Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-14T21:09:10Z No. of bitstreams: 1 JessicaPiresDePaivaBarreto_DISSERT.pdf: 1801241 bytes, checksum: b708db5acf9b75298b27ebb0f7e739f1 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-15T21:37:25Z (GMT) No. of bitstreams: 1 JessicaPiresDePaivaBarreto_DISSERT.pdf: 1801241 bytes, checksum: b708db5acf9b75298b27ebb0f7e739f1 (MD5) / Made available in DSpace on 2017-03-15T21:37:25Z (GMT). No. of bitstreams: 1 JessicaPiresDePaivaBarreto_DISSERT.pdf: 1801241 bytes, checksum: b708db5acf9b75298b27ebb0f7e739f1 (MD5) Previous issue date: 2016-07-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / A possibilidade de preparar diamante sint?tico aumentou o interesse da comunidade cient?fica para aplica??o destes materiais, devido as suas caracter?sticas peculiares. Entretanto, a dopagem do diamante sint?tico com N, P, B e F torna-o semicondutor podendo ser aplicado na eletroqu?mica. No decorrer das pesquisas ficou estabelecido que o diamante dopado com boro, BDD (sigla em ingl?s) ? um ?nodo que n?o favorece a adsor??o qu?mica das esp?cies na sua superf?cie. Por?m, recentemente a influ?ncia das caracter?sticas do filme (rugosidade, espessura, teor de boro e impurezas sp2) foi determinada; e estes par?metros podem afetar a efic?cia do ?nodo na produ??o de oxidantes fortes e na degrada??o de compostos org?nicos. Por estas raz?es, estudar a influ?ncia da raz?o sp3/sp2 fornece informa??es sobre a escolha de um ?nodo espec?fico de BDD para aplica??es eletroqu?micas. Este trabalho tem como objetivos comparar ?nodos de BDD com diferente raz?o sp3/sp2 para avaliar o desempenho na produ??o de persulfato aplicando diferentes densidades de corrente, bem como, abordar ? atua??o dessa esp?cie fortemente oxidante na degrada??o de um composto modelo, Acid Violet 7. Al?m disso, o desenvolvimento de um estudo toxicol?gico empregando Lactuca Sativa atrav?s da efici?ncia de descontamina??o do efluente sint?tico mediante persulfato eletroquimicamente gerado. Os resultados claramente demonstram que o eletrodo de BDD, contendo maior teor de grafite e maior propriedade de adsor??o na superf?cie, favorece a produ??o significativa do oxidante de interesse. O melhor tempo de eletr?lise para a produ??o m?xima/ideal da esp?cie foi de 120 minutos. O tratamento eletroqu?mico para o Acid Violet 7 usando eletrodos de BDD com diferente raz?o sp3/sp2 (175 e 329) mostrou que, para ambos os casos, a elimina??o da cor e a degrada??o da mat?ria org?nica foram atingidas, por?m um maior n?vel de mineraliza??o foi observado com o BDD 329, indicando uma melhor descontamina??o do efluente. Ap?s o tratamento eletroqu?mico, an?lises toxicol?gicas comprovaram que o efluente tratado com o BDD 175 permitiu a germina??o das sementes de Lactuca Sativa. Por?m, o resultado obtido ? contr?rio ao grau de mineraliza??o obtido com o BDD 329. Esse comportamento foi devido ? significativa produ??o de oxidantes e de ?cidos alif?ticos no final do tratamento eletroqu?mico com BDD 329, evitando a germina??o de Lactuca Sativa. / The possibility of preparing synthetic diamond has increased the interest of the scientific community for application of these materials due to their unique characteristics. However, the synthetic diamond films doping with N, P, B and F become the semiconductor for application in electrochemistry. During the research it was established that the boron-doped diamond, BDD is an anode that does not favor the chemical adsorption of the species on its surface. Recently, however, the influence of film characteristics (surface roughness, thickness, and impurities boron content sp2) was determined; and these parameters can affect the effectiveness of the anode in the production of strong oxidants and degradation of organic compounds. For these reasons, study the influence of ratio sp3/sp2 provides information about choosing a specific anode BDD for specific electrochemical applications. Thus, this work has as main objectives to compare anodes BDD with different ratio sp3/sp2 to evaluate performance in the production of persulfate by applying different current densities, as well as addressing the role that strongly oxidizing species during the degradation of a model compound, Acid Violet 7. Furthermore, the development of a toxicology study using Lactuca sativa through the decontamination efficiency of the synthetic effluent using electrochemically generated persulfate was performed. The results clearly show that BDD electrode containing higher graphite content and higher adsorption property on the surface favors the significant production of the oxidant of interest. The best electrolysis time for high production of persulfate was 120 minutes. The electrochemical treatment of the Acid Violet 7 using BDD electrodes with different sp3/sp2 ratio (175 and 329) showed that for both cases, the elimination of color and degradation of organic matter were affected for this parameter. However, a significant mineralization was observed with BDD 329 than that obtained with BDD 175, indicating a better decontamination of effluent. After the electrochemical treatment, the toxicological analyzes showed that the effluent treated with BDD 175 allowed the germination of Lactuca sativa. However, the result is opposite to the degree of mineralization obtained with BDD 329. This behavior was due to the production of significant concentrations of oxidizers and aliphatic acids at the end of electrochemical treatment with BDD 329, preventing seed germination Lactuca sativa.