the TiO2 films and on the investigation of the deposition mechanisms. The morphology of the film changed from granular to compact film by either increasing the total flow rate or decreasing the plasma power. In other words, adapting the energy density in the plasma allowed the control of the morphology of the TiO2 films. To our knowledge, it was the first time that the energy density parameters of the plasma were used to control the morphology of TiO2 films. The photocatalytic degradation rate for the degradation of MB under UV irradiation of the annealed TiO2 film turned out to be about 2 and 15 times higher than the one of the commercial TiO2 film and the as-deposited TiO2 films, respectively. In order to extend the light utilization to the visible light range, TiO2 films were doped with nitrogen using a room temperature argon/ammonia plasma discharge. XPS and SIMS results confirmed that the nitrogen has been incorporated in the TiO2 lattice mostly in Ti-N state. This was further confirmed by Raman spectroscopy and XRD. The plasma properties and the doping mechanism were studied by Optical Emission Spectroscopy. It is suggested that the NH radicals played a key role in the doping of TiO2. The concentration of nitrogen in the N-TiO2 coatings could be tuned by adapting the ratio of NH3 in the plasma or the plasma power. The band gap of our N-TiO2 coatings is lower than the one of undoped TiO2 coating. The photocatalytic degradation rate for N-TiO2 coating was more than 4 times higher than the one of the undoped TiO2 coating. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Este trabalho teve como objetivo obter nanocompósitos de nanotubos de carbono de paredes múltiplas (NTCPMs) com TiO2, e caracterizá-los quanto a sua estrutura, características ópticas e atividade fotocatalítica. Os nanocompósitos foram obtidos a partir de NTCPMs comerciais (Baytubes®), e dois diferentes TiO2: um comercial (P25) e um obtido na síntese de TiO2 tendo tetra propóxido de titânio (TTP) como precursor. Foram utilizados dois diferentes sistemas líquidos para a obtenção dos nanocompósitos NTCPM-TiO2: um, em pH ácido e outro, em pH alcalino. Os nanocompósitos obtidos a partir do TTP foram posteriormente tratados termicamente a 400 °C, 500 °C, 600 °C e 700 °C para formação de fases cristalinas de TiO2. Os nanocompósitos foram investigados quanto a sua atividade fotocatalítica, empregando-os como catalisadores na degradação do corante orgânico alaranjado de metila, em solução aquosa, sob radiação ultravioleta. Os resultados foram associados a características da estrutura dos nanocompósitos, utilizando técnicas como difração de raios X, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, espectroscopia Raman e espectroscopia por infravermelho e área superficial específica. A caracterização óptica foi obtida por espectroscopia fotoluminescente e espectroscopia por refletância difusa. A análise térmica foi empregada para quantificar a presença de NTCPMs no nanocompósito empregado como catalisador. O desempenho fotocatalítico dos nanocompósitos foi correlacionado com o efeito do pH dos sistemas líquidos empregados na sua obtenção, natureza da interação (química e/ou física) entre nanotubo de carbono e TiO2, fases presentes no TiO2, energia do gap óptico e presença de defeitos estruturais no TiO2. A maior eficiência na fotocatálise foi observada nos nanocompósitos NTCPMs-TiO2 obtidos a partir do TiO2 comercial, e nos obtidos a partir do precursor TTP tratado termicamente a 500 °C, ambos em meio ácido. Estes resultados puderam ser associados às menores energias de transição e nível de defeitos no TiO2 nesses nanocompósitos, quando comparados aos demais. / This study aimed to obtain nanocomposites from multi-walled carbon nanotubes (MWCNTs) with TiO2, and characterize them according to their structure, optical properties and photocatalytic activity. The nanocomposites were obtained from commercial MWCNTs (Baytubes®) and two different types of TiO2: a commercial one (P25) and one obtained by synthesizing TiO2 with titanium tetra propoxide (TTP) as a precursor. Two different fluid systems were used for obtaining the MWCNT-TiO2 nanocomposites: one with acid pH and the other with alkaline pH. The nanocomposites obtained from TTP were subsequently heat treated at 400 °C, 500 °C, 600 °C and 700 °C to form crystalline phases of TiO2. The nanocomposites were investigated for their photocatalytic activity, employing them as catalysts in the degradation of organic methyl orange dye in an aqueous solution under ultraviolet radiation. The results were associated with the characteristics of the nanocomposites’ structure, using techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, infrared spectroscopy, and specific surface area. Optical characterization was obtained by photoluminescence spectroscopy and diffuse reflectance spectroscopy. Thermal analysis was used to quantify the presence of MWCNTs in the nanocomposite employed as catalyst. The photocatalytic performance of the nanocomposites were correlated with the effect of the pH of the liquid systems employed for obtaining them, the nature of the interaction (chemical and/or physical) between the carbon nanotube and TiO2, the phases present in the TiO2, the optical energy gap and the presence of structural defects in TiO2. The highest photocatalytic efficiency was observed in the MWCNT-TiO2 nanocomposites obtained from commercial TiO2, and in those obtained from the TTP precursor heat treated at 500 °C, both in an acid medium. These results could be associated with the lower transition energy and level of defects in the TiO2 of these nanocomposites when compared to the other samples.

