Nanotechnology refers to the use of the materials or particles ranging from a few nanometers (nm) to 100 nanometers (nm) in a wide range of applications. Use of nanomaterials in cement composite to enhance the mechanical properties, fracture toughness and other functionalities has been studied for decades. In this regard, one of the carbon-based nanomaterials, Graphene Oxide (GO), has received attentions from researchers for its superior mechanical properties (e.g. tensile strength, yield strength, and Young's modulus). Although GO is not lucrative in increasing electrical conductivity (EC) of cement paste compared to that of graphene- another derivative of GO, reduced graphene oxide (rGO), might be a solution to increase EC. Another derivative of GO is the solution to the problem. In this research, the compressive strength and flexural strength of GO-cement composite (GOCC) and rGO-cement composite (rGOCC) have been investigated with 0.01% and 0.05% GO and rGO content. GOCC-0.05% showed 27% increase in compressive strength compared to the control cement paste after 28 days (d) of hydration. GOCC-0.01% showed only 3.4% increase in compressive strength compared to the control. rGOCC-0.05% showed 21% increase in compressive strength and 15.5% increase in Modulus of Rupture (MOR) compared to the control cement paste after 28 d of hydration. On the other hand, rGOCC-0.01% showed 7% increase in compressive strength and 0.35% increase in MOR after 28 d. GOCC-0.05% showed increasing trends in compressive strength after 28 d indicating continuation of hydration. Similarly, rGOCC-0.05% also showed increasing trends in compressive and flexural strength after 28 d, possibly due to the reason described earlier. Microstructural investigation on GOCC-0.05% and GOCC-0.01% by X-ray Diffraction (XRD) illustrated that the crystallite sizes of tobermorite-Å and jennite, which are mineralogical counterpart of disordered Calcium-Silicate-Hydrate (C-S-H), increases from 3 d to 28 d, representing the crystallite growth due to continued hydration. However, the crystallite size of GOCC-0.05% was smaller than that of GOCC-0.01% at both 3 d and 28 d, indicating finer nucleated grains. According to Hall-Petch equation, mechanical strength increases with decreasing particle size. Finer particles or grains can increase the strength in cement composites in several other ways: (1) GO acted as heterogeneous nucleation sites because of reactive functional groups. Activation energy was decreased by these "defects" in the cement paste, and consequently, numerous nuclei of C-S-H. with high surface area were formed, (2) because of finer grains, cracks are forced to move along a tortuous path, which makes the structure difficult to fail, and strength increased consequently (3) Finer grains of GOCC-0.05% created compacted hydration products decreasing porosity which can indirectly increase the strength. The above reasons, separately or in conjunction, might increase the strength of GOCC-0.05% and proved that GO is responsible for increasing heterogeneous nucleation sites during cement hydration. Early age hydration (EAH) characteristics were investigated for rGOCC specimens with 0.1% and 0.5% rGO content. Scanning Electron Microscope (SEM), Energy Dispersive X-ray analysis (EDX), and X-ray Diffraction (XRD) were employed to study the EAH characteristics. SEM/EDX, and XRD analysis were performed after 15 min, 1 h, 3 h and 24 h of hydration. (EAH) study on rGOCC-0.1% showed that at 15 min hydration, numerous precipitates of, possibly, C-S-H formed along the grain boundary (GB) of unhydrated cement grains. This served as visual confirmation of Thomas and Scherer's Boundary Nucleation and Growth (BNG) model that hydration of cement grains was initiated by the short burst of nucleation of C-S-H embryos along GB. EDX on rGOCC-0.1% and rGOCC-0.5% showed that Ca/Si ratio in C-S-H was ~2.0. This finding indicated that C-S-H structure in this study was concurrent with that of impure jennite. XRD analysis also evidently showed that jennite was present, possibly possessing a short range ordered (SRO) structure, referring to local crystalline structure in a very short area. After consulting Chen's work, it would be appropriate to say that C-S-H found in this study resembled more as C-S-H (II), which is disordered jennite. It was also observed that as expected with cement with nanomaterials, with continuing hydration, pore spaces