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Dans ce travail de recherche, des oxydes mixtes dopés par des métaux nobles ont été préparés et mis en œuvre dans la réaction d'oxydation catalytique du chlorure de vinyle (VC). Les catalyseurs d'oxyde composite de Co-Ce ont été préparés par des procédés sol-gel et testés pour l'activité d'oxydation du VC. L'analyse XPS a certifié que l'introduction de Ce favorisait la présence d'espèces de Co2 + et de Ce3 +, ce qui modifie l'environnement de coordination du réseau d'oxygène et génère plus de vacations d'oxygène. Les oxydes de cobalt modifiés par Ru ont été préparés et étudiés pour l'oxydation du VC. L'analyse XPS montre que le Ru4 + et le Co2 + modifie la concentration des espèces oxygènes sur la surface. Une proportion relative élevée de Co2+ et de Ru4+ perturbe également les lacunes en oxygène. Cela impacte l'activité catalytique et diminue la quantité de sous-produits chlorés. Des mousses cellulaires mésostructurées de phosphate de cobalt-SiO2 (CoPO-MCFs) ont été synthétisées avec succès par la méthode de croissance in situ. Les analyses XPS confirment une augmentation d'espèces d'oxygène de surface pour ce système catalytique. L'énergie apparente d'activation confirme cette tendance. L'influence de la morphologie des particules de Co3O4, sur l'activité catalytique du méthyl benzène et du chlorure de vinyle a été étudiée. Le Co3O4 cubique a montré une meilleure activité et une meilleure stabilité que celle de Co3O4 sphérique. La structure cubique, avec Co2 + exposée à la surface, est le site actif de l'oxydation / In this research works, composite oxides, noble metal supported oxides and noble supported MCFs were prepared, and their catalytic performances were investigated for the catalytic oxidation of vinyl chloride (VC). The Co-Ce composite oxide catalysts were prepared by citrate sol-gel methods, and tested for the activity of VC oxidation. The catalyst with high performance is the molar ratio of Co/Ce=7:3. The XPS analyse certified that the Ce introduction favored the presence of Co2+ and Ce3+ species, which changed the coordination environment of the oxygen lattice and generated more oxygen vacancies. At last, this catalyst exhibited a good performance and stability during 110 h of time on stream at 300 oC. Ru-modified cobalt oxides were prepared and studied for the VC oxidation. The XPS analyse certified that the Ru4+ will be in synergy with Co2+ concentration and this would also change the chemical coordination of oxygen on the surface. High relative proportion of Co2+ and Ru4+ will also devote to oxygen defects or vacancies. This would increased the catalytic activity and decrease the amount of chlorinated by-products.A novel heterostructured material, cobalt phosphate-SiO2 mesostructured cellular foams (CoPO-MCFs), was successfully synthesized by the in-situ growth method. The XPS confirmed a higher amount of surface oxygen species. The activation energy calculated from Arrhenius plots showed a lower value for VC oxidation. The influence of Co3O4 morphology, including cube and sphere, on catalytic activity of methylbenzene and vinyl chloride was studied. The Co3O4 cube had shown better activity and stability than that of the Co3O4 sphere. The cube structure, with Co2+ exposed on the surface, acted as the active site of the oxidation

Nanotubes (inner diameter of 8nm and outer diameter of 10nm with a length of up to several hundred nm) and nanowires (diameter 20 – 50nm and up to several μm in length) of TiO₂-B have been synthesised and characterised for the first time. These exhibit excellent properties as a host for lithium intercalation and are able to accommodate lithium up to a composition of Li₀.₉₈TiO₂-B for the nanotubes and Li₀.₈₉TiO₂-B for the nanowires. Following some irreversible capacity on the first cycle, which could be reduced to 4% for the nanowires, capacity retention for the nanowires is 99.9% and for the nanotubes is 99.5% per cycle. In both cases, the cycling occurs at ~1.6V versus lithium. The cycling performance was compared with other forms of bulk and nano-TiO₂, all of which were able to intercalate less lithium. Nanowires of VO₂-B (50 – 100nm in diameter and up to several μm in length) were synthesised by a hydrothermal reaction and characterised. By reducing the pressure inside the hydrothermal bomb, narrower VO₂-B nanowires with a diameter of 2 – 5nm and length of up to several hundred nm were created - some of the narrowest nanowires ever made by a hydrothermal reaction. These materials are isostructural with TiO₂-B and were also found to perform well in rechargeable lithium ion batteries, being able to intercalate 0.84Li for the ultra-thin nanowires and 0.57Li for the standard nanowires. The standard VO₂-B nanowires have a capacity retention of 99.8% and the ultra-thin nanowires have 98.4% per cycle after some irreversible capacity on the first cycle. This was found to improve markedly when different electrolytes were used. Macroporous Co₃O₄ (pore size 400nm with a surface area of 208m²/g) was prepared and cycled in rechargeable lithium cells with capacities of 1500mAh/g being achieved. The structure was found to break down on the first cycle and after this the material behaved in the manner of Co₃O₄ nanoparticles. Finally a new candidate for next generation rechargeable lithium batteries was examined; Li/O₂ cells. The cathode is composed of porous carbon in which Li⁺, e⁻ and O₂ meet to form Li₂O₂ on discharge. The reaction is reversible on charge. Capacities of 2800mAh/g can be achieved when 5%mole of αMnO₂ nanowires catalyst is used. Fade is high at 3.4% per cycle meaning that there is much work to do to develop these into a commercial prospect.