Este trabalho teve como objetivo obter nanocompósitos de nanotubos de carbono de paredes múltiplas (NTCPMs) com TiO2, e caracterizá-los quanto a sua estrutura, características ópticas e atividade fotocatalítica. Os nanocompósitos foram obtidos a partir de NTCPMs comerciais (Baytubes®), e dois diferentes TiO2: um comercial (P25) e um obtido na síntese de TiO2 tendo tetra propóxido de titânio (TTP) como precursor. Foram utilizados dois diferentes sistemas líquidos para a obtenção dos nanocompósitos NTCPM-TiO2: um, em pH ácido e outro, em pH alcalino. Os nanocompósitos obtidos a partir do TTP foram posteriormente tratados termicamente a 400 °C, 500 °C, 600 °C e 700 °C para formação de fases cristalinas de TiO2. Os nanocompósitos foram investigados quanto a sua atividade fotocatalítica, empregando-os como catalisadores na degradação do corante orgânico alaranjado de metila, em solução aquosa, sob radiação ultravioleta. Os resultados foram associados a características da estrutura dos nanocompósitos, utilizando técnicas como difração de raios X, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, espectroscopia Raman e espectroscopia por infravermelho e área superficial específica. A caracterização óptica foi obtida por espectroscopia fotoluminescente e espectroscopia por refletância difusa. A análise térmica foi empregada para quantificar a presença de NTCPMs no nanocompósito empregado como catalisador. O desempenho fotocatalítico dos nanocompósitos foi correlacionado com o efeito do pH dos sistemas líquidos empregados na sua obtenção, natureza da interação (química e/ou física) entre nanotubo de carbono e TiO2, fases presentes no TiO2, energia do gap óptico e presença de defeitos estruturais no TiO2. A maior eficiência na fotocatálise foi observada nos nanocompósitos NTCPMs-TiO2 obtidos a partir do TiO2 comercial, e nos obtidos a partir do precursor TTP tratado termicamente a 500 °C, ambos em meio ácido. Estes resultados puderam ser associados às menores energias de transição e nível de defeitos no TiO2 nesses nanocompósitos, quando comparados aos demais. / This study aimed to obtain nanocomposites from multi-walled carbon nanotubes (MWCNTs) with TiO2, and characterize them according to their structure, optical properties and photocatalytic activity. The nanocomposites were obtained from commercial MWCNTs (Baytubes®) and two different types of TiO2: a commercial one (P25) and one obtained by synthesizing TiO2 with titanium tetra propoxide (TTP) as a precursor. Two different fluid systems were used for obtaining the MWCNT-TiO2 nanocomposites: one with acid pH and the other with alkaline pH. The nanocomposites obtained from TTP were subsequently heat treated at 400 °C, 500 °C, 600 °C and 700 °C to form crystalline phases of TiO2. The nanocomposites were investigated for their photocatalytic activity, employing them as catalysts in the degradation of organic methyl orange dye in an aqueous solution under ultraviolet radiation. The results were associated with the characteristics of the nanocomposites’ structure, using techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, infrared spectroscopy, and specific surface area. Optical characterization was obtained by photoluminescence spectroscopy and diffuse reflectance spectroscopy. Thermal analysis was used to quantify the presence of MWCNTs in the nanocomposite employed as catalyst. The photocatalytic performance of the nanocomposites were correlated with the effect of the pH of the liquid systems employed for obtaining them, the nature of the interaction (chemical and/or physical) between the carbon nanotube and TiO2, the phases present in the TiO2, the optical energy gap and the presence of structural defects in TiO2. The highest photocatalytic efficiency was observed in the MWCNT-TiO2 nanocomposites obtained from commercial TiO2, and in those obtained from the TTP precursor heat treated at 500 °C, both in an acid medium. These results could be associated with the lower transition energy and level of defects in the TiO2 of these nanocomposites when compared to the other samples.

