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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
91

A mobilidade eletroforética e o perfil de potencial da membrana celular / Electrophoretic mobility and potential profile of cell menbrane

Izan Mascarenhas Silva Junior 30 August 2010 (has links)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo do presente trabalho foi estudar o comportamento dos potenciais superficiais e do perfil de potencial atraves da membrana de eritr ocito em func ao da forca i onica e das cargas superficiais, usando um modelo que leva em conta as cargas el etricas do glicoc alix e das proteınas citoplasm aticas, al em das cargas superficiais da bicamada lipıdica e os efeitos dos eletr olitos divalentes. Programas especıficos em linguagem C foram elaborados para o c alculo desses potenciais, tomando como dados num ericos resultados experimentais de medidas de mobilidade eletrofor etica de eritr ocitos para diferentes valores de forca i onica. Neste c alculo, o metodo para tratamento dos dados eletrofor eticos indicado por Hsu et al.[57] foi incluıdo em nosso modelo. A equac ao de Poisson-Boltzmann nao linear foi resolvida por computac ao num erica, usando o metodo de Runge-Kutta de quarta ordem, obtendo-se os perfis de potencial. Os resultados mostraram que a estimativa da densidade de carga el etrica na superfıcie de c elulas usando a equac ao cl assica de Helmholtz-Smoluchowski conduz a valores que nao conseguem refletir as forcas que regem o comportamento eletrofor etico das mesmas. O presente modelo gerou valores de potenciais superficiais e perfis de potencial para a membrana do eritr ocito bem distintos daqueles obtidos anteriormente para um modelo descrito por uma equac ao de Poisson-Boltzmann linear. Nossos resultados confirmam que a avaliac ao de parametros el etricos superficiais da membrana de eritr ocito, envolvendo dados oriundos de eletroforese, deve incluir c alculos hidrodin amicos al em de eletroest aticos, como sugerido por Hsu et al. [57]. / The aim of present work was to study the behavior of the surface potentials and the potential profile across erythrocyte membrane in function of ionic strength and surface charge, using a model which takes into account electrical charges on glycocalyx and citoplasmatic proteins, in addition surface charges on lipid bylayer and effects due to mono and divalent electrolytes. Programs in C language were build to estimate the surface potentials, and experimental values of electrophoretic mobilities of erythrocytes for different ionic strength were applied. For this calculation, the method indicated by Hsu et al. [57] for treating electrophoretic data was included in our model. The non linear Poisson-Boltzmann equation was solved by numerical computation, using the forth order Range-Kutta method, to give the potential profiles. Results showed that values of electric charge on cellular surface obtained by applying the classical Helmholtz-Smoluchowski equation were not able to represent the forces involved in the electrophoretic behavior of cells. The present model generate values for surface potentials and potential profiles different from those obtained in previous work for a model described by linear Poisson- Boltzmann equation. According to our results, the estimation of surface electric parameters for the erythrocyte membrane from electrophoretic data must ese hydrodynamics and electrostatics calculations, as suggested by Hsu et al. [57]
92

Estudo das características de dispersão de suspensões de carbonato de cálcio. / Study of dispersion characteristics of calcium carbonate suspensions.