were filled with hydration products such as C-S-H, ettringite, CH, sulfoaluminates etc,. Lastly, Electrical resistivity (ER) testing on 9 sets of rGOCC specimens was conducted. The specimen includes 0.5%, 1%, 5% rGO content, and the control conditioned in both oven dry (OD) and saturated surface dry (SSD). ER increased with the increase of rGO content from 0.5% and 1% compared to that of the control. However, the ER of rGOCC-5% was significantly decreased, showing 93% reduction compared to the control, which can be interpreted as a threshold value for sensing applications to be explored. As expected, large reduction of ER value occurred on the specimens with the SSD condition. This reduction can be attributed to the ionic conduction though the pore solution of the composites. As the rGO content increased, so did the potential nucleation sites for hydration (as can be seen in SEM images), which might block the number of contact points among the rGO, resulting in low conduction and high resistivity. However, as rGO content increased to 5%, the contact areas/points increased to a degree that could trump the nucleation seeding sites, resulting in decreased ER. The ER measured with the rGOCC specimens was comparable to that of cement composites incorporating carbon fibers (CF), and steel fibers, but higher content of rGO are required to have a similar ER range of those fiber cement composites. This might be due to smaller sizes of rGO sheets and lower aspect ratio compared to other nanofibers causing drastic reduction of electron tunneling mechanism compared to other fibers.

No description available.

This thesis investigates pool boiling heat transfer from bare and graphene-coated NiCr wires in a saturated liquid of FC 770, a fluorocarbon fluid. Of particular interest was the effect of graphene-oxide platelets, dip-coated onto the heater surface, in enhancing the nucleate boiling heat transfer (BHT) rates and the critical heat flux (CHF) value. In the course of the pool boiling experiment, the primary focus was on the reduction mechanism of graphene oxide. The transition from hydrophilic to hydrophobic behavior of the graphene oxide-coated surface was captured, and the attendant effects on surface wettability, porosity and thermal activity were observed. A parametric sensitivity analysis of these surface factors was performed to understand the CHF and BHT enhancement mechanisms. In the presence of graphene-oxide coating, the data indicated an increase of 50% in CHF. As the experiment continued, a partial reduction of graphene oxide occurred, accompanied by (a) further enhancement in the CHF to 77% larger compared to the bare wire. It was shown that the reduction of graphene oxide progressively altered the porosity and thermal conductivity of the coating layer without changing the wettability of FC 770. Further enhancement in CHF was explained in terms of improved porosity and thermal activity that resulted from the partial reduction of graphene-oxide. An implication of these results is that a graphene-oxide coating is potentially a viable option for thermal management of high-power electronics by immersion cooling technology. / Master of Science

Orientadores: Vitor Baranauskas, Helder José Ceragioli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-27T01:34:46Z (GMT). No. of bitstreams: 1 Silva_ThiagoFranchiPereirada_D.pdf: 9373432 bytes, checksum: 13a36b35d789088396a134f65246b3a9 (MD5) Previous issue date: 2015 / Resumo: Células solares orgânicas e inorgânicas representam uma excelente alternativa como fonte de energia renovável. Este trabalho consiste em aplicar nanoestruturas de carbono obtidas pela técnica HFCVD (Hot Filament Chemical Vapour Deposition) como componentes utilizados na construção e melhoria de células solares orgânicas (organic photovoltaics - OPVs) e células sensibilizadas por corante (dye-sensitized cells - DSCs). Foi obtido óxido de grafeno reduzido (rGO), carbono tipo diamante (DLC - diamondlike carbon) e diamante condutor nanoestruturado. Estes materiais foram caracterizados por microscopia eletrônica de varredura (SEM-FEG), microscopia de transmissão de alta resolução (HRTEM), espectroscopia Raman e análise termogravimétrica (TGA). O rGO foi empregado na construção das células DSC misturado na pasta de TiO2 em diferentes concentrações, produzindo o aumento de fotocorrente gerada e, consequentemente, o rendimento. O mesmo material foi empregado nas