A potencialidade do eletrodo de cobre em meio alcalino foi demonstrada para o determinação de etanol a +0,6 V vs Ag/AgCl. A participação de espécies solúveis de Cu(III) no processo eletrocatalítico envolvendo a oxidação do etanol foi demonstrada por experimentos utilizando eletrodo disco-anel. A influência do potencial de pré-tratamento no sinal anódico foi investigada e correlacionada com a morfologia dos filmes formados na superfície do eletrodo por EDS (Energy Dispersive X-Ray Spectroscopy), indicando que as espécies de Cu(III) são originadas a partir da oxidação da camada de CuO. As medidas de etanol foram realizadas por amperometria em 0,6 V (vs Ag/AgCl). A repetibilidade das medidas utilizando padrão aquoso de etanol 0,05 % (v/v) foi de 3 % (v/v) e os limites de detecção e quantificação foram de 0,005 % (v/v) e 0,01 % (v/v), respectivamente. Nas condições experimentais otimizadas, o sensor amperométrico foi utilizado para o monitoramento da concentração de etanol no ar exalado (BrAC), que foi convenientemente coletado em um balão de borracha (V = 3 L) e introduzido em uma solução de NaOH 1 mol L-1 (V = 10 mL). O sensor apresentou uma faixa linear para concentrações de etanol em ar exalado na faixa de 0,26 – 130 mg L-1, operando de acordo com os parâmetros analíticos especificados na Legislação Brasileira para a quantificação de etanol no ar exalado em condutores de veículos automotores. A constante de eliminação de etanol do corpo humano também foi investigada e os resultados concordaram com os valores da literatura. Empregando-se eletrodos de Cu e Au foram também desenvolvidas outras metodologias para a quantificação de dipirona, glicose e ácido ascórbico e sistemas em fluxo. Estudos sobre o desenvolvimento e propriedades de um sistema gerador-coletor foram realizados e o dispositivo foi utilizado em titulações de substâncias redutoras com iodo gerado eletroquimicamente. / A copper disc working electrode in alkaline solutions was demonstrated to act as a suitable amperometric sensor for ethanol determination at +0.6 V vs Ag/AgCl. The participation of free-soluble Cu(III) species in the electrocatalytic process involving the anodic oxidation of ethanol has been demonstrated by rotating ring-disc electrode voltammetry. The influence of the pretreatment potential on the anodic signal was investigated and a correlation with the morphology of the electrode surface characterized by Energy Dispersive X-Ray Spectroscopy (EDS) indicated that the Cu(III) species is originated from the oxidation of a CuO layer. Ethanol measurements were performed in the amperometric mode at 0.6 V (vs Ag/AgCl). The repeatability of the measurements for a 0.05 % aqueous ethanol solution was estimated as 3 %, and the detection and quantification limits were determined as 0.005 % and 0.01 %, respectively. At the optimum experimental conditions, the amperometric sensor was used to monitor the concentration of ethanol in breath (BrAC), which was conveniently collected in a rubber air balloon (volume = 3 L) and introduced in a 1 mol L-1 NaOH working solution (volume = 10 mL). The sensor can measure a person\'s breath ethanol over the concentration range 0.26 - 130 mg L-1 by operating it according to an established protocol, of which the analytical parameters are specified by the Brazilian Legislation for BrAC measurements in drivers. The rate of ethanol degradation in the body was followed, and the results agree with predictions in the literature. Methodologies for the determination of dipyrone, glucose and ascorbic acid were also developed by using Cu and Au electrodes. Features of a dual-band electrochemical cell were investigated towards the development of a generator-collector system, which was employed in titrations with electrogenerated iodine.