Gabriela Araujo Valencia 12 April 2017 (has links)
O presente trabalho tem como proposição investigar a hipótese de que a diminuição da tensão superficial do líquido favorece o comportamento reológico de suspensões concentradas, uma vez que as partículas estão mais próximas e a contribuição da força de capilaridade possivelmente aumenta. Como suspensões concentradas tendem ao comportamento viscoelástico, investigou-se métodos reológicos propícios para analisar possíveis consequências devido à alteração da tensão superficial da água. Foram utilizados dois carbonatos de cálcio equivalentes (P1 e P5) que se diferenciam pela distribuição granulométrica. Utilizou-se dois dispersantes de mercado e etilenoglicol como modificadores de tensão superficial. A análise de superfície pelo ensaio de potencial zeta, revelou carga superficial positiva. Embora os pós sejam equivalentes, a mobilidade eletroforética do P5 é menor. Verificou-se que o íon cálcio é determinante do potencial. Verificou-se contribuição eletrostática apenas dos dispersantes. O ensaio de gota pendente constatou diminuição da tensão superficial da água com os três aditivos. Ensaios de ascensão capilar pelo método de Washburn revelaram maiores ângulos de contato para ensaios com aditivos, sendo menor para P5. Avaliou-se geometrias e métodos reológicos a fim de selecionar bom conjunto para medidas de viscoelasticidade, sendo oscilatório de tensão e geometria vane escolhidos. O acréscimo dos dispersantes resultou em menores valores de G\' e tensões de escoamento, enquanto o etilenoglicol resultou em maiores. Não há relação clara entre valores calculados de ângulo de contato e mobilidade eletroforética. Os ensaio reológicos e de mobilidade relacionaram-se apenas para os dispersantes. A hipótese foi verificada pelos valores de tensão de escoamento e IPS. Para os dispersantes, foi possível observar comportamento próximo à hipótese, quanto menor foi a tensão superficial do líquido, menores valores de tensão para menores IPS. Explorou-se também a hipótese pelos ensaios de ângulo de contato, observou-se novamente curva próxima a hipótese. Embora necessidade de mais ensaios, o presente trabalho contribuiu para metodologia de exploração de características de superfície, dispersão e reológicas de suspensões concentradas. / The proposition of the present work is to investigate the hypothesis that the reduction of the surface tension of the liquid favors the rheological behavior of concentrated suspensions, since the particles are closer and the contribution of capillarity forces possibly increases. As concentrated suspensions tend to viscoelastic behavior, rheological methods were examined to analyze possible consequences due to changes of surface tension of the water. Two equivalent calcium carbonates (P1 and P5) were used and differ by particle-size distribution. Two market dispersants and ethylene glycol were used as surfactant. Surface analysis by the zeta potential test revealed positive surface charge and, although the powders are equivalent, the electrophoretic mobility of P5 is lower. The reults show that calcium is potential determining ion. Electrostatic contribution was found only for the dispersants. Pendant drop test showed a decrease in the surface tension of the water with the three additives. Washburn capillary rise technique estimated greater contact angles for tests with additives and lower ones for P5. Rheological geometries and methods were evaluated in order to select good set for viscoelasticity measurements, choosing oscillatory stress sweep and vane geometry. The addition of the dispersants resulted in lower values G \'and yield stress, while ethylene glycol resulted in higher values. There is no clear relation between contact angle and electrophoretic mobility. The rheological and eletrophoretic mobility showed relation only for dispersants. The hypothesis was verified by the values yield stress and IPS. For the dispersants, it was possible to observe behavior close to the hypothesis, the lower the surface tension of the liquid, the lower the yield stress for lower IPS. The hypothesis was also explored by the contact angle tests, a curve next to the hypothesis was observed again. Although the need for more tests, the present work contributed to the methodology of exploration of surface characteristics, dispersion and rheological characteristics of concentrated suspensions.
93

Synthèse et formulation d'encres électrophorétiques pour le papier électronique / Synthesis and formulation of electrophoretic ink for electronic paper applications

Mirbel, Déborah 17 December 2015 (has links)
Au cours de ces travaux de thèse, la synthèse et le comportement électrophorétiquede particules hybrides dispersées en présence d'un nouveau contrôleur de charge, latridodécylamine, en milieu électrophorétique (non-polaire), ont été étudiés pour des applicationsde type papier électronique. Dans le but de contrôler et comprendre les interactions présentesdans ce système, la tridodécylamine a tout d'abord été examinée seule dans le milieu souhaité.Il a été observé que ce tensioactif, solubilisé dans un milieu type huile paraffine, a uneconcentration micellaire critique approximative de 250 mM et apporte des charges dans lemilieu. Ensuite, la synthèse par polymérisation en dispersion ou par voie sol gel a permisd'obtenir des particules inorganiques, polymères ou hybrides type framboise, stables en milieunon-polaire. Leur comportement électrophorétique en présence du nouveau contrôleur decharge a été élucidé. En outre, il a été montré que des interactions acido-basiques avec lesgroupements hydroxyles des pigments inorganiques et le tensioactif donnent des particuleshybrides chargées négativement. Celles-ci ont par la suite été intégrées dans une encreélectrophorétique et testées dans un dispositif prototype innovant, le contrôle del'électrophorèse étant géré via un polymère ferroélectrique. / In this work, the synthesis and the electrophoretic behavior of hybrid particlesdispersed in apolar media, in the presence of a new charge control agent, the tridodecylamine,have been investigated for electronic paper applications. In order to control and to understandinteractions present in the system, the tridodecyamine was studied in the apolar medium. It hasbeen observed that this surfactant, solubilized in a non-polar medium, has a critical micelleconcentration of approximately 250mM and creates charges in the medium. Then, the synthesisby polymerisation in dispersion or by using a sol-gel process gave rise to the creation ofinorganic, polymeric or raspberry type hybrid particles, stable in non-polar media. Theirelectrophoretic behavior in the presence of tridodecylamine was elucidated. Acid-baseinteractions between hydroxyl groups from inorganic material surfaces and surfactant led to thecreation of negatively charged hybrid particles. These particles were integrated into anelectrophoretic ink and tested into an innovative electrophoretic device where theelectrophoresis is monitored via a ferroelectric polymer.
94