OPVs, em diferentes concentrações, para a substituição do fulereno PCBM (1-(3-metoxicarbonil)-propil-1-1-fenil- (6,6)metanofulereno) e também em conjunto com o fulereno, sendo observada também a melhoria no desempenho dos dispositivos em função da concentração. Com finalidade de substituir os contraeletrodos das células DSC, carbono tipo diamante foi depositado em substrato de alumínio (Al) e diamante condutor nanoestruturado depositado em substratos de nióbio (Nb). As células com contraeletrodos de Al com filme de DLC apresentaram sensibilidade à luz, com possibilidade de aplicação em sensores ópticos, enquanto as células com contraeletrodos de Nb com filme de diamante condutor apresentaram excelente desempenho, tornando possível a substituição dos contraeletrodos de platina / Abstract: Organic and inorganic solar cells comprise a promising solution as a renewable energy source. This work consists of applying carbon nanostructures obtained by HFCVD technique (Hot Filament Chemical Vapour Deposition) as components used in the construction and improvement of organic solar cells (organic photovoltaics - OPVs) and dye sensitized cells (dye-sensitized cells - DSCs). Reduced graphene oxide (rGO), carbon diamond-like (DLC - diamond- like carbon) and nanostructured conductor diamond was obtained. These materials were characterized by scanning electron microscopy (SEM-FEG), high resolution transmission microscopy (HRTEM), Raman spectroscopy and thermal gravimetric analysis (TGA). Reduced graphene oxide was used for the construction of the DSC cell at the TiO2 layer mixed in different concentrations, producing an increase in photocurrent generated and thus conversion efficiency. The same material was used in the OPVs at different concentrations for the replacement of fullerene PCBM (1- (3-methoxycarbonyl) -propyl-1-1-phenyl- (6,6) metanofulereno) and with the fullerene was also observed improvement in performance of the devices as a function of concentration. With aim of replacing the counterelectrode of DSCs cells, diamond-like carbon was deposited on aluminum substrate (Al) and nanostructured conductive diamond deposited on niobium (Nb) substrates. Cells with Al/DLC counterelectrode showed sensitivity to light, with the possibility of application in optical devices while cells with Nb/nanostructured conductive diamond counterelectrode showed excellent performance, with possibility to replace platinum counterelectrodes / Doutorado / Eletrônica, Microeletrônica e Optoeletrônica / Doutor em Engenharia Elétrica

A adoção de políticas de incentivo ao desenvolvimento de novas tecnologias de geração de energia tem sido consenso entre especialistas de gestão ambiental. Nesta perspectiva, sistemas de conversão como células a combustível de baixa temperatura de operação (60120 °C) constituem alternativas propícias para fornecimento de energia com emissão reduzida de poluentes. Em adição, o etanol representa uma opção atrativa como combustível devido às vantagens relacionadas à característica renovável e à consolidação da indústria de bioetanol em países como Brasil e Estados Unidos. Contudo, a oxidação do etanol resulta em perdas de eficiência por causa da dificuldade de clivagem da ligação carbono-carbono. Tradicionalmente, platina tem sido usada como catalisador em decorrência das elevadas energia de adsorção e densidade de corrente de troca. Entretanto, a melhora na cinética de reação requer maior utilização catalítica. Neste contexto, um processo de síntese de óxido de grafeno reduzido foi desenvolvido para estabilizar e suportar a fase metálica, aperfeiçoando a área eletroquimicamente ativa. Uma metodologia convencional de síntese química e processamento de óxido de grafeno, a partir de grafite, foi aprimorada visando à fabricação de materiais com características desejáveis aos processos eletrocatalíticos. As estratégias foram baseadas em princípios combinados para introdução controlada de defeitos, redução no estado de aglomeração com auxílio de funcionalização direcionada com surfactante brometo de cetiltrimetilamônio (CTAB) e manufatura de dispersões com aumentada estabilidade coloidal. A nova nanoestrutura forneceu elevada densidade de sítios ativos, que incorreu em valores de corrente mássica aumentados em torno de 2,5 e 5,4 vezes frente à platina suportada em negro de fumo e grafeno aglomerado, respectivamente. / In the last decade, the adoption of policies aimed at developing new