A potencialidade do eletrodo de cobre em meio alcalino foi demonstrada para o determinação de etanol a +0,6 V vs Ag/AgCl. A participação de espécies solúveis de Cu(III) no processo eletrocatalítico envolvendo a oxidação do etanol foi demonstrada por experimentos utilizando eletrodo disco-anel. A influência do potencial de pré-tratamento no sinal anódico foi investigada e correlacionada com a morfologia dos filmes formados na superfície do eletrodo por EDS (Energy Dispersive X-Ray Spectroscopy), indicando que as espécies de Cu(III) são originadas a partir da oxidação da camada de CuO. As medidas de etanol foram realizadas por amperometria em 0,6 V (vs Ag/AgCl). A repetibilidade das medidas utilizando padrão aquoso de etanol 0,05 % (v/v) foi de 3 % (v/v) e os limites de detecção e quantificação foram de 0,005 % (v/v) e 0,01 % (v/v), respectivamente. Nas condições experimentais otimizadas, o sensor amperométrico foi utilizado para o monitoramento da concentração de etanol no ar exalado (BrAC), que foi convenientemente coletado em um balão de borracha (V = 3 L) e introduzido em uma solução de NaOH 1 mol L-1 (V = 10 mL). O sensor apresentou uma faixa linear para concentrações de etanol em ar exalado na faixa de 0,26 – 130 mg L-1, operando de acordo com os parâmetros analíticos especificados na Legislação Brasileira para a quantificação de etanol no ar exalado em condutores de veículos automotores. A constante de eliminação de etanol do corpo humano também foi investigada e os resultados concordaram com os valores da literatura. Empregando-se eletrodos de Cu e Au foram também desenvolvidas outras metodologias para a quantificação de dipirona, glicose e ácido ascórbico e sistemas em fluxo. Estudos sobre o desenvolvimento e propriedades de um sistema gerador-coletor foram realizados e o dispositivo foi utilizado em titulações de substâncias redutoras com iodo gerado eletroquimicamente. / A copper disc working electrode in alkaline solutions was demonstrated to act as a suitable amperometric sensor for ethanol determination at +0.6 V vs Ag/AgCl. The participation of free-soluble Cu(III) species in the electrocatalytic process involving the anodic oxidation of ethanol has been demonstrated by rotating ring-disc electrode voltammetry. The influence of the pretreatment potential on the anodic signal was investigated and a correlation with the morphology of the electrode surface characterized by Energy Dispersive X-Ray Spectroscopy (EDS) indicated that the Cu(III) species is originated from the oxidation of a CuO layer. Ethanol measurements were performed in the amperometric mode at 0.6 V (vs Ag/AgCl). The repeatability of the measurements for a 0.05 % aqueous ethanol solution was estimated as 3 %, and the detection and quantification limits were determined as 0.005 % and 0.01 %, respectively. At the optimum experimental conditions, the amperometric sensor was used to monitor the concentration of ethanol in breath (BrAC), which was conveniently collected in a rubber air balloon (volume = 3 L) and introduced in a 1 mol L-1 NaOH working solution (volume = 10 mL). The sensor can measure a person\'s breath ethanol over the concentration range 0.26 - 130 mg L-1 by operating it according to an established protocol, of which the analytical parameters are specified by the Brazilian Legislation for BrAC measurements in drivers. The rate of ethanol degradation in the body was followed, and the results agree with predictions in the literature. Methodologies for the determination of dipyrone, glucose and ascorbic acid were also developed by using Cu and Au electrodes. Features of a dual-band electrochemical cell were investigated towards the development of a generator-collector system, which was employed in titrations with electrogenerated iodine.

Résumé du travail<p><p>L’étude des modifications de surfaces, et plus particulièrement des matériaux d’électrodes est un domaine en plein essor. Les modifications d’électrodes par voie organique ont des applications potentielles dans des domaines aussi variés que l’inhibition de la corrosion, l’électronique moléculaire, l’optoélectronique ou encore les biosenseurs.<p>Dans ce travail, nous nous sommes intéressés à l’électrode d’Au (111) modifiée par du 2-mercaptobenzimidazole. <p><p>Dans un premier temps, l’adsorption du MBI sur électrode d’Au (111) sous contrôle du potentiel a été examinée par des mesures de capacité, de voltampérométrie cyclique, de chronocoulométrie et de spectroscopie SNIFTIR in situ.<p>Les mesures de capacité révèlent qu’en milieu neutre, la molécule de MBI s’adsorbe en un film compact à des potentiels supérieurs à -0,3 V (vs. ECS). En deçà de cette valeur, le film se dilue progressivement lorsque le potentiel est rendu plus négatif, jusqu’à une valeur de -0,9 V où les molécules de MBI sont totalement désorbées de la surface.