Příprava a charakterizace katanionických komplexů / Preparation and characterization of catanionic complexes

Mušková, Alexandra January 2020 (has links)
The diploma thesis deals with the preparation and characterization of catanionic complexes and their possible application to pharmaceutics and medicine. The catanionic complexes were prepared by mixing two oppositely charged surfactants with the concentration of 20 mmol·dm­3 in various volume ratios. Two systems were analyzed – CTAB + SDS and Septonex + SDS. Both systems were prepared in an aqueous and physiological environment. The turbidimetric analyses provided results of the intensity of turbidity of the prepared mixtures. The size and stability of the prepared particles were determined by DLS and ELS measurements. CTAB-rich samples showed significant viscosity changes and they were therefore characterized by rheological measurements. The results of this work show that the asymmetry of alkyl chains, surfactant selection, temperature, and ionic strength have a significant influence on the properties and self-assembly of surfactants in catanionic complexes.
95

Frakcionace a molekulární organizace huminových kyselin / Fractionation and molecular organization of humic acids

Chytilová, Aneta January 2016 (has links)
Humic acids are part of the natural organic matter occurring all around us. The aim of this thesis is to study the molecular organization, conformation of humic acids in aqueous solutions, that always raise a number of questions. For a long time, the scientists all over the world argue, if humic acid are polymers, micelles or supramolecules. Over time, thanks to new technologies, their opinions are moving away from a polymer model and tend rather to supramolecular arrangement of humic acids. Studying humic complex systems is not easy, because they are polydisperse and heterogeneous, which significantly complicates any characterization. Moreover, its molecular organization is affected by many factors such as e.g. pH, ionic strength and etc. For the study of the conformation of humic acids, concentration series of IHSS (International humic substances asociation) Leonardite humic acids stamdards in four different mediums were prepared: 0,1 M NaOH, humic acids in water with pH modified to 12 (basic medium), 0,1 M NaOH + 0,1 M HCl, 0,1 M NaCl (neutral environment). Furthermore it has been performed the fractionation of humic acids for the purpose of simplifying the complicated structure. Prepared concentration series were characterized with several analytical methods such as ultraviolet and visible spectroscopy, dynamic light scattering, electrophoretic light scattering, microrheology, gel permeation chromatography, potentiometric pH determination and direct conductometry. Diploma thesis is built on the previous bachelor thesis in which different sample of humic acids was studied. The measured results indicate that the studied systems show supramolecular behavior and in some cases are subject to aggregation into larger units (micelles).
96

EFFECTS OF SOLUTION COMPOSITION (SALTS, PH, DIELECTRIC CONSTANT) ON POLYELECTROLYTE COMPLEX (PEC) FORMATION AND THEIR PROPERTIES

ZHANG, HUAN January 2018 (has links)
No description available.
97

The Electrophoretic Deposition of Conjugated Polymer Functionalized Carbon Nanotubes for Photovoltaic Applications