Submitted by Nilton Francelosi Azevedo Neto (nilton@fc.unesp.br) on 2018-11-22T13:54:33Z No. of bitstreams: 1 Azevedo Neto- Tese POSMAT-2018.pdf: 3312025 bytes, checksum: 69a53514543bbe65b47c2fd62ddb6168 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-11-22T16:48:03Z (GMT) No. of bitstreams: 1 azevedoneto_nf_dr_bauru.pdf: 3312025 bytes, checksum: 69a53514543bbe65b47c2fd62ddb6168 (MD5) / Made available in DSpace on 2018-11-22T16:48:03Z (GMT). No. of bitstreams: 1 azevedoneto_nf_dr_bauru.pdf: 3312025 bytes, checksum: 69a53514543bbe65b47c2fd62ddb6168 (MD5) Previous issue date: 2018-09-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A motivação para este trabalho foi buscar uma melhor compreensão sobre o processo de crescimento dos filmes de óxido de cobalto pela técnica de DC magnetron sputtering reativo. Os filmes de interesse foram depositados sobre substratos de sílica amorfa (a -SiO2 ), aluminato de lantânio (LaAlO3 ) e safira - c (Al2O3- c) usando diferentes valores de potência de deposição e fluxo de oxigênio . As condições de crescimento dos filmes foram analisadas utilizando simulação computacional do processo de sputtering reativo baseada no modelo de Depla, medidas da emissão óptica das espécies presentes no plasma e monitor amento da taxa de crescimento através de uma microbalança de quartzo. Os resultados de difração de raios X mostraram que em baixa potência é obtida a fase Co3O4 espinélio, enquanto que em alta potência os filmes apresentaram a fase CoO cúbica . A s simulações computacionais do processo de sputtering reativo indicaram que , quando as potências de deposição são baixas, o processo de crescimento dos filmes ocorre com o alvo no regime “envenenado” . Em contraste, altas potencias favorece m o regime metálico do alvo. Medidas de emissão do plasma de deposição mostraram que em baixa potência de deposição a intensidade da linha de emissão do oxigênio é alta , porém com o aumento da potência sua intensidade diminui e a d a linha do cobalto aumenta. O s filmes de Co 3 O 4 depositados sobre substratos cristalinos apresentaram resultados promissores . Medidas de difração de raios X de alta resolução , utilizando radiação síncrotron , indicaram que a deposição do Co 3 O 4 sobre Al2O3 - c resultou em crescimento epitaxial na qual a direção [ 111] do cristal de Co 3 O 4 é perpendicular à superfície do substrato de safira - c (0001). Enquanto que a deposição sobre LaAlO 3 resultou em crescimento com forte textura de orientação, com as direções [220] e [400] perpendiculares à superfície dos substratos . Os espectros Raman dessas amostras apresentaram picos de vibração bem definidos e característicos da fase Co 3 O 4 e a análise do Raman polarizado do s filmes de Co 3 O 4 sobre Al 2 O 3 - c concorda m com as regras de seleção para a orientação [111] . Para os filmes c om fase Co 3 O 4 , medidas de transmitância na região do UV - Vis - NIR mostraram alta absorção na região do visível e bandas de absorção no infravermelho próximo relacionadas a transições eletrônicas dos íons de Co 2+ e Co 3+ . Para esse crescimento observou - se também resposta intensa de fotocondutividade com exc itação em 405 nm e 532 nm em 10 K. Testes preliminares de fotocatálise indicaram que os filmes de Co 3 O 4 produzidos possuem uma pequena atividade fotocatalítica para degradação do corante Rodamina B. Neste trabalho uma correlação direta entre as condições de crescimento e as mudança s de fase do s filmes foi obtida, demonstrando a versatilidade da técnica de sputtering para crescimento de filmes de óxido de cobalto para estudos científicos e aplicações tecnológicas. / The motivation for this work was to obtain a better understanding of the growth process of cobalt oxides by the DC magnetron reactive sputtering technique. The films were dep osited on amorphous silica (a-SiO2), lanthanum aluminate (LaAlO3) and sapphire-c (c-Al2O3) substrates using different values of deposition power and oxygen flow. The conditions of growth of the films were analyzed using the optical analysis of the species present in the plasma and the monitoring of the growth rate through a quartz microbalance. The X-ray diffraction results showed that at lower