Made available in DSpace on 2015-07-13T12:10:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-12-19. Added 1 bitstream(s) on 2015-07-13T12:24:10Z : No. of bitstreams: 1 000827359_20160127.pdf: 77899 bytes, checksum: 6b02ed519f08e50aa9f14e869acaca5a (MD5) Bitstreams deleted on 2016-01-28T17:44:58Z: 000827359_20160127.pdf,. Added 1 bitstream(s) on 2016-01-28T17:45:38Z : No. of bitstreams: 1 000827359.pdf: 3546505 bytes, checksum: 1a55419c9034fdde19219a7bb38966d9 (MD5) / Este trabalho tem como principal objetivo obter nanoestruturas de titanato de sódio (Na2Ti6O13) puras e dopadas usando o método hidrotermal assistido por micro-ondas, visando aplicação fotocatalítica na descoloração do corante rodamina B. No processo de síntese hidrotérmica os parâmetros potência de irradiação de micro-ondas (450W), volume de solução (50 mL), concentração de TiO2 (~0,5 g) e NaOH (10 M) foram mantidos fixos. Na primeira etapa do trabalho utilizou-se o TiO2 (anatase) comercial como precursor para a formação dos nanotubos. Nesta etapa foi avaliado o efeito da temperatura e do tempo de reação nas características do produto formado. A faixa de temperatura usada para a obtenção dos nanotubos foi de 130 a 200 °C enquanto que o tempo de reação variou de 0,5 a 4h. Em todas as sínteses o produto formado foi o titanato de sódio (Na2Ti6O13) identificado pela presença de picos em 2θ iguais a 10, 24, 28, 48°, quando analisados por difratometria de raios X, DRX. Por análises de microscopia eletrônica de varredura de alta resolução, MEV, observou-se a morfologia de nanoestruturas 1D, que pelas imagens de microscopia de transmissão, MET, associada a análise de área superficial (BET), da ordem de 300 - 400 m2 g-1, ficou evidenciado serem nanotubos. Todas as amostras, preparadas nesta etapa, apresentaram atividade na descoloração da rodamina B, com destaque para as obtida a 130 °C por 3 h e 180 °C por 1 h. A caracterização óptica destas amostras indicou emissão na região visível dos espectros de fotoluminescência, principalmente no azul (proporção relativa de 3 a 7%), e também emissão no verde maior ou igual a do laranja. Também foi usado o isopropóxido de titânio como precursor, mantendo-se todas as condições da primeira etapa, obtendo-se amostras com os mesmos perfis estruturais e ópticos, as quais também se mostraram ativas ... / This work aims to obtain sodium titanate nanostructures (Na2Ti6O13), pure and doped, using the microwave assisted hydrothermal method, aiming photocatalytic application in rhodamine B dye discoloration. In hydrothermal synthesis process, parameters such power microwave irradiation (450W), volume (50 mL), TiO2 concentration (~ 0.5 g) and NaOH (10 M) were kept fixed. In the first stage of this study TiO2 (anatase) commercial was used as a precursor for nanotubes formation. In this step, the effects of temperature and reaction time in the product characteristics. The temperature range used for obtaining the nanotubes was 130 to 200 ° C while the reaction time varied from 0.5 to 4 hours. In all syntheses the product formed was sodium titanate (Na2Ti6O13) identified by the presence of peaks at 2θ equal to 10, 24, 28, 48 °, when analyzed by X-ray diffraction, XRD. For high-resolution electron microscopic analysis, SEM, it was observed that the morphology of 1D nanostructures, which by transmission microscopy images, MET, associated surface area analysis (BET), in the range 300-400 m2 g-1, be evidenced nanotubes. All samples prepared at this stage, were active in the rhodamine B discoloration, and that obtained at 130 ° C for 3 h and 180 ° C for 1 h were better. The optical characteristics of these samples showed emission in the visible region of the photoluminescence spectra, particularly in the blue (relative proportion of 3 to 7%) and also green emission that was greater than or equal to orange. The titanium isopropoxide was also used as a precursor, keeping all the conditions established at the first stage, obtaining samples with the same structural and optical profiles, which were also active for photocatalysis. The nanotubes obtained were modified with silver, which was added to the precursor solution synthesis (dopant) or after synthesis (surface modifier). It has been found that the presence ...