<p>La morphologie des voltampérogrammes subit des variations significatives au cours du temps. Ces changements montrent que l’adsorption du MBI s’accompagne d’une levée de reconstruction de la surface, qui passe d’une structure initiale (√3 x 22) à une structure (1 x 1). Une estimation de la quantité de MBI adsorbée est obtenue par intégration des courbes de densité de courant.<p>La courbe de densité de charge interfaciale a été extraite des mesures de chronocoulométrie. Cette courbe de densité de charge fournit des informations quant à l’évolution de l’excès superficiel en fonction du potentiel.<p>La qualité des spectres infrarouges relevés in situ nous a permis d’effectuer des analyses qualitatives et quantitatives. Celles-ci montrent une bonne corrélation avec les résultats électrochimiques et apportent une signature moléculaire du film adsorbé et des espèces issues de sa désorption. Des calculs basés sur la Théorie de la Fonctionnelle de la Densité (DFT) ont permis une bonne interprétation des spectres infrarouges du MBI et de certains de ses dérivés. En outre, nous avons pu déterminer l’orientation des molécules à la surface, et montré que celle-ci varie peu avec le potentiel.<p><p>Dans un second temps, nous nous sommes focalisés sur les propriétés de la monocouche auto-assemblée de MBI sur électrode d’Au (111), déterminées par voltampérométrie cyclique et spectroscopie infrarouge in situ. La monocouche est stable lorsque le potentiel est maintenu dans un domaine d’environ 800 mV. La monocouche auto-assemblée de MBI subit un processus de désorption réductive, influencé par le temps d’immersion de l’électrode dans la solution de surfactant ainsi que par le pH du milieu. Deux mécanismes de désorption réductive sont proposés, l’un valable en milieu neutre et basique, l’autre en milieu acide. Les résultats des mesures de spectroscopie infrarouge in situ apportent une preuve moléculaire de la validité des mécanismes proposés sur base des résultats électrochimiques.<p>Un rapide examen des potentialités de cette monocouche a été réalisé à l’aide de réactions sondes.<p>/<p>Abstract<p><p>Studies on surface modifications, and particularly of electrode material, are a growing field of interest. Organic modifications of electrode surfaces have potential applications in domains such as corrosion inhibition, molecular electronics, optoelectronics or biosensors.<p>In the present work, we focussed on the modification of Au(111) electrodes by 2-mercaptobenzimidazole (MBI).<p><p>In the first part, the adsorption, under potential control, of the MBI molecule onto the Au(111) electrode was studied by means of capacitance measurements, cyclic voltammetry, chronocoulometry and in-situ SNIFTIR spectroscopy.<p>Capacitance measurements indicate that in neutral solution, the MBI molecule is adsorbed as a compact film at potentials higher than -0.3 V (vs. SCE). Below this value, the film becomes progressively less dense when the potential is made more negative, until a value of -0.9 V where MBI molecules are totally desorbed from the surface.<p>The shape of the voltammograms evolves significantly with time. These changes show that a lift of the surface reconstruction occurs concomitantly to the adsorption of MBI. The initial (√3 x 22) reconstructed structure is lifted to the (1 x 1) unreconstructed one. The amount of adsorbed MBI is estimated by integration of the current density curves.<p>The interfacial charge density curve was obtained by chronocoulometry measurements. This curve provides useful data regarding the evolution of the surface concentration with the potential.<p>The quality of the infrared spectra obtained in situ allowed us to perform quantitative as well as qualitative analyses of the results. These analyses show a good correlation with the electrochemical results and provide molecular information on the adsorbed layer and on the species formed during the desorption process. Density Functional Theory (DFT) calculations were helpful in the interpretation of the infrared spectra of MBI and some of its derivatives. Additionally, we were able to determine the orientation of the molecules on the surface, and demonstrated that this orientation is slightly affected by the potential.<p><p>In the second part of the work, we investigated the properties of the self-assembled monolayer of MBI on Au(111) electrode by cyclic voltammetry and in situ infrared spectroscopy. The monolayer is stable within an 800 mV potential range. The self-assembled monolayer undergoes a reductive desorption process, which is affected by the pH of the medium and by the immersion time of the electrode into the surfactant solution. Two mechanisms were proposed for the reductive desorption, one being valid in neutral and basic media, the other in acidic conditions. The in situ infrared spectroscopic results provide molecular evidences supporting the mechanisms proposed on an electrochemical basis.<p>An exploratory examination of the potentialities of the monolayer is made by means of electrochemical probe reactions.<p> / Doctorat en sciences, Spécialisation chimie / info:eu-repo/semantics/nonPublished