Casagrande, Travis V. 10 1900 (has links)
<p><p lang="en-US">This experimental research thesis describes the combination of conjugated polymers and carbon nanotubes with the fields of electrophoretic deposition (EPD) and organic solar cells. Prior to these contributions, soluble conjugated polymers and carbon nanotubes that have been functionalized by them had not yet been deposited by EPD from solution or by using non-toxic solvents. Additionally, EPD had not yet been utilized to deposit the active layer in a solid organic photovoltaic device. <p lang="en-US">The EPD of soluble conjugated polymer functionalized carbon nanotubes from non-toxic solvents was achieved through an iterative process of experimentation and technique refinement. The developed EPD technique utilized the high pH region at the cathode substrate to neutralize positively charged weak polyelectrolytes macromolecules. Their functional groups were protonated using a minimized amount of acetic acid which also enabled their solubility. Deprotonation of the quaternary ammonium functional groups rendered them neutrally charged and insoluble tertiary amines. This mechanism facilitated the formation of coatings that were predictable and uniform in appearance and thickness. <p lang="en-US">Control over coating thickness was demonstrated by coatings spanning 100 nm to 10 μm. These coatings were produced by adjusting the applied voltage, solution concentration, and tuning the deposition duration. <p lang="en-US">Techniques for the fabrication of a photovoltaic device using an active layer produced by EPD were established though modifications of general organic photovoltaic device fabrication procedures. These modifications involved redesigning the photolithographic ITO etching pattern, adding an insulating barrier strip, thickening the aluminum electrode layer, and switching the top buffer layer from LiF to BCP.</p> / Master of Applied Science (MASc)
98

Caractérisation de petits ions, de (bio)macromolécules et de nanoparticules par les méthodes électrophorétiques : charge effective et dépendance de la mobilité électrophorétique en force ionique / Characterization of small ions, (bio)macromolecules and nanoparticles by electrophoretic methods : effective charge and ionic strength dependence of the electrophoretic mobility

Ibrahim, Amal 07 December 2012 (has links)
L'objectif principal de cette thèse a été d'étudier et de développer les méthodes électrophorétiques pour la détermination de la charge effective de petits ions, de (bio)macromolécules et de nanoparticules. En effet, la charge effective est un paramètre physico-chimique qui contrôle les interactions électrostatiques et qui permet d'accéder aux taux de condensation des contre-ions dans le cas de polyélectrolytes. Dans une première partie, différents modèles sur la mobilité électrophorétique (Nernst-Einstein, O'Brien-White-Ohshima, Yoon-Kim) ont été comparés pour la détermination de la charge effective à partir des valeurs expérimentales de mobilité électrophorétique et de rayon hydrodynamique. Trois autres méthodes expérimentales basées sur la sensibilité de détection UV en mode indirect, sur la sensibilité de détection en conductimétrie et sur la longueur des zones isotachophorétiques ont été étudiées. Ces méthodes ont été appliquées en particulier à la détermination de la charge effective de dendrimères greffés de la lysine et de polymères utilisés en délivrance de principe actif.Une étude du comportement électrophorétique en fonction de la force ionique nous a mené à proposer une représentation graphique, appelée « slope-plot », permettant de distinguer les solutés en fonction de leur nature (petits ions, polyélectrolytes, nanoparticules). Cette représentation peut s'avérer très utile pour l'optimisation des séparations en électrophorèse capillaire en fonction de la force ionique. / The main objective of this thesis was to study and develop electrophoretic methods for effective charge determination of small ions, (bio)macromolecules and nanoparticles. Effective charge is a physical parameter that controls the electrostatic interactions and allows for the determination of condensed counter-ion fraction in the case of polyelectrolytes. In a first part, different models of electrophoretic mobility (Nernst-Einstein, O'Brien-White-Ohshima, Yoon-Kim) have been compared for effective charge determination from experimental values of electrophoretic mobility and hydrodynamic radius. Three other experimental methods based on the sensitivity of UV detection in indirect mode and in conductivity detection, or on the length of the isotachophoretic zones, were studied. These methods were applied to effective charge determination of dendrigraft poly-L-lysines and on drug delivery polymeric systems. A study of the ionic strength dependence of the electrophoretic mobility leads us to propose a graphical representation, called the slope-plot, allowing for the distinction between solutes according to their nature (small ions, polyelectrolytes, nanopaticles). The slop-plot can also be used for the optimization of electrophoretic separations according to the ionic strength.
99