Made available in DSpace on 2014-12-02T11:16:38Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-01-16Bitstream added on 2014-12-02T11:21:05Z : No. of bitstreams: 1 000775296_20150116.pdf: 449463 bytes, checksum: 43558585e6fb22e6d593a800fe0eebb0 (MD5) Bitstreams deleted on 2015-01-23T10:59:21Z: 000775296_20150116.pdf,Bitstream added on 2015-01-23T10:59:53Z : No. of bitstreams: 1 000775296.pdf: 2220721 bytes, checksum: 20bda960969f72c4be9130ed074b0799 (MD5) / O presente trabalho reporta os principais resultados obtidos na construção e caracterização de eletrodos de titânio recobertos com nanotubos de óxido de titânio modificados com nanopartículas de platina (TiO2/Pt) e eletrodos de cobre recobertos com nanopartículas de óxido de cobre (Cu/Cu2O) com vistas a sua aplicação na redução fotoeletrocatalítica de CO2 em meio aquoso e semicondutores em pó de CuNbO3-CuO, Cu0,85Zn0,15Nb2O6 e ZnNb2O6-Nb2O5 construídos e testados na redução fotocatalítica de CO2, com vistas a geração de produtos com maior valor agregado, tal como metanol. Os eletrodos TiO2/Pt e Cu/Cu2O foram construídos por meio de técnicas de eletroquímicas, enquanto que os semicondutores em pó CuNbO3-CuO, Cu0,85Zn0,15Nb2O6 e ZnNb2O6-Nb2O5 foram preparados utilizando a técnica de síntese por combustão e calcinação posterior. A redução fotoeletrocatalítica e fotocatalítica de CO2 não foi satisfatória sobre eletrodos de TiO2/Pt e semicondutor ZnNb2O6-Nb2O5, respectivamente. No entanto, o eletrodo de Cu/Cu2O apresentou grande eficiência na redução de CO2, atingindo 80% de remoção em meio de Na2CO3 0,3 mol L-1 pH 9 a +0,2 V, em solução tampão de NaHCO3/Na2CO3 0,1 mol L-1 pH 8, utilizando luz UV 125 W e potencial de +0,2 V mostrou uma reação praticamente seletiva para metanol, gerando 5,63 mmol L-1, correspondendo a 20% de conversão. Os semicondutores em pó CuNbO3-CuO e Cu0,85Zn0,15Nb2O6 também se mostraram bastante eficientes para a geração de metanol por redução de CO2 dissolvido em Na2CO3 0,1 mol L-1 pH8 utilizando luz visível de 450 W, chegando a formar 7,0 mmol L-1 e 3,2 mmol L-1 de metanol respectivamente. Os resultados obtidos neste trabalho mostram que ambas as técnicas podem ser empregadas para a redução do CO2, usando para isto os semicondutores Cu/Cu2O, CuNbO3-CuO e Cu0,85Zn0,15Nb2O6 e, poderia ser uma potencial alternativa para os problemas ambientais além de contribuir como fonte... / This present work reports the main results obtained with the construction and characterization of TiO2 nanotubes modified by platinum nanoparticle electrode (TiO2/Pt) and copper covered by copper oxide nanoparticles electrode (Cu/Cu2O) for application in the photoelectrocatalytic reduction of dissolved CO2 and CuNbO3-CuO, Cu0,85Zn0,15Nb2O6 and ZnNb2O6-Nb2O5 powders semiconductors constructed and applied in the photocatalytic reduction of dissolved CO2 for the generation of products with higher added value. The TiO2/Pt and Cu/Cu2O electrodes were prepared by electrochemical techniques, whereas the CuNbO3-CuO, Cu0,85Zn0,15Nb2O6 and ZnNb2O6-Nb2O5 powder semiconductors were prepared using the combustion synthesis technique and submitted to annealed. The CO2 reduction by photoelectrocatalysis and photocatalysis were not satisfactory when using the TiO2/Pt electrode and the ZnNb2O6-Nb2O5 semiconductor, respectively. However, the Cu/Cu2O electrode shows a high efficiency in the CO2 reduction obtaining 80% of removal in 0.3 mol L-1 Na2CO3 pH 9 and +0.2 V, and, it showed a practically selective reaction to methanol (producing 5.63 mmol L-1), corresponding to 20% of conversion at ambient of 0.1 mol L-1 NaHCO3/Na2CO3 butter solution pH 8, using UV light of 125 W and +0,2 V. The CuNbO3-CuO and Cu0,85Zn0,15Nb2O6 powder semiconductors also showed a good efficiency to the methanol formation throughout dissolved CO2 reduction in 0.1 mol L-1 Na2CO3 pH 8 using visible light of 450 W, and forming 7 mmol L-1 and 3.2 mmol L-1 of methanol, respectively. The results obtained in this work show that both techniques can be employed for the CO2 reduction, using for this the Cu/Cu2O, CuNbO3-CuO and Cu0,85Zn0,15Nb2O6 semiconductors, and it could be a potential alternative to the environmental problems and contribute as raw material source for the production of fuels, for instance.