technologies for clean energy production has been a broad consensus among environment experts. From this perspective, low-temperature fuel cells (60120 °C) would appear to be promising systems to provide continuous and low-carbon power supply. As an alternative fuel, ethanol would be an appealing option due to renewability and mass production scalability. Nevertheless, the sluggish kinetics of ethanol electro-oxidation represents a major roadblock for the development of direct ethanol fuel cells. Platinum has been the most commonly used catalyst because of the highest energy adsorption and exchange current density. Optimizing reaction kinetics by tuning catalyst utilization has been applied to achieve improved performance on platinum-based catalysts. In this context, reduced graphene oxide sheets were developed to stabilize and support platinum nanoparticles, as well as to enhance the electrochemically active surface area. A conventional wet chemical methodology for synthesizing and processing graphene oxide from graphite was improved for assembling bi and/or tridimensional nanostructures with relevant microstructural features to electrocatalysis. The approach for reducing mass-transport resistances was based on a three-step design strategy aimed at the controlled introduction of defects, in situ cetyltrimethylammonium bromide (CTAB) surfactant functionalization/intercalation and a manufacturing perspective on graphene dispersions from a basic solution thermodynamics theory. The unique nanoarchitecture provided a high density of active sites, which incurred in a mass current value increased by about 2.5 and 5.4 times compared to platinum supported on state-of-the-art carbon black and restacked graphene, respectively.

Orientador: Antonio Riul Júnior / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-09-02T14:50:41Z (GMT). No. of bitstreams: 1 Ly_KallyCheinSheng_M.pdf: 2442128 bytes, checksum: 86716c6c19fa3a9db425b32c36463141 (MD5) Previous issue date: 2017 / Resumo: Materiais biomiméticos são inspirados em estruturas biológicas para a obtenção de propriedades e funcionalidades específicas. Dentre os materiais biomiméticos, os que são capazes de se regenerar (self-healing) despertaram grande interesse pelo potencial de aplicação em diversas áreas. Para ilustrar, alguns materiais autorregeneráveis poliméricos apresentam regeneração múltipla, necessitando apenas de água para que a regeneração ocorra em alguns minutos, aumentando consideravelmente a proteção mecânica da superfície contra desgastes, danos mecânicos entre outros. Entretanto, múltiplas imersões em água ou em meios aquosos pode degradar o material e neste contexto este projeto visa incorporar a hidrofobicidade a um sistema regenerável. Desta forma, o material regenerável hidrofóbico, durante sua regeneração imersa em água, poderá diminuir a interação da superfície não danificada com a água, reduzindo corrosões e degradações devido a meios aquosos. Estudamos a nanoestruturação de materiais através da técnica de automontagem por adsorção física (LbL, do inglês Layer-by-Layer) utilizando os polieletrólitos poli(etileno imina) (PEI) e poli(ácido acrílico) (PAA), a fim de produzir revestimentos capazes de se regenerar a danos mecânicos micrométricos. Adicionalmente, foram incorporados a estes dois materiais nanofolhas de óxido de grafeno reduzido (rGO) funcionalizados com poli(cloridrato de alilamina) (GPAH) e poli(estireno-sulfonato de sódio) (GPSS), com o intuito de verificarmos um aumento de resistência a abrasão do material e alterações nas propriedades elétricas na nanoestrutura formada para aumentar o potencial de aplicação em eletrônica flexível. A arquitetura molecular (GPAH-PEI/GPSS-PAA)60 foi caracterizada com espectroscopia Raman, medidas de ângulo de contato, microscopia de força atômica, medidas elétricas e nanoindentação. Foi observada boa regeneração do material após 15 minutos de imersão em água a temperatura ambiente em um dano mecânico da ordem de 10 micrômetros. Também observamos boa hidrofobicidade do filme LbL (GPAH-PEI/GPSS-PAA)60 ( teta = 136º), e medidas de microscopia de força atômica e perfilometria indicaram, respectivamente, rugosidade superficial de 55 nm em uma área de (2 ?m x 2 ?m) e espessura de filme de 30 ?m. A análise Raman apontou para uma forte interação das nanofolhas de rGO com os polímeros, corroborando o tem caráter elétrico isolante do filme (GPAH-PEI/GPSS-PAA)60, que apresentou