Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2016-01-06T17:51:26Z No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) Disserta??o Completa Times New Roman - Com Assinatura da Ban.pdf: 4476480 bytes, checksum: 309e034f51cd7605224651743ecee1cd (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2016-01-07T12:06:06Z (GMT) No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) Disserta??o Completa Times New Roman - Com Assinatura da Ban.pdf: 4476480 bytes, checksum: 309e034f51cd7605224651743ecee1cd (MD5) / Made available in DSpace on 2016-01-07T12:06:06Z (GMT). No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) Disserta??o Completa Times New Roman - Com Assinatura da Ban.pdf: 4476480 bytes, checksum: 309e034f51cd7605224651743ecee1cd (MD5) Previous issue date: 2012 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (Capes) / Filmes finos de di?xido de estanho dopados com antim?nio foram confeccionados pelo m?todo de deposi??o t?rmica sobre micro tela de a?o ASTM 316 objetivando a confec??o de anodos perme?veis a fluido para uso em reatores filtro-prensa. Os ?xidos nas formas de filmes suportados e de p? foram investigados pelas t?cnicas de energia dispersiva de raios-X (EDX), difratometria de raios-X (DRX) e microscopia eletr?nica de varredura (MEV). O estudo de EDX revelou que a raz?o efetiva Sb/Sn nos filmes ? maior que a nominal, enquanto que o DRX revelou que o SnO2 est? presente na forma da estrutura da cassiterita, que n?o h? presen?a de picos relacionados a ?xidos de antim?nio e que o aumento da concentra??o de Sb leva a uma diminui??o da cristalinidade dos filmes. O estudo de MEV revelou que os filmes apresentam estrutura compacta e n?o-porosa. A caracteriza??o eletroqu?mica dos anodos 316/Sb-SnO2 conduzida numa c?lula do tipo eletr?lito polim?rico s?lido (EPS) empregando-se a membrana Nafion? 117 da Dupont revelou a partir da voltametria c?clica e das curvas de polariza??o que o sobrepotencial para a rea??o de desprendimento de oxig?nio (RDO) aumenta com a concentra??o de antim?nio. O estudo envolvendo a an?lise da durabilidade dos anodos conduzido em condi??es galvanost?ticas (20 mA cm-2) revelou que a vida ?til do anodo aumenta com a concentra??o de Sb passando por um ponto de m?ximo. O anodo 316/Sb-SnO2 alojado em c?lula do tipo EPS na condi??o de ?zero-gap? e na aus?ncia de eletr?litos l?quidos foi aplicado na degrada??o eletroqu?mica do corante t?xtil Cibacron? Marinho F-4G considerado como poluente modelo. A cin?tica de descolora??o seguiu o modelo de pseudo-primeira ordem representativo do controle difusional atrav?s da microestrutura do ?nodo sob influ?ncia da turbul?ncia causada pelo desprendimento de oxig?nio. Foi verificada uma descolora??o superior a 90% e uma degrada??o do composto parental maior que 50% ap?s 3,5 h de eletr?lise. A an?lise das curvas cronopotenciom?tricas indicou que a desativa??o dos anodos ? fortemente influenciada pela disponibilidade dos radicais hidroxilas adsorvidos na superf?cie do eletrodo. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2012. / ABSTRACT Thin films of tin dioxide doped with antimony were prepared by the thermal decomposition method onto a stainless steel fine mesh (ASTM 316) in order to obtain a fluid permeable anode for application in filter-press reactors. Films and powders of Sb-SnO2 were investigated using the energy dispersive X-ray (EDX), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The EDX revealed that the effective Sb/Sn molar ratio in films is greater than the nominal composition, while the XRD has revealed that SnO2 is present in the crystalline form of the cassiterite structure. In addition, it was verified the absence of peaks accounted for the antimony oxides even for higher amounts of Sb, while the addition of Sb lead to a decrease in the film crystallinity. SEM images showed that the thin films are rather compact. The electrochemical characterization of the fluid permeable anode composed of 316/Sb-SnO2 was carried out in an SPE cell using the Nafion? 117 membrane as the electrolyte. Cyclic voltammograms and polarization curves showed the overpotential for the oxygen evolution reaction (OER) increases upon increasing the antimony concentration. The endurance test carried out under galvanostatic conditions (20 mA cm-2) has revealed that the anode service life increases upon increasing the Sb concentration passing through a maximum. The 316/Sb-SnO2 anode housed in an SPE cell in the zero-gap condition and in the absence of liquid electrolytes was applied on degradation of the Cibacron? Marinho F-4G dye, considered as the pollutant model. Discoloration kinetics was described by the pseudo-first order model describing the diffusion control across the anode microstructure under the influence of the turbulence caused by the OER. A discoloration percentage higher than 90% and a degradation percentage of the parental compound greater than 50% were both achieved after 3.5 h of electrolysis. Analysis of the chronopotentiometric curves indicated the anode deactivation is considerable effected by the availability of the hydroxyl radicals adsorbed on the anode surface.

Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-19T13:34:45Z No. of bitstreams: 5 fab.pdf: 3600092 bytes, checksum: 62e73afe3033394e17b7ea0fbf24fbf8 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2015-02-20T10:44:39Z (GMT) No. of bitstreams: 5 fab.pdf: 3600092 bytes, checksum: 62e73afe3033394e17b7ea0fbf24fbf8 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) / Made available in DSpace on 2015-02-20T10:44:39Z (GMT). No. of bitstreams: 5 fab.pdf: 3600092 bytes, checksum: 62e73afe3033394e17b7ea0fbf24fbf8 (MD5) license_url: 52 bytes, checksum: 3d480ae6c91e310daba2020f8787d6f9 (MD5) license_text: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) license.txt: 2110 bytes, checksum: b4c884761e4c6c296ab2179d378436d4 (MD5) Previous issue date: 2013-02-20 / Eletrodos perme?veis a fluidos (EPF) foram confeccionados mediante a eletrodeposi??o do di?xido de chumbo (PbO2) sobre substratos constitu?dos de tecido de carbono (TC) do tipo sarja empregando-se diferentes condi??es experimentais. Foi investigada a influ?ncia dos diferentes tipos de pr?-tratamento do TC na eletross?ntese dos filmes de PbO2. Os substratos pr?-tratados foram caracterizados empregando-se a t?cnica de voltametria c?clica (VC), enquanto que os filmes de PbO2 suportados sobre o TC pr?-tratado foram caracterizados pelas t?cnicas de difratometria de raios-X (DRX), microscopia ?tica (MO), microscopia eletr?nica de varredura (MEV), e a voltametria. Foi verificado que o pr?-tratamento do TC empegando-se o isopropanol ? o mais apropriado para a eletross?ntese dos filmes de PbO2 visando a obten??o de um EPF. O estudo de caracteriza??o ?ex-situ? (DRX, MO e MEV) revelou que as condi??es experimentais mais satisfat?rias para a forma??o da fase ?-PbO2 sobre o TC pr?-tratado, de modo a se obter um EPF, s?o: pH ? 2; 40 oC ? T < 70 oC, e 40 mA cm-2. O comportamento eletroqu?mico do EPF (TC/?-PbO2) foi investigado na condi??o de ?zero-gap? empregando-se a membrana Nafion? 117 (DuPont) como eletr?lito s?lido e a ?gua destilada como fase l?quida. A an?lise das curvas de polariza??o registradas em condi??es quase-estacion?rias para o processo eletr?dico misto da rea??o de desprendimento de oxig?nio (RDO) acompanhada pela rea??o de forma??o de oz?nio (RFO) revelou a presen?a de duas inclina??es de Tafel distribu?das nos dom?nios dos baixos e dos altos sobrepotenciais. Foi obtido um valor de 16 kJ mol-1 para a entalpia de ativa??o aparente determinada no dom?nio dos elevados sobrepotenciais. O estudo envolvendo a quantifica??o do oz?nio produzido com o anodo do tipo TC/?-PbO2 empregando-se um prot?tipo de reator do tipo filtro-prensa revelou que este tipo de EPF n?o ? adequado para o processo da produ??o eletroqu?mica de oz?nio. Entretanto, a grande estabilidade qu?mica e mec?nica apresentada pelo TC/?-PbO2 aliada ao seu grande sobrepotencial para o processo da RDO permite inferir que reatores do tipo filtro-prensa empregando-se este tipo de anodo s?o bastante promissores para processos de interesse ambiental envolvendo a combust?o de poluentes org?nicos presentes em ?guas. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2011. / ABSTRACT Electrodes permeable to fluids (EPF) were fabricated by electrodeposition of lead dioxide (PbO2) on substrates made of twill type woven carbon (TC) using different experimental conditions. There has been investigated the influence of the different types of pre-treatment on TC in the electrosynthesis of PbO2 films. The pretreated substrates were characterized using the technique of cyclic voltammetry (VC), while the PbO2 films supported on pre-treated TC were characterized by the techniques of X-ray diffraction (DRX), optical microscopy (MO), scanning electron microscopy (MEV) and voltammetry. It was observed that the pre-treatment of TC using isopropanol is the most suitable electrosynthesis of PbO2 films for obtaining an EPF. The characterization study "ex-situ" (DRX, MO e MEV)) revealed that the experimental conditions more suitable for the formation of phase ?-PbO2 on the TC pre-treated in order to obtain an EPF, are pH ? 2; 40 oC ? T < 70 oC, e 40 mA cm-2. The electrochemical behavior of EPF (TC/?-PbO2) was investigated in the condition of "zero-gap" employing the Nafion? 117 membrane (DuPont) as solid electrolyte and distilled water as the liquid phase. The analysis of polarization curves recorded in quasi-stationary conditions for the mix electrode process of from the mixture of oxygen detachment reaction (RDO) accompanied by the reaction of ozone formation (RFO) has revealed the presence of two Tafel slopes distributed in the areas of low and high overpotentials. There was obtained a value of 16 kJ mol-1 for the apparent activation enthalpy determined in the field of high overpotentials. The study involving the measurement of ozone produced in the anode-type TC/?-PbO2 employing a prototype reactor of the filter-press revealed that this type of EPF is not suitable for the process of electrochemical production of ozone. However, the high chemical and mechanical stability provided by the TC/?-PbO2 combined with its large overpotential for the process of RDO allows to infer that reactors of filter-press employing this type of anode are very promising for processes of environmental interest involving the combustion of organic pollutants in waste water.