A presente Tese, elaborada pela integração de artigos científicos publicados ou submetidos em periódicos internacionais, tem por objetivo geral investigar as potencialidades e limitações de resíduos industriais, acadêmicos e agroindustriais na obtenção de catalisadores para degradação de poluentes orgânicos. Foram utilizados resíduos industriais (banhos de galvanização, areias de fundição e petroquímico), acadêmicos (soluções residuais de aula de fotografia contendo prata e solução residual das aulas de química analítica contendo metais) e agro-industriais (casca de arroz, casca de acácia esgotada, pó de fumo) na preparação dos fotocatalisadores suportados. Os sólidos foram caracterizados por um conjunto de técnicas espectroscópicas, volumétricas, microscópicas, eletroquímicas visando descrever os catalisadores do ponto de vista, elementar, estrutural, textural e morfológico, como espectroscopia de emissão de raios X por dispersão de energia (SEM-EDX), espectroscopia de retroespalhamento Rutherford (RBS), espectroscopia de reflectância difusa no ultravioleta (DRS-UV), espectroscopia de espalhamento de raios X em baixo ângulo (SAXS), espectroscopia de fotoelétrons excitados por raios X (XPS), porosimetria de nitrogênio e medidas de potencial zeta (ZP). Os sistemas foram avaliados na fotodegradação de corante (rodamina B), fenol e fármacos sob radiação ultravioleta e visível. Para fins de comparação, titânia comercial P25 (Degussa) foi empregada como catalisador. Além disso, o efeito da reutilização dos catalisadores e atividade fotocatalitica frente a amostras reais foram estudados. O catalisador suportado preparado a partir do resíduo da indústria petroquímica e suportado em sílica apresentou a melhor atividade fotocatalítica na degradação de todas as moléculas testadas, tal como RhB (67 % sob radiação UV e 61 % sob radiação visível), fármaco guaifenesin ( 49 % UV e 45 % visível) e fenol (44 % UV), enquanto que o P25 comercial apresentou 93 % e 14 %, respectivamente, para a radiação ultravioleta e visível. / This thesis, developed by the integration of scientific papers published or submitted in international journals, has the objective to investigate the potential and limitations of industrial waste, academics and agroindustrial to obtain catalysts for degradation of organic pollutants. Industrial waste (galvanic baths, foundry sands and petrochemical), academics (residual solutions of class photograph containing silver and residual solution of analytical chemistry classes containing metals) and agroindustrial (rice husk, exhausted bark acacia, tobacco dust) were used in the preparation of the supported photocatalyst. The solids were characterized by a set of spectroscopic, volumetric, microscopic electrochemical techniques in order to describe elementary structural, textural and morphological properties, such as Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), Rutherford backscattering spectrometry (RBS), diffuse reflectance spectroscopy in the ultraviolet (DRS-UV), small-angle X-ray scattering (SAXS), X-ray Photoelectron Spectroscopy (XPS), nitrogen porosimetry and zeta potential (ZP) measurements. The catalyst activity was evaluated on the dye (RhB), phenol and drugs photodegradation under ultraviolet and visible radiation. For comparative reasons, P25 (Degussa) was also employed as the catalyst. Furthermore, the effect of reuse of catalysts and photocatalytic activity compared to real samples were also evaluated. The silica supported catalyst prepared from petrochemical waste and supported on silica showed the best photocatalytic activity in the degradation of all tested molecules, such as RhB (67% and 61% under UV and visible radiation, respectively), guaifenesin drug (49% UV and 45 % visible radiation) and phenol (44 % UV radiation), while the commercial P25 showed 93 % and 14 %, to ultraviolet and visible radiation, respectively.