Made available in DSpace on 2014-12-02T11:16:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-03-25Bitstream added on 2014-12-02T11:21:04Z : No. of bitstreams: 1 000773454.pdf: 4924956 bytes, checksum: 02d75baef0f2f594f53a30b850a17b92 (MD5) / Este trabalho se baseou na síntese de catalisadores de TiO2 modificados com cátions de nióbio estruturalmente através do método Pechini e superficialmente através da deposição de nióbio metálico por sputtering, caracterização destes catalisadores para verificar estas modificações, e a avaliação da atividade fotocatalítica na redução do CO2 a metanol e da descoloração de soluções do corante Rodamina-B. A modificação do TiO2 busca obter um aumento no tempo de recombinação do par elétron/buraco e consequentemente uma maior atividade fotocatalítica. A modificação em substituição do Ti4+ pelo Nb5+ visa promover a geração de níveis doadores de elétrons na estrutura cristalina e a modificação por deposição de nanopartículas de nióbio metálico por sputtering que atuarão como aceitadores de elétrons sobre a superfície dos catalisadores, modificações estas, que atuarão na redução do CO2. Partindo destas premissas, primeiramente foram sintetizados os catalisadores nas concentrações 0,0%; 0,5%; 1,0%; 2,5% (m/m) de nióbio, e posteriormente 5,0%; 10,0% e 20,0% (m/m) de nióbio através dos métodos citados. Os catalisadores obtidos foram caracterizados utilizando difratometria de Raios X (DRX - Rigaku Rint-2000), área de superfície SBET (B.E.T. - Micrometrics ASAP 2010), espectroscopia RAMAN (HORIBA-HR 800), FEG/SEM (JEOL modelo JSM-7500F) e XPS (UNI-SPECS UHV) para analisar as características da superfície. Após a caracterização, os catalisadores foram submetidos a dois ensaios fotocatalíticos. O primeiro para avaliar a ocorrência da redução de CO2 e o segundo visou avaliar a capacidade dos mesmos na descoloração oxidativa do corante Rodamina-B utilizando espectroscopia na região do UV-vis para obtenção dos resultados. Para verificar e quantificar a possível formação de radicais carbonila e álcool, cada amostra foi analisada por TOC (O.I. Analytical Aurora model 1030) e GC-FID... / This work was based on synthesis of TiO2 photocatalysts powders modified with Nb structurally by Pechini and superficially by metallic Nb depositing by sputtering, characterization of these photocatalysts powders to verify these changes, and evaluation of photocatalytic activity in the reduction of CO2 to methanol and decolorization of of dye rhodamine-B solutions. The TiO2 modification tries to achieve an increase in the recombination time of the electron-hole pair and hence a higher photocatalytic activity. The modification to replace Ti4+ by Nb5+ aims to promote the generation of donor levels of electrons in the crystal structure and modification for nanoparticles deposition of metallic Nb by sputtering to act as acceptor of electrons on the photocatalysts powders surface, changes them, who will serve in reducing CO2. Starting from these premises first photocatalysts powders were synthesized in the compositions of 0.0 %, 0.5 %, 1.0 %, 2.5 % (w/w) of Nb and subsequently 5.0% , 10.0 % and 20.0% (w/w) of Nb with the methods mentioned. The photocatalysts powders were characterized using X-ray diffraction (XRD-Rigaku Rint-2000) , surface area SBET (EST-Micrometrics ASAP 2010) , Raman spectroscopy (HORIBA HR-800 ) , FEG / SEM (JEOL JSM-7500F) and XPS (UNI-SPECS UHV) to analyze the surface characteristics. After characterizing the photocatalysts poder underwent two photocatalytic tests. The first to assess the occurrence of CO2 reduction and the second aimed at evaluating the capacity in the oxidative bleaching of the dye rhodamine-B using spectroscopy in the UV-vis region to obtain the results. To verify and quantify the possible formation of carbonyl and alcohol radicals, each sample was analyzed for TOC (Aurora Analytical model HI 1030) and FID-GC (Varian CP- 3800). Through the techniques used for characterization of photocatalyst powders was observed that the predominant crystalline phase is anatase and Ti was replaced by Nb...