powers the Co3O4 phase was obtained, while at high er power s the films presented the CoO cubic phase. The computational simulations of the reactive sputtering process indicated that, at low deposition power, the gro wth process of the films occurs with the target in the "poisoned" regime, while in high powers it favors the metallic regime of the target. Plasma emission measurements showed that at low deposition power the oxygen intensity is high while at high power it s intensity decreases and that of cobalt increases. The Co 3 O 4 films deposited on crystalline substrates showed promising results. High - resolution X-ray diffraction measurements using synchrotron radiation indicated that the deposition of Co3O4 on c-Al2O3 resulted in epitaxial growth , in which the direction [111] is perpendicular to the surface of the c - sapphire (0001) substrates. However, the deposition on LaAlO 3 resulted in growth with strong texture in the directions [220] and [400]. The Raman spectra of these samples showed well - defined vibration peaks characteristic of the Co3O4 phase . The polarized Raman analysis of Co 3 O 4 deposited on c-Al2O3 agrees with the selection rules for the [111] orientation, in agreement with the high resolution X-ray diffraction analysis . In the optical transmittance measurements , t he films with Co 3 O 4 phase displayed high absorption bands in the region of the visible and near - infrared . These bands are related to el ectronic transitions of the Co2+ and Co3+ ions. For these films , strong photoconductivity responses were observed for excitations at 405 nm and 532 nm at 10 K . Preliminary photocatalysis tests indicated that the Co3O4 films produced by sputtering have a small photocatalytic activity for Rhodamine B (RhB) dye degradation. Concluding , a direct correlation between the growth conditions and the phase changes of the films was obtained, demonstrating the versatility of the sputtering technique for the growth of cobalt oxide films for scientific studies and technological applications.

Les travaux de recherche actuels menés dans le domaine des supercondensateurs s’orientent vers l’augmentation des densités d’énergie, notamment via le développement de supercondensateurs hybrides "oxydes de métaux de transition / carbones activés". Dans ce contexte, les présents travaux avaient pour objectif d’évaluer les propriétés d’oxydes de cobalt nanométriques en tant que matériaux d’électrode positive pour supercondensateur hybride.Ces oxydes de cobalt, de structure spinelle, sont préparés par précipitation de nitrate de cobalt en milieu basique (T < 90 °C). Ils possèdent une formule chimique du type HxLiyCo3-δO4•zH2O et présentent une bonne conductivité électronique grâce à la présence d’ions H+, Li+ et Co4+. Les analyses par DRX, ATG, RMN et les mesures de conductivité électroniques ont mis en évidence une réorganisation de la structure spinelle de ces matériaux sous l’effet d’un traitement thermique, conduisant à une augmentation du rapport Co4+/Co3+ ainsi qu’à une amélioration des propriétés de transport électrique. L’association d’une conductivité électronique élevée et d’une forte surface spécifique confère à ces oxydes des performances prometteuses en tant que matériaux d’électrode.L’étude des propriétés électrochimiques a montré la présence de deux modes de stockage des charges, l’un électrostatique (double couche électrochimique) et l’autre faradique via l’oxydation et la réduction du cobalt. Elle a également permis de déterminer la signature électrochimique de ces oxydes (capacité, fenêtre de potentiels), prérequis indispensable à leur intégration dans une cellule complète. Finalement, un supercondensateur hybride "oxyde de cobalt / carbone activé" a été assemblé et équilibré, donnant lieu à des performances attractives (61,6 F/g sur 1,60 V). / Investigations on supercapacitors are focusing on increasing energy densities, in particular with the development of hybrid supercapacitors "metal oxides / activated carbons". In this field, the present work aims at evaluating nanometric cobalt oxides as positive electrode material for hybrid supercapacitors.These oxides, with spinel structure, are synthesized by