função trabalho ~ 5,2 eV e condutividade elétrica da ordem de 10-7 S/cm, que acreditamos resultar das fortes interações das nanofolhas com os polímeros. Por fim, medidas de nanoindentação indicaram que a incorporação de nanofolhas de GPSS e GPAH aumentou em 10 vezes a dureza do nanocompósito formado, sem comprometer a regeneração / Abstract: Biomimetic materials are inspired in biological structures to obtain specific properties and functionalities and among them, those capable of self-healing brought great interest due to high potential of application in different areas. To illustrate, some polymeric self-healing materials present multiple regeneration in the presence of water, with the regeneration occurring within a few minutes, increasing considerably the mechanical protection of a surface against wear and mechanical damage among others. Nevertheless, multiple immersions in water or in aqueous media can degrade the material and in this context this project aims the incorporation of hydrophobicity to a self-healing system. In this way, the self-healing, hydrophobic material during its immersion in water may decrease the interaction of the damaged surface with water, reducing corrosion and degradation due to aqueous media. We study the nanostructuration f materials through the layer-by-layer (LbL) technique using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA) in order to produce self-healing coatings from micrometric mechanical damages. In addition, we also incorporate to these materials reduced graphene oxide (rGO) functionalized with poly(allylamine hydrochloride) (GPAH) and poly(styrene-sodium sulfonate) (GPSS), with the purpose of verifying an increase in the mechanical abrasion resistance of the material and changes in the electrical properties of the nanostructures formed to increase the potential application in flexible electronics. The molecular architecture (GPAH-PEI/GPSS-PAA)60 was characterized by Raman spectroscopy, contact angle measurements, atomic force microscopy, electrical measurements and nanoindentation. It was observed good self-healing capacity after 15 min f immersion in water at room temperature in a mechanical scratch of the order of 10 micrometers. It was also observed good hydrophobicity in the (GPAH-PEI/GPSS-PAA)60 LbL film ( teta = 136º) and atomic force microscopy and perfilometer indicate, respectively, surface roughness of 55 nm in a (2 ?m x 2 ?m) area and film thickness of 30 ?m. Raman analysis pointed out to a strong physical interaction between the rGO nanoplatelets with the polymeric materials, corroborating the strong insulating nature of (GPAH-PEI/GPSS-PAA)60 film that displayed a work function of 5.2 eV and electrical conductivity of 10-7 S/cm, which we believe results from the strong interactions of the nanosheets with the polymers. Finally, nanoindentation measurements indicated that the incorporation of GPAH and GPSS nanoplatelets increased hardness by 10 times, without compromising the regeneration / Mestrado / Física / Mestra em Física / 1543078/2015 / CAPES

Orientador: Miguel Ángel Ramírez Gil / Resumo: O óxido de grafeno reduzido (OGR) é um nanomaterial que possui propriedades como elevada área superficial e resistência mecânica, e é altamente dispersível em água. A literatura é muito escassa sobre a aplicação deste nanomaterial em materiais da construção civil, como argamassas cimentícias. Este trabalho abordou a influência do OGR nas propriedades mecânicas, físicas e microestruturais em argamassas cimentícias com dosagens já testadas para o óxido de grafeno (OG) 0,03%, 0,05%, 0,07% e 0,09% (em relação ao peso de cimento), em idades de 7, 28 e 91 dias. Com adição de 0,05% de OGR, a resistência à compressão teve aumentos 12,0%, 9,6%, e 7,8%, respectivamente, em todas as idades de cura, em relação a amostra sem adição de OGR. Em relação a resistência à compressão diametral e absorção de água por capilaridade, não houve melhoras aos 7 e 28 dias de cura, somente aos 91 dias, nas amostras com as maiores dosagens de OGR de 0,07% e 0,09%, apresentando um aumento de 16% da resistência à tração por compressão diametral. Na absorção de água por capilaridade aos 91 dias de cura, houve uma redução de 18,2% e 27,3%, com adição de 0,07 e 0,09%, respectivamente. As microestruturas mais favoráveis para bons resultados foram as que os cristais de hidratação se assemelham a bastonetes, lâminas, flocos e cristais lamelares que se sobrepõem