Semiconductor-based heterogeneous photocatalysis, as one of the advanced oxidation processes that makes use of semiconductors and inexhaustible solar light, has recently been extensively studied and applied to water decontamination. However, due to low light absorption efficiencies and severe electron-hole recombination, modifications on semiconductor structures are required in order to enhance their photocatalytic performance. Heterogeneous photocatalyst composites, taking advantage of the improved light absorption efficiency as well as the facilitated electron-hole separation at the interface between different semiconductors, have been proven to be a promising strategy. In this study, novel NaNbO3/Bi2WO6 photocatalyst composites with a type-II heterogeneous alignment were successfully prepared via a facile wet impregnation method. The as-prepared photocatalysts were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance UV-Vis spectroscopy (DRS), photocurrent (PC) and electrochemical impedance spectroscopy (EIS) analyses. The 30 wt% NaNbO3/Bi2WO6 composite exhibited the best performance for degrading an RhB (rhodamine B) aqueous solution under visible light irradiation (λ > 410 nm), which was ca. 40 times and ca. 2.5 times that of the pristine NaNbO3 and Bi2WO6, respectively. The improved photocatalytic activity may be attributed to the enhanced electron-hole separation efficiency in Bi2WO6 with the assistance of NaNbO_3, as well as the dye-sensitization effect of RhB itself. Radical quenching experiments revealed that h+ played the predominant role, and O2•- functioned as well to some degree. The produced intermediates during the reaction and RhB degradation pathway were speculated and investigated as well. The excellent stability and reusability were verified by repetitively running for five times. Based on experimental results, a plausible functioning mechanism was proposed. Effects of several operation parameters on the catalyst performance including initial RhB concentration, catalyst dosage, reaction temperature and initial pH were also discussed. This study provides solid evidence for NaNbO3 to be a promising candidate for photocatalysis and gives out a novel photocatalytic mechanism of Bi2WO6-based type-II heterostructures.

The oxidation kinetics of m-substituted phenols by TiO2/UV were investigated. An attempt was made to correlate Swain-Lupton parameters (R) for aromatic substituents with the oxidation kinetic constants, based upon molecular structure and reactivity theory. Irradiation experiments were carried out with suspended aqueous TiO 2 powder and substrate mixture in a Rayonet Photochemical Reactor. Langmuir-Hinshelwood model was applied to obtain apparent kinetic rate constants. A linear correlation is observed between Langmuir-Hinshelwood kinetic parameters and Hammett constants for m-chloro, m-bromo and m-fluoro phenols. The changes in p values of Hammett plots at pH 3 suggest that the main degradation pathway may involve a positively charged intermediate, such as a radical cation formed by direct electron transfer to the positive holes at low pH. At high pH levels, however, substrate speciation, surface charge of the semiconductor, and bandgap shift appear to lead to a change in the degradation mechanism.