precipitation of cobalt nitrate in a basic medium (T < 90 °C). They exhibit formulae such as HxLiyCo3-δO4•zH2O and good electronic properties thanks to the presence of H+, Li+ and Co4+ ions. XRD, TGA, NMR analysis as well as electronic measurements have highlighted a structural reorganization of the spinel structure under thermal treatment, resulting in increase of the Co4+/Co3+ ratio and an enhancement of the electronic transport properties. The high electronic conductivity together with a huge specific surface area imparts these oxides promising performances as electrode material.The study of the electrochemical properties underlines two charge storage mechanisms, one electrostatic (electrochemical double layer) and the other one faradic through the oxidation and the reduction of cobalt. The electrochemical signature (capacity, potential window) of these oxides was also determined in order to develop a complete cell. Finally, a hybrid supercapacitor "cobalt oxide / activated carbon" was assembled and balanced, revealing attractive performances (61,6 F/g over 1,60 V).

Made available in DSpace on 2016-06-02T19:55:32Z (GMT). No. of bitstreams: 1 4381.pdf: 2748711 bytes, checksum: 4ba9831d0665b24b6f48f775d30927d2 (MD5) Previous issue date: 2012-04-13 / Universidade Federal de Minas Gerais / The minimization of the emissions of nitrogen oxides (NOx) is a subject of crucial interest, since them cause serious environmental problems which affect human health, vegetation and fauna. With the purpose to abate NOx, processes involving their catalytic reduction show strong potential. In the case of the reduction of NO with CO a meaningful advantage arises, once both pollutants are removed simultaneously. In order to obtain efficient and stable catalysts for this reaction, many studies have been done with the aim to improve the catalytic activity by achieving a better favorable metal-support interaction to the occurrence of the reaction and a better distribution of the active phases on the support. In this context, the objective of this study was to prepare Cu, Fe and Co based catalysts supported on TiO2, CeO2 and ZrO2 to be applied in the abatement of NO with CO. The addition of the precursors of the active phases was made during the synthesis of the support via the sol-gel method (in situ addition). Furthermore, catalysts with the same composition were prepared by conventional methods. Results from the N2 adsorption/desorption measurements show that the sol-gel method was efficient to prepare supports with improved textural properties. H2-TPR and UVVIS-DRS data evidenced the presence of Cu, Fe or Co oxides in the respective catalysts, which mostly did not show characteristic X-ray diffraction peaks of those oxide phases, suggesting their high dispersion on the supports. In general, results of the reduction of NO to N2 with CO revealed that the catalysts prepared via sol-gel are as active as those prepared by conventional routes, which demonstrate the great potential of the catalysts preparation via the sol-gel in situ procedure, which diminishes the number of the synthesis steps saving time and energy. In general, among the studied supports, ceria presented a more favorable metal-support interaction. In the presence of O2, SO2 and water steam, catalysts 6,5Cu/CeP, 5,5CuZrSG and 8,4Fe/TiC showed no significant changes in their activity and selectivity, indicating that they present high stability to be used under the severe conditions of real processes. / A minimização das emissões de óxidos de nitrogênio (NOx) é assunto de interesse crucial, pois geram graves problemas ambientais que afetam à saúde humana, à flora e à fauna. Para abater os NOx, processos envolvendo à sua redução catalítica apresentam forte potencial. No caso da redução catalítica de NO com CO, tem-se a vantagem adicional de minimizar as emissões de ambos poluentes. Para a obtenção de catalisadores eficientes e estáveis para essa reação, muitos estudos têm sido desenvolvidos no sentido de aumentar a atividade por meio de uma interação metalsuporte mais favorável ao processo reativo e de se conseguir uma melhor distribuição da fase ativa no suporte. Nesse contexto, o objetivo do