Made available in DSpace on 2018-06-27T18:55:46Z (GMT). No. of bitstreams: 2 Jose Dilmar Obregon do Carmo.pdf: 12505165 bytes, checksum: af1796162335333199c5ad137e5f502d (MD5) Jose Dilmar Obregon do Carmo.pdf.jpg: 2961 bytes, checksum: 88959577b2ee0395315a4b7ca4bf32e4 (MD5) Previous issue date: 2009-05-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The titanium oxide (TiO2) is known as a material of excellent photocatalytic activity and its applications in fields that involve the removal of gases, decomposition of organic compounds, water purification and decomposition of pollutants. The nanotubes of titania and titanates have attracted particular attention in the scientific world because of its potential for application by submitting a larger surface area and number of hydroxyl groups when compared to the precursor oxide (TiO2), opening a new horizon for implementation, especially for photocatalysis. This study aimed to evaluate the photocatalytic performance of samples of inorganic nanotubes of formula NTTi, NTTiH, NTTiOx NTTi-Ag, NTTiH-Ag and Ag-NTTiH on effect of ultraviolet light, before the bacteria Escherichia coli (ATCC 12228) and Staphylococcus aureus (ATCC 6538) as a model, well known for being the point genetic. The results found in this work, agree with most publications viewed until now. Samples NTTi-Ag, NTTiH-Ag and Ag-NTTiH, showed better photocatalytic effect, shown in the diffusion test on Mueller Hinton agar, when compared to the halo of inhibition of the antibiotic ampicillin. And there was a low performance of the titanates nanotubes (TTNT), specially of the show NTTi, NTTiH and NTTiOx front the bacteria Escherichia coli and Staphylococcus aureus, probably due to structural form of nanotubes, probably favoring greater recombination of electron pair/gap (e¯/h+). The results at times 60/90/120 min, should be probably the effect of ultraviolet light (λ 365 nm) and not the effect of the nanotubes and ultraviolet light. The samples with silver showed a halo of inhibition around 1 to 3 mm, more than 5 mm of the hole where they were placed in 50μl solution of microorganisms Escherichia coli and Staphylococcus aureus. This part of the study observed the synergism of the nanotubes with silver and ultraviolet light at all times. / O óxido de titânio (TiO2) é conhecido como um material de excelente atividade fotocatalítica e suas principais aplicações envolvem a remoção de gases,a decomposição de compostos orgânicos e de poluentes, assim como a purificação da água. Os nanotubos de titanatos (ou titânia) têm atraído, em especial, a atenção do mundo científico, devido ao seu potencial de aplicação. São importantes por apresentarem uma maior área superficial e elevado número de grupos hidroxilas, quando comparados ao óxido precursor (TiO2), abrindo, assim, um novo horizonte para aplicação, principalmente da fotocatálise. Este trabalho teve como objetivo avaliar o desempenho fotocatalítico das amostras de nanotubos inorgânicos de fórmulas NTTi, NTTiH, NTTiOx, NTTi-Ag, NTTiH-Ag e Ag-NTTiH, sob efeito da luz ultravioleta, frente às bactérias Escherichia coli (ATCC 12228) e Staphylococcus aureus (ATCC 6538) como modelo.Os resultados dos testes fotocatalíticos, encontrados nessa pesquisa, concordam com a maioria das publicações conhecidas até agora. As amostras NTTi-Ag, NTTiH-Ag e Ag-NTTiH demostraram melhor efeito fotocatalítico, comprovado no teste de difusão em Agar Mueller Hinton, quando comparado ao halo de inibição do antibiótico ampicilina. Observou-se um baixo desempenho dos nanotubos de titanatos (TTNT), principalmente das amostras NTTi, NTTiH e NTTiOx frente às bacterias Escherichia coli e Staphylococcus aureus. É muito provável que isso tenha acontecido devido à forma estrutural desses nanotubos, favorecendo uma maior recombinação do par elétron/lacuna (e¯/h+). Os resultados encontrados, nos tempos 60/90/120 minutos, acredita-se que seja devido ao efeito da luz ultravioleta ( 365 nm) e não ao efeito dos nanotubos e luz ultravioleta. As amostras com prata apresentaram um halo de inibição (1 a 3 mm) a mais do que os 5 mm do orifício onde foram colocados 50μl da solução dos microorganismos Escherichia coli e Staphylococcus aureus. Nesta parte do estudo, notou-se o sinergismo dos nanotubos com prata e a luz ultravioleta em todos os tempos.