Brominated flame retardants have been widely used in industry. There is a rapidly growing public concern about their ubiquity in the environment. This project investigated the possible removal treatments of polybrominated diphenyl ethers (PBDEs) using two treatment methods: (I) photocatalysis by TiO2 and (II) phytoremediation by Oryza sativa and Phragmites australis, and a combined system involving these two technologies. Advanced oxidation process (AOP) is a promising technology for removing emerging chemicals. In this case, nano-scaled titanium (IV) oxide was applied to evaluate its capability in the degradation of BDE-209 under visible light. The residual PBDE congeners after reaction were analyzed by gas chromatography-mass spectrometry (GC-MS). The half-life for removing BDE-209 by TiO2 was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be pH 12 (93% ± 1%), at least 5 mg/L (93 ± 1.70%) of humic acid and in the form of anatase/rutile TiO2 (82% ± 3%). Incomplete removal of PBDEs by water treatment plants and point-source contamination may lead to their discharge into water bodies and ultimately into soils. Consequently, the second part of the project was phytoremediation of PBDEs. Uptake of BDE-209 by rice cultivars, namely Fengmeizhan, Hefengzhan and Guangyinzhan, and common reed were examined by 60-day cultivation in sterilized BDE-209 spiked soil. Hefengzhan possessed the greatest ability in the removal and accumulation of BDE-209 among the three cultivars, especially when associated with Glomus intraradices, at pH 7. A series of plant-contamination sorption analyses were also employed for pathway studies of PBDEs uptake by rice. A partition-limited model was applied for describing and estimating the uptake of BDE-209 by rice roots. The average quasi-equilibrium factors (apt) of BDE-47, -99 and -209 in root uptake were 1.44 × 10-3 , 0.966 × 10 -3 and 0.115 × 10-3 in sand (< 1), implying a non-equilibrium state of the movement of molecules and a dominant passive transport uptake. From the result of sorption analysis of dead and fresh roots, the apoplastic pathway likely dominated the transport of PBDEs into root cells. These results provide essential information on the uptake mechanism of PBDEs into plants. Based on the results from photocatalysis and phytoremediation, a combined photocatalysis (TiO2 and visible light) and constructed wetland system (Oryza sativa (Hefengzhan) and Phragmites australis (common reed) was set up for comparing PBDEs removal efficiencies. The removal percentages of BDE-209 in the combined system were found to be promoted when compared to the individual systems, which could be explained by enhanced biodegradability of PBDEs in photocatalysis. Therefore, the proposed advanced wastewater treatment technology (combined photocatalysis and constructed wetland systems) might help to degrade and eliminate BDE-209 in the wastewater, and thus reduce the risks of marine contamination by discharging these incompletely or partially treated wastewaters containing PBDEs.

Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-09-27T11:47:25Z No. of bitstreams: 1 DissMD.pdf: 3874080 bytes, checksum: f245af64331a5190649cede80208ac01 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-04T18:10:35Z (GMT) No. of bitstreams: 1 DissMD.pdf: 3874080 bytes, checksum: f245af64331a5190649cede80208ac01 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-04T18:10:41Z (GMT) No. of bitstreams: 1 DissMD.pdf: 3874080 bytes, checksum: f245af64331a5190649cede80208ac01 (MD5) / Made available in DSpace on 2016-10-04T18:10:51Z (GMT). No. of bitstreams: 1 DissMD.pdf: 3874080 bytes, checksum: f245af64331a5190649cede80208ac01 (MD5) Previous issue date: 2015-03-30 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / This dissertation studies the application of rutile substrate as an alternative support for anatase films, specifically, on the growth and properties of anatase films. The films were utilized as catalysts for the photodegradation of water contaminants (Atrazine and Rhodamine B). Ti4+ precursor resin was prepared by the polymeric precursor method and deposited by spin coating onto polycrystalline rutile and rutile coated glass substrates. The films were calcined at different temperatures (350 °C to 500 °C) to form anatase TiO2 films. The influence of temperature on the properties of the films has been reported in this study. A comparative study of the films was also done using X-ray diffraction technique (XRD), grazing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). XRD and GIXRD results confirmed the formation of anatase on the (101) plane depending on the calcination temperature. Bandgap modification of the films with respect to calcination temperature was measured by UV visible diffuse reflectance spectroscopy. The bandgaps were in the range of 2.74 to 2.85 eV. Photocatalytic activity of the films supported on rutile substrate was studied for the degradation of Atrazine (ATZ) and Rhodamine B (Rhod-B) under UV light. Further, the stability of the films was evaluated on four consecutive cycles where the films maintained their photocatalytic properties in all cases. The kinetics of Rhod-B and ATZ degradation followed a pseudo first order and first order exponential decay respectively. The films calcined at 450 °C and 500 °C showed superior photocatalytic activity for Rhod-B degradation than the films calcined at 350 °C and 400 °C. This is attributed to the adequate crystallinity of anatase. For ATZ degradation, the films were also efficient but no specific trend was observed. The results can contribute towards the development of TiO2 films on rutile phase substrates. / Esta dissertação estuda a aplicação de substratos de rutilo como suportes alternativos para filmes de anatase, especificamente, sobre o crescimento e propriedades de filmes de anatase sobre rutilo. Os filmes foram utilizados como catalisadores para a fotodegradação de contaminantes de água (Atrazina e Rodamina B). A resina de Ti4+ foi preparada pelo método de precursores poliméricos e depositada por spin coating sobre rutilo policristalino e em substratos de vidro revestido de rutilo. As amostras foram calcinadas a diferentes temperaturas (350 a 500 °C) para formar filmes de anatase TiO2. Um estudo comparativo dos filmes foi feito usando a técnica de difração de raios X (DRX), difração de raios X com ângulo rasante (DRXR), microscopia de força atômica (AFM) e microscopia eletrônica de varredura (MEV). Os resultados de DRX e DRXR confirmaram a formação de anatase nos filmes ao longo do plano (101) dependendo da temperatura de calcinação. Modificações do bandgap dos filmes de acordo com a temperatura de calcinação foram medidas por reflectância difusa de UV-visível onde os bandgaps variou de 2,74 para 2,85 eV. Atividade fotocatalítica dos filmes imobilizados sobre substrato de rutilo foi estudada para a degradação de Atrazina (ATZ) e Rodamina B (Rhod-B) sob luz UV. Além disso, a estabilidade dos filmes foi avaliada em quatro ciclos consecutivos onde os filmes mantiveram suas propriedades fotocatalíticas em todos os ciclos. As cinéticas de degradação de Rhod-B e de ATZ seguiram um ajuste de pseudo-primeira ordem e decaimento exponencial de primeira ordem, respectivamente. Os filmes que foram calcinados a 450 °C e 500 °C mostraram atividade fotocatalítica superior para a degradação de Rhod-B aos filmes calcinados a 350 °C e 400 °C. Isto foi atribuído à cristalinidade adequada da fase anatase. Para ATZ, os filmes foram eficientes mas nenhuma tendência especifica foi observada. Os resultados podem contribuir para o desenvolvimento de filmes de TiO2 imobilizados sobre substratos de rutilo.

Resumo: Esse estudo investigou a cinética de coagulação floculação do TiO2 em suspensão aquosa de baixa força iônica (água destilada)e força iônica média (água de abastecime to público),em função do pH e da adição de sulfato de alumínio. A coagulação floculação do TiO2 ocorre quando o pH é ajustado próximo ao pH do potencial isoelétrico, pela compressão da camada de difusão ou pela adsorção hidrólise com íons Al 3+ . Em suspensões de TiO2 com baixa força iônica,a coagulação ocorre a um determinado pH (4,0 e 7,0), uma vez que ele depende basicamente da superfície do óxido. Com adição de um coadjuvante de sedimentação (por ex. sulfato de alumínio), a qual a força iônica é alta,a coagulação floculação ocorre muito rápido. O tempo de decantação do material em suspensão foi de 2:00 h, foi comparada a cinética de sedimentação da decantação simples com a realizada em Jar Test sob a influência de agitação rápida (eletrocinético) e lenta (ortocinético) antes de permitir a sedimentação. O melhor desempenho foi em Jar Test,turbidez final de 10 NTU. / Abstract: This study investigated the coagulation-flocculation kinetics of TiO2 in an aqueous Suspension of low-strength ionic solution (distilled water) and a medium strength ionic solution (tap water) as a function of pH and of the addition of aluminum sulfate. Coagulation-flocculation of TiO2 