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-02-02T11:57:40Z No. of bitstreams: 1 JorgeLeandroAquinoDeQueiroz_DISSERT.pdf: 3260207 bytes, checksum: 6a06a1293286a9a580545ad1da83aacf (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-02-06T20:15:36Z (GMT) No. of bitstreams: 1 JorgeLeandroAquinoDeQueiroz_DISSERT.pdf: 3260207 bytes, checksum: 6a06a1293286a9a580545ad1da83aacf (MD5) / Made available in DSpace on 2017-02-06T20:15:36Z (GMT). No. of bitstreams: 1 JorgeLeandroAquinoDeQueiroz_DISSERT.pdf: 3260207 bytes, checksum: 6a06a1293286a9a580545ad1da83aacf (MD5) Previous issue date: 2016-07-27 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Neste trabalho foi estudada a oxida??o eletroqu?mica de tr?s ?cidos carbox?licos: f?rmico (FA), ac?tico (AA) e ox?lico (AO) com o ?nodo de diamante dopado com boro suportado em ni?bio. Estes ?cidos s?o comumente acumulados durante ou no final de diversos processos de oxida??o avan?ada, uma vez que s?o mais persistentes que os poluentes iniciais tratados atrav?s destes m?todos. O ?nodo de BDD ? considerado um dos melhores materiais eletrocatal?ticos para estes processos, uma vez que atua eficientemente na gera??o de esp?cies fortemente oxidantes, como os radicais hidroxila, per?xido de hidrog?nio e persulfatos. O sil?cio ? o substrato mais utilizado para deposi??o da camada de diamante, entretanto este ? um material fr?gil. Sendo assim, o ni?bio se mostra como uma alternativa promissora devido a sua estabilidade qu?mica e mec?nica. Solu??es sint?ticas contendo os tr?s ?cidos carbox?licos foram submetidas a experimentos de oxida??o an?dica tendo como par?metros investigados a densidade de corrente aplicada (30, 60, 90 e 120 mA cm-2) e a influ?ncia do eletr?lito de suporte utilizado (?cido percl?rico e sulf?rico), bem como os efeitos das diferen?as estruturais dos ?cidos. A degrada??o dos compostos org?nicos foi analisada atrav?s da demanda qu?mica de oxig?nio (COD), carbono org?nico total (TOC) e HPLC, enquanto as esp?cies oxidantes foram detectadas utilizando t?cnicas reportadas na literatura. Os par?metros de efici?ncia (TCE, MCE e consumo energ?tico) tamb?m foram obtidos. Estudos eletroanal?ticos mostraram que podem ocorrer, para estes ?cidos tanto os processos de oxida??o direta quanto indireta. A densidade de corrente se mostrou determinante na efici?ncia de remo??o, sendo obtidas as maiores remo??es de COD em maiores densidades (60,7% para o AA; 77,8% para o FA e 86,1% para o OA utilizando 120 mA cm-2). O eletr?lito de suporte tamb?m influenciou na efici?ncia de remo??o, sendo que o processo foi mais eficiente com a utiliza??o do H2SO4 devido ? participa??o dos persulfatos, o que levou a maiores remo??es de COD (34,5% pra o AA; 82,5% para o FA e 93,5% para o OA utilizando 120 mA cm-2) quando comparado com o ?cido percl?rico. Por fim, os par?metros de efici?ncia obtidos mostraram que o consumo energ?tico depende apenas da densidade de corrente aplicada, e n?o da estrutura do ?cido (maiores j implicam em maiores consumos energ?ticos); a efici?ncia total de corrente, por outro lado, sofre influ?ncia da estrutura do composto org?nico. / In this work, the electrochemical oxidation of three carboxylic acids was studied ? formic acid (FA), acetic acid (AA) and oxalic acid (OA) with niobium supported boron doped diamond anode. These acids are usually accumulated during or in the end of various advanced oxidation processes, since they are more persistent compounds than the initial pollutants. BDD anode is considered one of the best electrocatalytic materials for these processes, since that it acts efficiently on the generation of strongly oxidant species, such as hydroxil radicals, hydrogen peroxide and persulfates. Silicon is the most used substrate for the deposition of the diamond layer, but it is a fragile material. Therefore, niobium is shown as a promising alternative due to its chemical and mechanical stability. Synthetic solutions containing the three carboxylic acids were submitted to anodic oxidation experiments aiming to investigate operating parameters such as current density (30, 60, 90 e 120 mA cm-2) and supporting electrolyte (perchloric and sulfuric acids) as well as the effects of the structural differences of the acids. The degradation of the organic compounds was analyzed by means of chemical oxygen demand (COD), total organic carbon (TOC) and HPLC, while the oxidant species were detected using techniques reported on literature. Efficiency parameters (TCE, MCE and energy consumption) were also obtained. Electroanalytical studies shown that both direct and indirect oxidation processes can occur for these acids. The current density was determinant on the removal efficiency, since great COD removals were obtained on higher densities (60.7% for AA; 77.8% for FA and 86.1% for OA by applying 120 mA cm-2). The supporting electrolyte also influenced on the removal efficiency, since the process was more efficient by using H2SO4 as supporting electrolyte due to the participation of persulfates, which led to higher COD removals (34,5% for AA; 82,5% for FA and 93,5% for OA by applying 120 mA cm-2) when compared to HClO4. Finally, the efficiency parameters obtained shown that energy consumption depends only of the applied current density, and not of the acid structures (higher j implies on higher energy consumptions); the total current efficiency, on other hand, is influenced by the organic compound structure.