Le dépôt chimique en phase vapeur assisté par plasma est appliqué pour préparer des couches minces amorphes de TiO2 à basse température. Un recuit à 300 °C pendant un temps minimum de 4,5 h permet de former la phase cristalline anatase. Les principales caractéristiques de ces couches minces comme leur structure cristalline, leur microstructure, leur largeur de bande interdite et leur hydrophilie de surface, sont déterminées. Leurs performances fonctionnelles comme photocatalyseurs sont d'abord examinées selon le test breveté par Pilkington, consistant à éliminer sous irradiation UV de l'acide stéarique préalablement adsorbé sur les couches de TiO2 ici déposées sur des plaquettes de silicium. Des membranes M100 (couche continue de TiO2) et M800 (couche de TiO2 couvrant les grains de support) sont préparées sur les couches de surface macroporeuses de supports poreux en alumine, de tailles moyennes de pores respectives, 100 nm et 800 nm. Ces membranes sont testées en condition "statique", avec la diffusion d'un soluté organique dilué dans l'eau. Pour le bleu de méthylène, on montre que la quantité de composé détruit par unité de surface de membrane et par unité de temps est égale à 2 × 10-8 mol m-2 s-1 pour la membrane M100 et 1 × 10-8 mol m-2 s- 1 pour la membrane M800. Ces membranes sont également testées dans des conditions "dynamiques", à savoir en procédé baromembranaire, avec deux configurations différentes (couche photocatalytique du côté de l'alimentation ou du côté du perméat) et trois composés organiques différents (bleu de méthylène, acide orange 7 et phénol). La modélisation du procédé (adsorption et réaction photocatalytique) est finalement réalisée à partir des données expérimentales disponibles. / Plasma-enhanced chemical vapor deposition is applied to prepare amorphous TiO2 thin films at low temperature. Post-annealing at 300 °C for minimal staying time 4.5 h is required to form crystalline anatase phase. Characteristics of the TiO2 thin films including crystalline structure, microstructure, band gap and surface hydrophilicity, are determined. Functional performance of these anatase thin films as photocatalysts is first examined with patented Pilkington assessment by removing, under UV irradiation, stearic acid initially adsorbed on TiO2 layers here deposited on silicon wafers. Membranes M100 (TiO2 continuous layer) and M800 (TiO2-skin on support grain) are prepared on the macroporous top layer of porous alumina supports with an average pore size of 100 nm and 800 nm, respectively. These membranes are tested in “static” condition under the effect of diffusion of an organic solute in water. For Methylene Blue it is shown that the quantity of destroyed compound per unit of membrane surface area and per unit of time is equal to 2×10−8 mol m-2 s-1 for M100 and 1×10−8 mol m-2 s-1 for M800. These membranes are also tested in “dynamic” conditions, i.e. pressure-driven membrane processes, with two different configurations (photocatalytic layer on the feed side or on the permeate side) and three different organics (Methylene Blue, Acid Orange 7 and phenol). Process modelling (adsorption and photocatalysis reaction) is finally carried out from the available experimental outputs.

No description available.

The technology of semiconductor-based photocatalytic water splitting to produce hydrogen using solar energy has been considered as one of the most important approaches to solve the world energy crisis. Therefore, the development of the effective semiconductor photocatalysts has undergone considerable research. However, the traditional photocatalysts suffer from the negative effects from rapid charge recombination, which reduces the excited charges by emitting light or generating phonons. Efficient charge separation and fast charge transport, avoiding any bulk/surface recombination, are fundamentally important for photocatalytic hydrogen generation through water splitting. Here, we have introduced assembled layered materials as photocatalyst systems with their unique physicochemical properties to realize the effective charge separation and high photocatalytic activity. Using graphene as a two-dimensional supporting matrix, we have succeeded in selective anchoring of semiconductor and metal nanoparticles as separate catalytically active sites on the graphene surface. The ability of graphene to capture, transfer and store electrons and its potential to serve as a conductive support are demonstrated. The TiO₂ semiconductor/metals nanocrystals-graphene ensemble makes it possible to carry out selective catalytic processes at the separate sites and provides the potentials for applications in water splitting reactions. After demonstrating the positive role of graphene in such photocatalytic system, we then fabricate a simple but highly cooperative ensemble with CdS and MoS₂ nanocrystals dispersed on graphene sheets. It is demonstrated that CdS nanocrystals can also capture visible light energy and facilitate excited electron transfer to MoS₂ (as metal substituent) for catalytic hydrogen production via the 2-D graphene which plays a key role as an efficient electron mediator. Hexagonal multilayer MoS₂ with a layered structure in this system serves to provide active sites for hydrogen evolution by its exposed Mo edges. Hence, multilayer MoS₂ is an ideal cocatalyst of semiconductors for hydrogen generation. This crystalline-layered structure also shows semiconducting properties, however, its characteristic indirect band gap displays a poor light capture and emission ability with excited electrons and holes with different momentum. In contrast, single layer MoS₂ shows a direct band gap behavior. Our studies have clearly shown that single layer MoS₂ prepared with lithium intercalation indeed displays encouraging results in hydrogen evolution due to the direct band gap and quantum confinement effects. In addition, the exfoliated single layer MoS₂ exhibits extraordinary enhanced activity and stability in combination with the Eosin Y sensitized system when compared to those of multilayer MoS₂ and bulk MoS₂ counterparts, which is attributed to the improvement of the density of surface active sites with stronger adsorption for the Eosin Y molecules on the single layer MoS₂. In addition, this multifunctional catalyst on graphene sheet can also create adsorption sites on a defective basal surface of single layer MoS₂ through adsorption of Eosin Y where electron transfer from photoexcited Eosin Y molecule to graphene via the 2-D MoS₂ mainly takes place. Thus, the photo-generated electrons are then effectively transported to the exposed active sites of MoS₂ for the proton reduction to hydrogen molecule. It is believed the above novel assembled molecular layered systems may be applicable for a wide range of catalytic,photocatalytic and electrocatalytic reactions.

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 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.

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.