tornando-se compactos e/ou densos. / Abstract: Reduced graphene oxide (RGO) is a nanomaterial that has properties such as high surface area and strength, it can be highly dispersible in water. The literature is very scarce on the application of this nanomaterial in civil construction materials, such as cement mortar. This work deals with the influence of RGO on the mechanical, physical and microstructural properties of cement mortar with already tested dosages for 0.03%, 0.05%, 0.07% and 0.09% graphene oxide (GO) (in relation to the weight of cement), with ages 7, 28 and 91 days. With addition of 0.05% RGO, the resistance of compression had increases of 12.0%, 9.6%, and 7.8%, respectively, in all curing ages, in relation to the sample without addition of RGO. The resistance by diametrical compression and water absorption by capillarity did not improve at 7 and 28 days of cure, only at 91 days of cure, in samples with higher RGO values of 0.07% and 0.09%, there was an average increase of 16.0% in the resistance by diametrical compression. / Mestre

Ces dernières années, les énormes progrès réalisés en nanotechnologie ainsi qu’en science des matériaux ont conduit à la préparation de nombreuses nouvelles nanoparticules sans réellement connaître l’ensemble des propriétés associées à leurs dimensions. La première partie de notre travail vise à évaluer les risques et les problèmes associés aux nanomatériaux, en termes de toxicité, en utilisant des nanoparticules de ZnO. Nous avons tout d’abord étudié la capacité de ces nanoparticules à générer des espèces réactives d’oxygènes (EROs) sous irradiation UV en utilisant trois types des quantum dots (QDs) comme modèles, ZnO, ZnO dopé avec des ions Cu2+ et ZnO avec des ions Cu2+ adsorbés à sa surface. Les trois types des QDs ont montré une forte capacité à générer des EROs mais ceux modifiés par les ions Cu2+ en périphérie sont les plus producteurs. Ces QDs inhibent également le plus fortement la croissance de la bactérie E. coli. La toxicité n’est cependant pas dépendante des EROs photo-produits ni du zinc (+2) libéré par les QDs et montre qu’un mécanisme plus complexe doit être considéré. Dans une second partie, nous avons tenté d’améliorer l’activité photocatalytique de nanobâtonnets de ZnO en les associant à de l’oxyde de graphène réduit (rGO). Des nanocomposites ZnO/rGO ont été préparés par voie solvothermale et utilisés pour la phototodégradation du colorant Orange II comme modèle de polluant. Les résultats obtenus montrent que le photocatalyseur ZnO/rGO est très efficace sous irradiation solaire ou visible et qu’il est peu sensible à des variations de pH ou à la présence de perturbateurs dans le milieu. Finalement, le photocatalyseur est très stable et peut être réutilisé plus de dix fois sans perte notable d’activité. / In recent years, tremendous advances in nanotechnology and materials science have led to the synthesis of many new nanoparticles without really knowing all the properties associated with their dimensions. The first part of our work aims to evaluate the risks and problems associated with nanomaterials, in terms of toxicity, using ZnO nanoparticles. We first studied the ability of these nanoparticles to produce reactive oxygen species (ROS) under UV irradiation using three ZnO-based quantum dots (QDs) as models, ZnO, ZnO doped with Cu2+ ions and ZnO with chimisorbed Cu2+ ions at their periphery. The three QDs have a strong capacity of generating ROS but those modified with Cu2+ at their surface were found the be the highest producers. These dots were also found to inhibit more markedly the growth of the E. coli bacteria. The toxicity does neither depend on the amount of photo-generated ROS nor on the amount of Zn(+2) leaked by the QDs, thus indicating that a more complex mechanism should be considered. In a second part, we tried to improve the photocatalytic efficiency of ZnO nanorods by associating these nanomaterials with reduced graphene oxide (rGO). ZnO/rGO composites were prepared by a solvothermal method and applied for the photodegradation of Orange II used as model pollutant. Results obtained demonstrate that the ZnO/rGO photocatalyst is highly efficient under solar and under visible light irradiation and weakly sensitive to pH changes and to the presence of perturbators in the reaction medium. Finally, the photocatalyst is stable and can be reused up to ten times without significant loss of catalytic activity.