Síntese e caracterização de eletrodos de TiO2/WO3, nanotubos de TiO2/WO3 e nanotubos de TiO2/titanato para aplicação no tratamento fotoeletrocatalítico dos interferentes endócrinos bisfenol-A e propil / Synthesis and characterization of TiO2/ WO3, TiO2 nanotubes/WO3 and TiO2 nanotubes/titanate electrodes for application in the photoelectrocatalytic treatment of the endocrine desruptors bisphenol-A and propylparaben

Alysson Stefan Martins 26 October 2017 (has links)
Tecnologias efetivas para o tratamento de águas e efluentes representam um dos grandes desafios da nossa sociedade; dentre as opções, a fotoeletrocatálise pode ser considerada como uma técnica alternativa e de interesse. Nesse contexto, o presente trabalho teve como objetivo desenvolver eletrodos de TiO2 modificados visando o tratamento fotoeletrocatalítico de interferentes endócrinos. Realizou-se inicialmente a síntese de nanotubos de TiO2 (TiO2-NT) sobre substrato de Ti metálico via anodização eletroquímica em eletrólito NaH2PO4/HF. Para minimizar as limitações inerentes ao TiO2 realizou-se a eletrodeposição de WO3 sobre os nanotubos de TiO2 (Ti/TiO2-NT/WO3) e diretamente sobre o substrato de Ti metálico. Este último revelou a formação de uma camada fina de TiO2 sobre a superfície, posterior ao tratamento térmico, formando um compósito (Ti/TiO2/WO3). A análise de difração de raios-X confirmou a formação da fase monoclínica de WO3 para ambas as sínteses e a fase anatase para os eletrodos de Ti/TiO2-NT/WO3. Para as duas sínteses, as medidas de energia dispersiva de raios-X revelaram uma quantidade crescente de W na composição dos eletrodos com o aumento do tempo de eletrodeposição. Teores elevados de W (acima de 1,2 %) apresentaram uma diminuição expressiva nos valores de fotocorrente. No entanto, baixos teores de W (entre 0,4 e 1,2 %) indicaram um aumento de 20 % nos valores de fotocorrente para os eletrodos de Ti/TiO2-NT/WO3 (20 mA cm-2) e Ti/TiO2/WO3 (17 mA cm-2) comparados aos não modificados, no potencial de +2,0 V. As análises de reflectância difusa mostraram uma baixa energia de bandgap (&asymp; 2,90 eV, eletrodos de Ti/TiO2-NT/WO3) e um aumento na absorção da irradiação UV-Vis. Posteriormente, os eletrodos modificados foram aplicados na oxidação fotoeletrocatalítica (FE) dos compostos bisfenol-A (BPA) e propilparabeno (PPB), sob irradiação UV-Vis. O método FE apresentou um excelente desempenho em condições ácidas, aplicando-se potencial de +1,50 V e +0,50 V para os eletrodos Ti/TiO2-NT/WO3 e Ti/TiO2/WO3, respectivamente. A mineralização dos compostos BPA e PPB foi superior a 80 % tanto para o Ti/TiO2-NT/WO3 como para o Ti/TiO2/WO3. Quanto à taxa de remoção, o BPA e PPB foram completamente removidos após 45 e 60 min, respectivamente, para os eletrodos de Ti/TiO2/WO3 e após 30 minutos para os eletrodos de Ti/TiO2-NT/WO3. Adicionalmente, os eletrodos apresentaram um baixo consumo energético e boa estabilidade química. Comparada à técnica de fotocatálise (FC), a FE revelou uma eficiência de mineralização 2 vezes superior para o Ti/TiO2-NT/WO3 e mais de 20 % superior para o Ti/TiO2/WO3. Logo, as modificações dos eletrodos de TiO2 com WO3 constituíram importantes contribuições para o desempenho dos materiais, sendo um passo importante para a aplicação em tratamentos alternativos de descontaminação de águas residuárias. Ainda foi de interesse neste trabalho propor um método para a inserção de nanotubos (TiNT) e nanofolhas (TiNS) de titanatos no interior de nanotubos de TiO2 via eletroforese. O estudo possibilitou o desenvolvimento de um método simples e eficiente para a modificação de nanoestruturas complexas. A movimentação do contra eletrodo sobre a superfície do eletrodo de trabalho, adaptado com uma escova nas laterais, reduziu a espessura da camada de TiNS/TiNT. O potencial aplicado (20 V) e a estimulação mecânica