Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-03-08T18:31:35Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) jose_geraldo_mendes_castro_junior.pdf: 20723597 bytes, checksum: f867ab4f1cb9235c24c8c6d16d42c22c (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-03-09T18:46:17Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) jose_geraldo_mendes_castro_junior.pdf: 20723597 bytes, checksum: f867ab4f1cb9235c24c8c6d16d42c22c (MD5) / Made available in DSpace on 2018-03-09T18:46:17Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) jose_geraldo_mendes_castro_junior.pdf: 20723597 bytes, checksum: f867ab4f1cb9235c24c8c6d16d42c22c (MD5) Previous issue date: 2017 / Eletrodos de di?xido de chumbo (PbO2) suportados sobre tecido de carbono e tela de a?o inoxid?vel foram utilizados na degrada??o eletroqu?mica dos f?rmacos paracetamol (PCT) e dipirona (DPN), utilizando-se uma c?lula eletroqu?mica do tipo eletr?lito polim?rico s?lido (EPS) munida de eletrodos perme?veis a fluidos (EPFs). Todos os estudos foram conduzidos na condi??o de batelada empregando-se a ?gua livre de eletr?litos. Os estudos eletroqu?micos de degrada??o dos f?rmacos foram conduzidos em fun??o da densidade de corrente aparente (jap) (ex., 5, 10, 20, 100, 150 e 200 mA cm-2) e da concentra??o inicial (ex., 10, 30 e 50 mg L 1). As amostras tratadas foram analisadas pelas t?cnicas de espectrofotometria na regi?o do UVVis, cromatografia l?quida de alta efici?ncia (CLAE) e demanda qu?mica de oxig?nio (DQO). Verificou-se para os diferentes casos envolvendo as baixas densidades de corrente que a remo??o das bandas de absor??o no UV-Vis, a remo??o da concentra??o dos f?rmacos (CLAE) e a redu??o da DQO (grau de mineraliza??o) n?o foram significativos. Contrariamente, no caso das elevadas densidades de corrente evidenciou-se uma significante melhora na degrada??o dos f?rmacos em decorr?ncia da atua??o do oz?nio gerado eletroquimicamente. Os melhores resultados foram obtidos para baixas concentra??es dos f?rmacos. Redu??es superiores a 95 % de DQO para o PCT e superiores a 75 % para a DPN foram obtidas. Eletrodos de PbO2 dopados com n?quel (ex., Ni-PbO2) suportados sobre tecido de carbono e tela de a?o inoxid?vel foram confeccionados e caracterizados. A an?lise de microscopia eletr?nica de varredura (MEV) revelou o aparecimento de defeitos superficiais, com a varia??o da concentra??o nominal do Ni no banho eletrol?tico utilizado no preparo do eletrodo por eletrodeposi??o. An?lises de difratometria de raios-X (DRX) corroboraram os resultados de MEV revelando, em alguns casos, picos mais alargados e de menor intensidade (ex., redu??o no tamanho m?dio dos cristalitos) com a varia??o da concentra??o nominal do Ni, indicando assim uma interfer?ncia no processo de eletrodeposi??o do PbO2. Curvas de polariza??o em condi??es quaseestacion?rias foram obtidas para o processo eletr?dico da rea??o de desprendimento de oxig?nio (RDO) sendo verificado que n?o houve influ?ncia significativa do dopante sobre esta rea??o, a qual ocorre em paralelo ao processo de degrada??o oxidativa dos f?rmacos. Verificou-se que a produ??o de oz?nio foi ligeiramente favorecida em algumas concentra??es do dopante e em altas densidades de corrente. No entanto, n?o foi verificada influ?ncia significativa sobre o grau de mineraliza??o dos f?rmacos PCT e DPN mediante uso de eletrodos dopados com Ni. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / Lead dioxide (PbO2) electrodes supported on carbon cloth and stainless-steel mesh substrates were used in the electrochemical degradation of the drugs paracetamol (PCT) and dipyrone (DPN), using a solid polymer electrolyte electrochemical cell (SPE) having fluid-permeable electrodes (FPEs). All studies were conducted in batch condition using the electrolyte-free water. The electrochemical degradation of the drugs was accomplished as a function of the apparent current density (ex., 5, 10, 20, 100, 150 and 200 mA cm-2) and the initial concentration (ex., 10, 30 and 50 mg L-1). The treated samples were analyzed using the UV-Vis spectrophotometry technique, the high-performance liquid chromatography (HPLC), as well as the chemical oxygen demand (COD). For the different cases involving the application of low current density values, it was not verified significant changes accounting for the removal of the UV-Vis absorption band, the drug concentration (HPLC), and the COD decrease (ex., the degree of mineralization). In contrast, in the case of high current densities, a significant improvement in the degradation of the drugs was evidenced as a result of the influence of the electrochemically generated ozone. The best findings were obtained for low drug concentrations. Reductions of above 95% COD for PCT and above 75% for DPN were obtained. Nickel-doped PbO2 electrodes (ex., Ni-PbO2) supported on carbon cloth and stainlesssteel mesh were fabricated and characterized. Scanning electron microscopy (SEM) revealed the appearance of surface defects with a reduction in crystal size with the different Ni concentration in the electrolytic bath used to prepare the electrode by electrodeposition. X-ray diffraction (XRD) analyzes corroborated with the SEM results revealing the formation of broader peaks with lower intensity, in some cases, (ex., reduction in the average crystallite size) with the variation of the nominal dopant concentration in the electrolytic bath, thus indicating an interference in the electrodeposition process for PbO2. Quasi-stationary polarization curves were obtained for the electrode process of the oxygen evolution reaction (OER) and it was verified that there was no significant influence of the dopant on this reaction, which occurs in parallel to the process comprising the oxidative degradation of the drugs. It was found that the ozone generation was slightly favored in some concentrations of the dopant and in higher current densities. However, no significant influence was verified on the degree of mineralization of PCT and DPN by the use of Ni-PbO2 electrodes.