A adoção de políticas de incentivo ao desenvolvimento de novas tecnologias de geração de energia tem sido consenso entre especialistas de gestão ambiental. Nesta perspectiva, sistemas de conversão como células a combustível de baixa temperatura de operação (60120 °C) constituem alternativas propícias para fornecimento de energia com emissão reduzida de poluentes. Em adição, o etanol representa uma opção atrativa como combustível devido às vantagens relacionadas à característica renovável e à consolidação da indústria de bioetanol em países como Brasil e Estados Unidos. Contudo, a oxidação do etanol resulta em perdas de eficiência por causa da dificuldade de clivagem da ligação carbono-carbono. Tradicionalmente, platina tem sido usada como catalisador em decorrência das elevadas energia de adsorção e densidade de corrente de troca. Entretanto, a melhora na cinética de reação requer maior utilização catalítica. Neste contexto, um processo de síntese de óxido de grafeno reduzido foi desenvolvido para estabilizar e suportar a fase metálica, aperfeiçoando a área eletroquimicamente ativa. Uma metodologia convencional de síntese química e processamento de óxido de grafeno, a partir de grafite, foi aprimorada visando à fabricação de materiais com características desejáveis aos processos eletrocatalíticos. As estratégias foram baseadas em princípios combinados para introdução controlada de defeitos, redução no estado de aglomeração com auxílio de funcionalização direcionada com surfactante brometo de cetiltrimetilamônio (CTAB) e manufatura de dispersões com aumentada estabilidade coloidal. A nova nanoestrutura forneceu elevada densidade de sítios ativos, que incorreu em valores de corrente mássica aumentados em torno de 2,5 e 5,4 vezes frente à platina suportada em negro de fumo e grafeno aglomerado, respectivamente. / In the last decade, the adoption of policies aimed at developing new technologies for clean energy production has been a broad consensus among environment experts. From this perspective, low-temperature fuel cells (60120 °C) would appear to be promising systems to provide continuous and low-carbon power supply. As an alternative fuel, ethanol would be an appealing option due to renewability and mass production scalability. Nevertheless, the sluggish kinetics of ethanol electro-oxidation represents a major roadblock for the development of direct ethanol fuel cells. Platinum has been the most commonly used catalyst because of the highest energy adsorption and exchange current density. Optimizing reaction kinetics by tuning catalyst utilization has been applied to achieve improved performance on platinum-based catalysts. In this context, reduced graphene oxide sheets were developed to stabilize and support platinum nanoparticles, as well as to enhance the electrochemically active surface area. A conventional wet chemical methodology for synthesizing and processing graphene oxide from graphite was improved for assembling bi and/or tridimensional nanostructures with relevant microstructural features to electrocatalysis. The approach for reducing mass-transport resistances was based on a three-step design strategy aimed at the controlled introduction of defects, in situ cetyltrimethylammonium bromide (CTAB) surfactant functionalization/intercalation and a manufacturing perspective on graphene dispersions from a basic solution thermodynamics theory. The unique nanoarchitecture provided a high density of active sites, which incurred in a mass current value increased by about 2.5 and 5.4 times compared to platinum supported on state-of-the-art carbon black and restacked graphene, respectively.