da superfície foram importantes para a incorporação das nanoestruturas dentro dos poros de TiO2-NTs. Como resultado, os eletrodos apresentaram um aumento da hidrofobicidade e uma melhora na capacidade de oxidação direta comparado ao eletrodo não modificado. / Effective technologies for the water and wastewater treatment represent a challenges for our society; among the options, the photoelectrocatalysis can be considered a promising and interesting alternative. In this context, the objective of this study was to develop modified TiO2 electrodes for the photoelectrocatalytic treatment of endocrine disruptors. The synthesis of TiO2 nanotubes (TiO2-NT) on metallic Ti substrate was carried out via electrochemical anodization in NaH2PO4 /HF electrolyte. In order to minimize the limitations inherent of TiO2, the electrodeposition of WO3 was performed on the TiO2 nanotubes (Ti/TiO2-NT/WO3) and also in the metallic Ti substrate. The deposition on the Ti metallic produced a thin layer of TiO2 on the surface, subsequent to the heat treatment, generating a composite (Ti/TiO2/WO3). The X-ray diffraction analysis (XRD) confirmed the monoclinic phase of WO3 for both the syntheses and the anatase phase of TiO2 for the Ti/TiO2-NT/WO3 electrodes. For the two syntheses, the X-ray dispersive energy (EDX) analisys indicated an increasing amount of tungsten (W) in the composition of the electrodes with increasing of electrodeposition time. High W content (above 1.2%) showed a significant decrease in the photocurrent values. However, low content of W (between 0.4 and 1.2 %) indicated an increase of 20 % in the photocurrent values for the electrodes Ti/TiO2-NT/WO3 (20 mA cm-2) and Ti/TiO2/WO3 (17 mA cm-2) compared to the unmodified ones, at the potential of +2.0 V. Difuse reflectance analysis indicated low bandgap energy (&asymp; 2.90 eV, Ti/TiO2-NT/WO3 electrodes) and an increase in the UV-Vis irradiation absorption. The best electrodes modified with WO3 to the both syntheses were applied in the photoelectrocatalytic oxidation (PEC) of bisphenol-A (BPA) and propylparaben (PPB) compounds, under UV-Vis irradiation. The PEC method presented an excellent performance in acidic conditions, applying a bias potential of +1.50 V and +0.50 V for Ti/TiO2-NT/WO3 and Ti/TiO2/WO3 electrodes, respectively. The mineralization of BPA and PPB compounds was greater than 80% for both Ti/TiO2-NT/WO3 and Ti/TiO2/WO3. In relation to the removal rate, BPA and PPB were completely removed after 45 and 60 min, respectively, for Ti/TiO2/WO3 electrodes and after 30 minutes for Ti/TiO2-NT/WO3 electrodes. Additionally, the electrodes presented a low energy consumption and good chemical stability. Compared to the photocatalysis (PC), the PEC was 2 times higher to the mineralization efficiency for Ti/TiO2-NT/WO3 and almost 20% higher for Ti/TiO2/WO3. Thus, the modifications of the TiO2 electrodes with WO3 represent an important contribution to the performance of materials and, therefore, a positive step for the application in alternative treatments of decontamination of wastewater. It was also of interest in this work to propose a new method for the insertion of nanotubes (TiNT) and nanosheets (TiNS) of titanates inside of TiO2 nanotubes via electrophoretic deposition. In this study was developed a simple and efficient method for the modification of complex nanostructures. The movement of the counter electrode on the surface of the working electrode, adapted with a brush on the edges, reduced the thickness of the TiNS/TiNT layer. The potential applied (20 V) and the mechanical stimulation in the surface were important for the incorporation of TiNS/TiNT into the pores of TiO2-NTs. As a result, the electrodes increased the hydrophobicity and an improvement to the direct oxidation capacity compared to the unmodified electrode.
100