Holographic sensors are photonic layered structures contained in analyte sensitive lms that upon illumination produce monochromatic reflections (λ). The present work reports the fabrication of oxygen and ammonia sensors in Nafi on membranes and hydrocarbon and volatile organic compound sensors in poly(dimethylsiloxane) (PDMS) films. A holographic recording technique was developed to suit these materials consisting of the in situ formation of nanoparticles of 18nm average diameter and their subsequent ordered ablation with a 300mJ laser. The wavelength of the monochromatic reflections depends principally on the refractive index of the resulting layers (n) and the separation between them (Λ). Changes in these parameters are generated by the analyte-sensor interactions and their magnitude can be correlated to the analyte concentration. The strength of these interactions is determined by the thermodynamic properties of the analytes, such as the cohesive energy density (δ^2), and this, was coupled with a photonic model for the prediction of the holographic response. After exposure to different concentrations of the analytes, the kinetics of the responses were determined and the lowest detection limits (LDL) established as follows: Hydrocarbons in PDMS holograms 1% (v/v) in 3s for a range of concentrations from 0-100%; ammonia in Nafi on holograms 0.16% in 100s in the 0-12.5% range; the LDL for oxygen sensing could not be determined although the response was recorded down to 12.5% and up to 100% in 100s. Holographic sensors show competitive responses comparable to commercially available gas sensors for biomedical diagnostics and industrial process monitoring because of their facile fabrication and their shared sensing platform allowing multiplexing.

No description available.

No description available.

No description available.

No description available.

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

Two new bis(perfluoroalkyl)arylsulfonyl imide monomers, which contain the aryl diazonium moiety and intramolecular zwitterionic fragment, have been designed and prepared for the first time from perfluoro(3-oxa-4-pentene)sulfonyl fluoride. As promising monomer candidates for high-performance proton exchange membrane fuel cell electrolytes, these two monomers have furnished perfluorinated electrolytes that include the polymers from perfluorinated sulfonic acid or perfluorinated sulfonimide monomers. The synthesis strategies and NMR analysis are summarized and discussed in details.

No description available.

No description available.