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-02T20:34:02Z No. of bitstreams: 1 KayniLima.pdf: 2329691 bytes, checksum: f4483166f9b35c9a8cce0606f988ddb5 (MD5) / Made available in DSpace on 2017-06-02T20:34:02Z (GMT). No. of bitstreams: 1 KayniLima.pdf: 2329691 bytes, checksum: f4483166f9b35c9a8cce0606f988ddb5 (MD5) Previous issue date: 2016-07-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The present work describes the development of a novel platform for the electrocatalysis of isoniazid (INH) employing a glassy carbon electrode (GCE) modified with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) adsorbed on reduced graphene oxide (rGO). The modified electrode (GCE/OGr/DDQ) was covered with a Náfion® film to avoid the leaching out of the composite from electrodic surface. The materials rGO, DDQ and rGO/DDQ were characterized by Fourier transform infrared spectroscopy (FTIR) and the analytical response of the sensor for the analyte was studied by cyclic voltammetry (CV) and amperometry techniques. The sensor showed excellent electrocatalytic activity for INH oxidation with a decrease in the overpotential about 660 mV vs Ag/AgCl and anodic peak current about 4 times higher than the observed response at an electrode unmodified. The increase of the reaction rate for INH was attributed to the efficient electron transfer between the studied specie and immobilized material on the surface of the GCE surface. The number of electrons determined in the INH oxidation process on the modified electrode was equal to 2. Under the optimized operational and experimental conditions, the sensor showed a wide linear range for INH from 0.5 to 380 µmol L-1 for n = 16 (r2 = 0.999); good sensibility and limit of detection equal to 0.42 µA µmol-1 L, and 0.15 µmol L-1, respectively. The proposed sensor was successfully applied for INH determination in drug samples used in the tuberculosis treatment and results obtained in studies of addition and recovery showed that the proposed method has good accuracy with recovery values between 98.46 and 101 % to INH. / O presente trabalho descreve o desenvolvimento de uma nova plataforma para a eletrocatálise de isoniazida (INH) empregando um eletrodo de carbono vítreo (ECV) modificado com 2,3-dicloro-5,6-diciano-p-benzoquinona (DDQ) adsorvido em óxido de grafeno reduzido (OGr). O eletrodo modificado (ECV/OGr/DDQ) foi coberto com um filme de náfion® para evitar o lixiviamento do compósito da superfície eletródica. Os materiais OGr, DDQ e OGr/DDQ foram caracterizados por Espectroscopia no infravermelho com transformada de Fourier (FTIR) e a resposta analítica do sensor para o analito foi estudada através das técnicas voltametria cíclica (CV) e amperometria. O sensor apresentou uma excelente atividade eletrocatalítica para a oxidação de INH com uma diminuição do sobrepotencial cerca de 660 mV vs Ag/AgCl e corrente de pico anódica quatro vezes maior que a resposta observada em um eletrodo não modificado. O aumento na velocidade de reação para a INH foi atribuído à eficiente transferência eletrônica entre a espécie estudada e os materiais imobilizados na superfìcie do ECV. O número de elétrons determinado no processo de oxidação de INH sobre o eletrodo modificado foi igual a 2. Sob as condições experimentais e operacionais otimizadas, o sensor apresentou uma relação linear para a INH de 0,5 à 380 µmol L-1 para n=16 (r2 = 0,999); boa sensibilidade e limite de detecção igual a 0,42 µA µmol-1 L e 0,15 µmol L-1, respectivamente. O sensor proposto foi utilizado com sucesso para a determinação INH em amostras de medicamentos utilizadas no respectivo tratamento da tuberculose e os resultados obtidos nos estudos de adição e recuperação mostraram que o método proposto apresenta boa exatidão com valores de recuperação entre 98,46 e 101% para a INH.