occurs when the pH is adjusted close to the isoelectric potential (iep), by compression of the diffusion layer or by adsorption-hydrolysis with Al 3+ ions. In TiO2 suspensions with low electric strength,coagulation takes place at certain pH (4,0 a d 7,0) since it depends basically on the oxide surface.With the addition of sedimentation aid (e.g.,aluminum sulfate), in which the ionic strength is high, coagulation-flocculation, takes place very fast. The decantation time of the material in suspension was of 2h. The sedimentation kinetic of the simple decantation was compared to that carried out in Jar Test under influence of fast stirring (electrokinetic) and slow stirring (ortokinetic) before sedimentation set up.The best performance was in Jar Test,final turbidez of 10 NTU. / Orientador: Ariovaldo de Oliveira Florentino / Coorientador: José Pedro Serra Valente / Banca: Pedro Magalhães Padilha / Banca: Cassio Luis Fernandes de Oliveira / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Mestre

Orientador: Leinig Antonio Perazolli / Co-orientador: Ossamu Hojo / Banca: Leandro Martins / Banca: Marcelo Henrique Armoa / Resumo: Este trabalho se baseou na síntese de catalisadores de TiO2 modificados com cátions de nióbio estruturalmente através do método Pechini e superficialmente através da deposição de nióbio metálico por sputtering, caracterização destes catalisadores para verificar estas modificações, e a avaliação da atividade fotocatalítica na redução do CO2 a metanol e da descoloração de soluções do corante Rodamina-B. A modificação do TiO2 busca obter um aumento no tempo de recombinação do par elétron/buraco e consequentemente uma maior atividade fotocatalítica. A modificação em substituição do Ti4+ pelo Nb5+ visa promover a geração de níveis doadores de elétrons na estrutura cristalina e a modificação por deposição de nanopartículas de nióbio metálico por sputtering que atuarão como aceitadores de elétrons sobre a superfície dos catalisadores, modificações estas, que atuarão na redução do CO2. Partindo destas premissas, primeiramente foram sintetizados os catalisadores nas concentrações 0,0%; 0,5%; 1,0%; 2,5% (m/m) de nióbio, e posteriormente 5,0%; 10,0% e 20,0% (m/m) de nióbio através dos métodos citados. Os catalisadores obtidos foram caracterizados utilizando difratometria de Raios X (DRX - Rigaku Rint-2000), área de superfície SBET (B.E.T. - Micrometrics ASAP 2010), espectroscopia RAMAN (HORIBA-HR 800), FEG/SEM (JEOL modelo JSM-7500F) e XPS (UNI-SPECS UHV) para analisar as características da superfície. Após a caracterização, os catalisadores foram submetidos a dois ensaios fotocatalíticos. O primeiro para avaliar a ocorrência da redução de CO2 e o segundo visou avaliar a capacidade dos mesmos na descoloração oxidativa do corante Rodamina-B utilizando espectroscopia na região do UV-vis para obtenção dos resultados. Para verificar e quantificar a possível formação de radicais carbonila e álcool, cada amostra foi analisada por TOC (O.I. Analytical Aurora model 1030) e GC-FID... / Abstract: This work was based on synthesis of TiO2 photocatalysts powders modified with Nb structurally by Pechini and superficially by metallic Nb depositing by sputtering, characterization of these photocatalysts powders to verify these changes, and evaluation of photocatalytic activity in the reduction of CO2 to methanol and decolorization of of dye rhodamine-B solutions. The TiO2 modification tries to achieve an increase in the recombination time of the electron-hole pair and hence a higher photocatalytic activity. The modification to replace Ti4+ by Nb5+ aims to promote the generation of donor levels of electrons in the crystal structure and modification for nanoparticles deposition of metallic Nb by sputtering to act as acceptor of electrons on the photocatalysts powders surface, changes them, who will serve in reducing CO2. Starting from these premises first photocatalysts powders were synthesized in the compositions of 0.0 %, 0.5 %, 1.0 %, 2.5 % (w/w) of Nb and subsequently 5.0% , 10.0 % and 20.0% (w/w) of Nb with the methods mentioned. The photocatalysts powders were characterized using X-ray diffraction (XRD-Rigaku Rint-2000) , surface area SBET (EST-Micrometrics ASAP 2010) , Raman spectroscopy (HORIBA HR-800 ) , FEG / SEM (JEOL JSM-7500F) and XPS (UNI-SPECS UHV) to analyze the surface characteristics. After characterizing the photocatalysts poder underwent two photocatalytic tests. The first to assess the occurrence of CO2 reduction and the second aimed at evaluating the capacity in the oxidative bleaching of the dye rhodamine-B using spectroscopy in the UV-vis region to obtain the results. To verify and quantify the possible formation of carbonyl and alcohol radicals, each sample was analyzed for TOC (Aurora Analytical model HI 1030) and FID-GC (Varian CP- 3800). Through the techniques used for characterization of photocatalyst powders was observed that the predominant crystalline phase is anatase and Ti was replaced by Nb... / Mestre

