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Previous issue date: 2016-07-20 === Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) === A oxida??o eletroqu?mica ? um tipo de processo que pode ocorrer diretamente no ?nodo, a partir de uma transfer?ncia direta com a superf?cie, ou tamb?m atrav?s de uma oxida??o indireta mediante a gera??o de esp?cies ativas de oxig?nio as quais podem ser fisicamente adsorvidas (na forma de radicais hidroxila (?OH), ou quimicamente adsorvidas (oxig?nio se apresenta em estrutura de ?xido), na superf?cie do eletrodo. Esse processo est? relacionado ao tipo do material an?dico utilizado e a sua atividade eletrocatal?tica. Por?m, essa atividade pode ser tamb?m, prejudicada devido ? forma??o de filmes polim?ricos, rea??es paralelas de produ??o de oxidantes bem como, a rea??o de evolu??o de oxig?nio. Dentre os materiais eletrocatal?ticos mais estudados encontra-se os filmes de diamante dopado com boro (DDB). O eletrodo de DDB possui excelentes propriedades tais como estabilidade eletroqu?mica a elevadas densidades de correntes, estabilidade a corros?o, superf?cie inerte com baixas propriedades de adsor??o e dureza. A alta efici?ncia do DDB para remo??o dos compostos org?nicos ? atribu?da ? capacidade de produzir uma grande quantidade de radicais hidroxilas mediante a eletr?lise da ?gua. Estes radicais apresentam alta reatividade com os compostos org?nicos, devido ? sua fraca intera??o (fracamente adsorvido) com o filme de DDB s?o tamb?m, n?o seletivos e mineralizam completamente poluentes org?nicos com uma alta efici?ncia de corrente. Entretanto, alguns compostos org?nicos s?o de f?cil degrada??o em rela??o a outros, bem como, alguns compostos org?nicos tamb?m interagem com a superf?cie do DDB. Assim, devido ? necessidade de entender o processo qu?mico em escala molecular, a inclus?o de estudos te?ricos computacionais esta sendo de maior interesse, na qual s?o desenvolvidos c?lculos f?sico-qu?micos advindos da qu?mica qu?ntica, utilizando a Teoria do Funcional da Densidade (DFT). A DFT trata sistemas com muitos el?trons usando fun??es que representam a densidade eletr?nica das mol?culas a fim de se obter: propriedades eletr?nicas, cargas at?micas e energias dos intermedi?rios que comp?e a superf?cie de energia potencial de uma rea??o qu?mica, avaliar a estabilidade de modo comparativo entre compostos e entender os mecanismos de rea??o seguidos e propostos. Assim, o objetivo deste trabalho foi o uso de DDB para o estudo do comportamento eletroqu?mico de compostos org?nicos (hidroquinona, catecol, resorcinol, ?cido ac?tico, ?cido f?rmico e ?cido ox?lico) bem como o entendimento do processo de degrada??o, dos mesmos quando eletrolisados. Al?m disso, estudos computacionais referentes ao comportamento das esp?cies qu?micas frente ao eletrodo de DDB com a inten??o de obter as configura??es de intera??o do composto org?nico na superf?cie do eletrodo ou no entendimento de desvendar as intera??es entre as esp?cies oxidantes fortes em solu??o com os compostos org?nicos durante sua degrada??o. === The Electrochemical Oxidation is a kind of process that can occur directly at the anode from a direct transfer to the surface, or also by means of indirect oxidation by the generation of active oxygen species which can be physically adsorbed (in form of hydroxyl radical (? OH)), or chemically adsorbed (oxygen is present in oxide structure) on the electrode surface. this process is related to the type of anode material used and its electrocatalytic activity. However, this activity can also be impaired due to the formation of polymeric films, production of parallel oxidant reactions as well reaction of oxygen evolution. Among the most studied electrocatalytic material is diamond films doped with boron (BDD). the BDD electrode has excellent electrochemical properties such as stability at high current densities, corrosion stability, inert surface with low adsorption properties, and hardness. The high efficiency of the BDD for removal of organic compounds is attributed to their ability to produce a large amount of hydroxyl radicals by the electrolysis of water. These radicals have high reactivity with organic compounds, due to their weak interaction (weakly adsorbed) with the film BDD, they are also not selective and completely mineralize organic pollutants with a high current efficiency. However, some organic compounds are easy to degradation than others, as well as certain organic compounds also interact with the surface of BDD. Thus, because of the need to understand the chemical process at the molecular level, including computational theoretical studies that are of most interest, which are developed physico-chemical calculations arising from quantum chemistry, using Density Functional Theory (DFT). The DFT is systems with many electrons using functions representing the electron density of molecules in order to obtain electronic, atomic charges and derivatives of energy the potential energy surface of a chemical reaction, to evaluate the stability of the compounds and understand the reaction mechanisms followed and proposed. The objective of this work was the use of BDD to study the electrochemical behavior of organic compounds (hydroquinone, catechol, resorcinol, acetic acid, formic acid and oxalic acid) as well as the understanding of the degradation process of the same when in electrolysis. Moreover, computational studies on the behavior of chemical species across the BDD electrode with the intention of obtaining the organic compound interaction settings on the surface of the electrode or the understanding to unravel the interactions between strong oxidizing species in solution with organic compounds during its degradation.
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