Este trabalho teve como objetivo obter nanocompósitos de nanotubos de carbono de paredes múltiplas (NTCPMs) com TiO2, e caracterizá-los quanto a sua estrutura, características ópticas e atividade fotocatalítica. Os nanocompósitos foram obtidos a partir de NTCPMs comerciais (Baytubes®), e dois diferentes TiO2: um comercial (P25) e um obtido na síntese de TiO2 tendo tetra propóxido de titânio (TTP) como precursor. Foram utilizados dois diferentes sistemas líquidos para a obtenção dos nanocompósitos NTCPM-TiO2: um, em pH ácido e outro, em pH alcalino. Os nanocompósitos obtidos a partir do TTP foram posteriormente tratados termicamente a 400 °C, 500 °C, 600 °C e 700 °C para formação de fases cristalinas de TiO2. Os nanocompósitos foram investigados quanto a sua atividade fotocatalítica, empregando-os como catalisadores na degradação do corante orgânico alaranjado de metila, em solução aquosa, sob radiação ultravioleta. Os resultados foram associados a características da estrutura dos nanocompósitos, utilizando técnicas como difração de raios X, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, espectroscopia Raman e espectroscopia por infravermelho e área superficial específica. A caracterização óptica foi obtida por espectroscopia fotoluminescente e espectroscopia por refletância difusa. A análise térmica foi empregada para quantificar a presença de NTCPMs no nanocompósito empregado como catalisador. O desempenho fotocatalítico dos nanocompósitos foi correlacionado com o efeito do pH dos sistemas líquidos empregados na sua obtenção, natureza da interação (química e/ou física) entre nanotubo de carbono e TiO2, fases presentes no TiO2, energia do gap óptico e presença de defeitos estruturais no TiO2. A maior eficiência na fotocatálise foi observada nos nanocompósitos NTCPMs-TiO2 obtidos a partir do TiO2 comercial, e nos obtidos a partir do precursor TTP tratado termicamente a 500 °C, ambos em meio ácido. Estes resultados puderam ser associados às menores energias de transição e nível de defeitos no TiO2 nesses nanocompósitos, quando comparados aos demais. / This study aimed to obtain nanocomposites from multi-walled carbon nanotubes (MWCNTs) with TiO2, and characterize them according to their structure, optical properties and photocatalytic activity. The nanocomposites were obtained from commercial MWCNTs (Baytubes®) and two different types of TiO2: a commercial one (P25) and one obtained by synthesizing TiO2 with titanium tetra propoxide (TTP) as a precursor. Two different fluid systems were used for obtaining the MWCNT-TiO2 nanocomposites: one with acid pH and the other with alkaline pH. The nanocomposites obtained from TTP were subsequently heat treated at 400 °C, 500 °C, 600 °C and 700 °C to form crystalline phases of TiO2. The nanocomposites were investigated for their photocatalytic activity, employing them as catalysts in the degradation of organic methyl orange dye in an aqueous solution under ultraviolet radiation. The results were associated with the characteristics of the nanocomposites’ structure, using techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, infrared spectroscopy, and specific surface area. Optical characterization was obtained by photoluminescence spectroscopy and diffuse reflectance spectroscopy. Thermal analysis was used to quantify the presence of MWCNTs in the nanocomposite employed as catalyst. The photocatalytic performance of the nanocomposites were correlated with the effect of the pH of the liquid systems employed for obtaining them, the nature of the interaction (chemical and/or physical) between the carbon nanotube and TiO2, the phases present in the TiO2, the optical energy gap and the presence of structural defects in TiO2. The highest photocatalytic efficiency was observed in the MWCNT-TiO2 nanocomposites obtained from commercial TiO2, and in those obtained from the TTP precursor heat treated at 500 °C, both in an acid medium. These results could be associated with the lower transition energy and level of defects in the TiO2 of these nanocomposites when compared to the other samples.