presente estudo foi preparar catalisadores para a redução de NO com CO à base de óxido de Cu, Fe ou Co, suportados em TiO2, CeO2 ou ZrO2, com a adição do precursor da fase ativa durante a preparação do suporte via processo sol-gel (adição in situ). Além disso, catalisadores de mesma composição foram preparados por rotas convencionais. Resultados de medidas de adsorção/dessorção de N2 dos suportes mostram que o método sol-gel utilizado é mais eficiente no preparo de suportes com propriedades texturais melhoradas. Análises de RTP-H2 e ERD-UVVIS evidenciaram a presença dos óxidos de Cu, Fe ou Co em todos os catalisadores, os quais, em sua maioria, não apresentaram picos de difração de raios X característicos dessas fases, o que sugeriu sua alta dispersão no suporte. Em geral, os resultados da redução de NO a N2 com CO mostraram que os catalisadores preparados pelo método sol-gel in situ são tão ativos quanto os catalisadores preparados por métodos convencionais, o que demonstra o forte potencial desse procedimento, que resulta no uso de um número menor de etapas na preparação do catalisador, com a consequente economia de tempo e energia. De maneira geral, dentre os suportes estudados a céria mostrou uma relação metal-suporte mais favorável ao processo de óxidoredução. Os catalisadores 6,5Cu/CeP, 5,5Cu-ZrSG e 8,4Fe/TiC, na presença de O2, SO2 e vapor de água não apresentaram alteração significativa da sua atividade e seletividade, mostrando uma alta estabilidade para atuar sob as drásticas condições dos processos reais.

In this project, the TMP method was employed to produce “active sites.” These active sites are for influencing and controlling the Co₃O₄ growth. One of the aims was to investigate what effect the grafting of the molecular precursor has on the nature and distribution of active sites on the various support materials. The second aim was to investigate the effect an increase in molecular precursor loading, in various impregnation steps, has on the nature and distribution of the active sites. The third aim was to investigate the effect of the steric constraints of ligand groups, by changing the molecular precursor, on the nature and distribution of active sites. The fourth aim was to use the different aspects discussed above and apply them to investigate what effect the above-mentioned modifications have on Co₃O₄ morphology. While another aim was to investigated what effect varying the quantity of Co(NO₃)₂•6H₂O has on Co₃O₄ morphology. Lastly, we investigated what effect varying the impregnation procedure and calcination temperature have on the Co₃O₄ morphology. The effect the support has on the phase of titanium molecular precursor was investigated using molecular precursor, ⁱPrOTi[OSi(O[superscript(t)]Bu₃)]₃. The supports used were Silica 922, NanoDur, Aerosil 200, Stöber spherical silica, SBA-15, mod MCM-41 and sMCM-41. The molecular precursor ⁱPrOTi[OSi(O[superscript(t)]Bu₃)]₃ was revealed to be in the orthorhombic TiO₂ with space group P(cab), normal brookite lattice, on Silica 922 after calcination but only an isolated area displaying this morphology. Generally we do not observe any TiO₂ on the support, which indicates that we have produce site-isolated sites, suggesting the TMP method has been successful on all of the various supports. The emphasis is placed on the effect of this molecular precursor and the respective support has on the Co₃O₄ morphology in Chapter 3. In this Chapter, a unique morphology was observed on Silica 922 which showed Co₃O₄ nanorods of cubic Co₃O₄ in the space group Fd-3m. Silica 922 was used for the remainder of the thesis to investigate the effect the quantity of molecular precursor has on the nature of active sites and Co₃O₄ morphology in Chapter 4. This support was also used to investigate the effect the amount of Co(NO₃)₂•6H₂O has on Co₃O₄ morphology in Chapter 5. This support was lastly used to investigate the steric constraints of the ligand groups, Ti[OSi(O[superscript(t)]Bu)₃]₄ (TiSi4), ⁱPrOTi[OSi(O[superscript(t)]Bu)₃]₃ (TiSi3), (OtBu)₃TiOSi(O[superscript(t)]Bu)₃ (TiSi) and the least sterically constrained Ti(OⁱPr)₄ has on the loading of precursor and Co₃O₄ morphology in Chapter 6.