Síntese e caracterização de eletrodos de TiO2/WO3, nanotubos de TiO2/WO3 e nanotubos de TiO2/titanato para aplicação no tratamento fotoeletrocatalítico dos interferentes endócrinos bisfenol-A e propil / Synthesis and characterization of TiO2/ WO3, TiO2 nanotubes/WO3 and TiO2 nanotubes/titanate electrodes for application in the photoelectrocatalytic treatment of the endocrine desruptors bisphenol-A and propylparaben

Martins, Alysson Stefan 26 October 2017 (has links)
Tecnologias efetivas para o tratamento de águas e efluentes representam um dos grandes desafios da nossa sociedade; dentre as opções, a fotoeletrocatálise pode ser considerada como uma técnica alternativa e de interesse. Nesse contexto, o presente trabalho teve como objetivo desenvolver eletrodos de TiO2 modificados visando o tratamento fotoeletrocatalítico de interferentes endócrinos. Realizou-se inicialmente a síntese de nanotubos de TiO2 (TiO2-NT) sobre substrato de Ti metálico via anodização eletroquímica em eletrólito NaH2PO4/HF. Para minimizar as limitações inerentes ao TiO2 realizou-se a eletrodeposição de WO3 sobre os nanotubos de TiO2 (Ti/TiO2-NT/WO3) e diretamente sobre o substrato de Ti metálico. Este último revelou a formação de uma camada fina de TiO2 sobre a superfície, posterior ao tratamento térmico, formando um compósito (Ti/TiO2/WO3). A análise de difração de raios-X confirmou a formação da fase monoclínica de WO3 para ambas as sínteses e a fase anatase para os eletrodos de Ti/TiO2-NT/WO3. Para as duas sínteses, as medidas de energia dispersiva de raios-X revelaram uma quantidade crescente de W na composição dos eletrodos com o aumento do tempo de eletrodeposição. Teores elevados de W (acima de 1,2 %) apresentaram uma diminuição expressiva nos valores de fotocorrente. No entanto, baixos teores de W (entre 0,4 e 1,2 %) indicaram um aumento de 20 % nos valores de fotocorrente para os eletrodos de Ti/TiO2-NT/WO3 (20 mA cm-2) e Ti/TiO2/WO3 (17 mA cm-2) comparados aos não modificados, no potencial de +2,0 V. As análises de reflectância difusa mostraram uma baixa energia de bandgap (&asymp; 2,90 eV, eletrodos de Ti/TiO2-NT/WO3) e um aumento na absorção da irradiação UV-Vis. Posteriormente, os eletrodos modificados foram aplicados na oxidação fotoeletrocatalítica (FE) dos compostos bisfenol-A (BPA) e propilparabeno (PPB), sob irradiação UV-Vis. O método FE apresentou um excelente desempenho em condições ácidas, aplicando-se potencial de +1,50 V e +0,50 V para os eletrodos Ti/TiO2-NT/WO3 e Ti/TiO2/WO3, respectivamente. A mineralização dos compostos BPA e PPB foi superior a 80 % tanto para o Ti/TiO2-NT/WO3 como para o Ti/TiO2/WO3. Quanto à taxa de remoção, o BPA e PPB foram completamente removidos após 45 e 60 min, respectivamente, para os eletrodos de Ti/TiO2/WO3 e após 30 minutos para os eletrodos de Ti/TiO2-NT/WO3. Adicionalmente, os eletrodos apresentaram um baixo consumo energético e boa estabilidade química. Comparada à técnica de fotocatálise (FC), a FE revelou uma eficiência de mineralização 2 vezes superior para o Ti/TiO2-NT/WO3 e mais de 20 % superior para o Ti/TiO2/WO3. Logo, as modificações dos eletrodos de TiO2 com WO3 constituíram importantes contribuições para o desempenho dos materiais, sendo um passo importante para a aplicação em tratamentos alternativos de descontaminação de águas residuárias. Ainda foi de interesse neste trabalho propor um método para a inserção de nanotubos (TiNT) e nanofolhas (TiNS) de titanatos no interior de nanotubos de TiO2 via eletroforese. O estudo possibilitou o desenvolvimento de um método simples e eficiente para a modificação de nanoestruturas complexas. A movimentação do contra eletrodo sobre a superfície do eletrodo de trabalho, adaptado com uma escova nas laterais, reduziu a espessura da camada de TiNS/TiNT. O potencial aplicado (20 V) e a estimulação mecânica da superfície foram