Orientador: Maria Aparecida Zagheti Bertochi / Co-orientador: Alberto Adriano Cavalheiro / Banca: Sônia Maria Zanetti / Banca: Diogo Pascoali Volanti / Banca: Talita Manzon Anselmo / Banca: Milady Renata Aparecida da Silva / Resumo: Este trabalho tem como principal objetivo obter nanoestruturas de titanato de sódio (Na2Ti6O13) puras e dopadas usando o método hidrotermal assistido por micro-ondas, visando aplicação fotocatalítica na descoloração do corante rodamina B. No processo de síntese hidrotérmica os parâmetros potência de irradiação de micro-ondas (450W), volume de solução (50 mL), concentração de TiO2 (~0,5 g) e NaOH (10 M) foram mantidos fixos. Na primeira etapa do trabalho utilizou-se o TiO2 (anatase) comercial como precursor para a formação dos nanotubos. Nesta etapa foi avaliado o efeito da temperatura e do tempo de reação nas características do produto formado. A faixa de temperatura usada para a obtenção dos nanotubos foi de 130 a 200 °C enquanto que o tempo de reação variou de 0,5 a 4h. Em todas as sínteses o produto formado foi o titanato de sódio (Na2Ti6O13) identificado pela presença de picos em 2θ iguais a 10, 24, 28, 48°, quando analisados por difratometria de raios X, DRX. Por análises de microscopia eletrônica de varredura de alta resolução, MEV, observou-se a morfologia de nanoestruturas 1D, que pelas imagens de microscopia de transmissão, MET, associada a análise de área superficial (BET), da ordem de 300 - 400 m2 g-1, ficou evidenciado serem nanotubos. Todas as amostras, preparadas nesta etapa, apresentaram atividade na descoloração da rodamina B, com destaque para as obtida a 130 °C por 3 h e 180 °C por 1 h. A caracterização óptica destas amostras indicou emissão na região visível dos espectros de fotoluminescência, principalmente no azul (proporção relativa de 3 a 7%), e também emissão no verde maior ou igual a do laranja. Também foi usado o isopropóxido de titânio como precursor, mantendo-se todas as condições da primeira etapa, obtendo-se amostras com os mesmos perfis estruturais e ópticos, as quais também se mostraram ativas ... / Abstract: This work aims to obtain sodium titanate nanostructures (Na2Ti6O13), pure and doped, using the microwave assisted hydrothermal method, aiming photocatalytic application in rhodamine B dye discoloration. In hydrothermal synthesis process, parameters such power microwave irradiation (450W), volume (50 mL), TiO2 concentration (~ 0.5 g) and NaOH (10 M) were kept fixed. In the first stage of this study TiO2 (anatase) commercial was used as a precursor for nanotubes formation. In this step, the effects of temperature and reaction time in the product characteristics. The temperature range used for obtaining the nanotubes was 130 to 200 ° C while the reaction time varied from 0.5 to 4 hours. In all syntheses the product formed was sodium titanate (Na2Ti6O13) identified by the presence of peaks at 2θ equal to 10, 24, 28, 48 °, when analyzed by X-ray diffraction, XRD. For high-resolution electron microscopic analysis, SEM, it was observed that the morphology of 1D nanostructures, which by transmission microscopy images, MET, associated surface area analysis (BET), in the range 300-400 m2 g-1, be evidenced nanotubes. All samples prepared at this stage, were active in the rhodamine B discoloration, and that obtained at 130 ° C for 3 h and 180 ° C for 1 h were better. The optical characteristics of these samples showed emission in the visible region of the photoluminescence spectra, particularly in the blue (relative proportion of 3 to 7%) and also green emission that was greater than or equal to orange. The titanium isopropoxide was also used as a precursor, keeping all the conditions established at the first stage, obtaining samples with the same structural and optical profiles, which were also active for photocatalysis. The nanotubes obtained were modified with silver, which was added to the precursor solution synthesis (dopant) or after synthesis (surface modifier). It has been found that the presence ... / Doutor