importantes para a incorporação das nanoestruturas dentro dos poros de TiO2-NTs. Como resultado, os eletrodos apresentaram um aumento da hidrofobicidade e uma melhora na capacidade de oxidação direta comparado ao eletrodo não modificado. / Effective technologies for the water and wastewater treatment represent a challenges for our society; among the options, the photoelectrocatalysis can be considered a promising and interesting alternative. In this context, the objective of this study was to develop modified TiO2 electrodes for the photoelectrocatalytic treatment of endocrine disruptors. The synthesis of TiO2 nanotubes (TiO2-NT) on metallic Ti substrate was carried out via electrochemical anodization in NaH2PO4 /HF electrolyte. In order to minimize the limitations inherent of TiO2, the electrodeposition of WO3 was performed on the TiO2 nanotubes (Ti/TiO2-NT/WO3) and also in the metallic Ti substrate. The deposition on the Ti metallic produced a thin layer of TiO2 on the surface, subsequent to the heat treatment, generating a composite (Ti/TiO2/WO3). The X-ray diffraction analysis (XRD) confirmed the monoclinic phase of WO3 for both the syntheses and the anatase phase of TiO2 for the Ti/TiO2-NT/WO3 electrodes. For the two syntheses, the X-ray dispersive energy (EDX) analisys indicated an increasing amount of tungsten (W) in the composition of the electrodes with increasing of electrodeposition time. High W content (above 1.2%) showed a significant decrease in the photocurrent values. However, low content of W (between 0.4 and 1.2 %) indicated an increase of 20 % in the photocurrent values for the electrodes Ti/TiO2-NT/WO3 (20 mA cm-2) and Ti/TiO2/WO3 (17 mA cm-2) compared to the unmodified ones, at the potential of +2.0 V. Difuse reflectance analysis indicated low bandgap energy (&asymp; 2.90 eV, Ti/TiO2-NT/WO3 electrodes) and an increase in the UV-Vis irradiation absorption. The best electrodes modified with WO3 to the both syntheses were applied in the photoelectrocatalytic oxidation (PEC) of bisphenol-A (BPA) and propylparaben (PPB) compounds, under UV-Vis irradiation. The PEC method presented an excellent performance in acidic conditions, applying a bias potential of +1.50 V and +0.50 V for Ti/TiO2-NT/WO3 and Ti/TiO2/WO3 electrodes, respectively. The mineralization of BPA and PPB compounds was greater than 80% for both Ti/TiO2-NT/WO3 and Ti/TiO2/WO3. In relation to the removal rate, BPA and PPB were completely removed after 45 and 60 min, respectively, for Ti/TiO2/WO3 electrodes and after 30 minutes for Ti/TiO2-NT/WO3 electrodes. Additionally, the electrodes presented a low energy consumption and good chemical stability. Compared to the photocatalysis (PC), the PEC was 2 times higher to the mineralization efficiency for Ti/TiO2-NT/WO3 and almost 20% higher for Ti/TiO2/WO3. Thus, the modifications of the TiO2 electrodes with WO3 represent an important contribution to the performance of materials and, therefore, a positive step for the application in alternative treatments of decontamination of wastewater. It was also of interest in this work to propose a new method for the insertion of nanotubes (TiNT) and nanosheets (TiNS) of titanates inside of TiO2 nanotubes via electrophoretic deposition. In this study was developed a simple and efficient method for the modification of complex nanostructures. The movement of the counter electrode on the surface of the working electrode, adapted with a brush on the edges, reduced the thickness of the TiNS/TiNT layer. The potential applied (20 V) and the mechanical stimulation in the surface were important for the incorporation of TiNS/TiNT into the pores of TiO2-NTs. As a result, the electrodes increased the hydrophobicity and an improvement to the direct oxidation capacity compared to the unmodified electrode.

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