Ce travail de thèse concerne l’application d’une nouvelle technologie de préparation de catalyseurs propres Co/Al2O3 pour la synthèse de Fischer Tropsch (FT). Les matériaux sont préparés à l’aide d’un procédé de revêtement à sec dans un mélangeur à haut cisaillement le «Picomix». Les conditions opératoires, les supports en alumine, la taille des cristallites de cobalt et la teneur en charge de cobalt ont été optimisés pour augmenter l’activité catalytique du Co/Al2O3. De même, une modélisation DEM a été effectuée pour décrire le comportement des poudres dans le mélangeur. Les résultats expérimentaux montrent une très bonne adhésion des nanoparticules de Co3O4 à la surface des particules de Al2O3 pour une vitesse de rotation élevée pendant une courte période. Les particules γ-Al2O3 traitées thermiquement présentent une résistance mécanique améliorée des catalyseurs, mais une activité catalytique relativement faible. La taille des cristallites de Co3O4 a diminué de 64nm à 11nm après broyage dans un broyeur à boulets planétaire à 600 rpm/min pendant 40h. Enfin, le catalyseur optimal a été obtenu à 5000 rpm/min pendant 5min avec 5% en poids de cobalt. Le catalyseur obtenu présente des résultats catalytiques : conversion élevée en CO (37%) , sélectivité élevée en hydrocarbures en C5+ (75%) et faible sélectivité en CH4 (13%) à 250oC. La modélisation numérique par DEM a révélé que les paramètres liés aux conditions opératoires, la géométrie du dispositif et aux propriétés intrinsèques des particules avaient un impact sur le comportement des particules et la qualité de l’enrobage des matériaux / This thesis concerns the application of a novel preparation technology for Co/Al2O3 clean catalysts applied in Fischer Tropsch (FT) synthesis. The catalysts were prepared using a dry coating process in a high shear mixer “Picomix”. The operating conditions, alumina supports, cobalt crystallite size and cobalt loading content were optimized to increase the catalytic activity of Co/Al2O3 catalysts. Besides, DEM modeling was performed to describe the behavior or powders in the mixer. Experimental results showed a very good adhesion of the nano Co3O4 particles on the surface of Al2O3 particles after processed in the mixer under a high rotational speed and a short time. The heat-treated Al2O3γ particles presented enhanced mechanical strength of catalysts, however, exhibited relatively low catalytic activity. The Co3O4 crystallite size decreased from 64 nm to 11 nm after milling in planetary ball mill under 600 rpm for 40 h. Finally, the optimal catalyst was prepared by mixing milled-Co3O4 and Al2O3γ particles in “Picomix” under 5000 rpm for 5 min with 5 wt.% of Co. The obtained catalyst presented high CO conversion (37 %), high C5+ hydrocarbons selectivity (75 %) and low CH4 selectivity (13 %) in FT synthesis reaction at 250 oC. The DEM mumerical modeling revealed that the parameters related to operating condition, device geometry, and particle intrinsic properties had an impact on particle behavior and coating quality of materials

The main objective of nanotechnology is to build self-powered nanosystems that are ultrasmall in size, exhibit super sensitivity, extraordinary multi functionality, and extremely low power consumption. As we all know that 21st century has brought two most important challenges for us. One is energy shortage and the other is global warming. Now to overcome these challenges, it is highly desirable to develop nanotechnology that harvests energy from the environment to fabricate self-power and low-carbon nanodevices. Therefore a self-power nanosystem that harvests its operating energy from the environment is an attractive proposition. This is also feasible for nanodevices owing to their extremely low power consumption. One advantageous approach towards harvesting energy from the environment is the utilization of semiconducting piezoelectric materials, which facilitate the conversion of mechanical energy into electrical energy. Among many piezoelectric materials ZnO has the rare attribute of possessing both piezoelectric and semiconducting properties. But most applications of ZnO utilize either the semiconducting or piezoelectric property, and now it’s time to fully employ the coupled semiconducting-piezoelectric properties to form  the basis for electromechanically coupled nanodevices. Since wurtzite zinc oxide (ZnO) is structurally noncentral symmetric and has the highest piezoelectric tensor among tetrahedrally bonded semiconductors, therefore it becomes a promising candidate for energy harvesting applications. ZnO is relatively biosafe and biocompatible as well, so it can be used at large scale without any harm to the living environment. The synthesis of another transition metal oxide known as Co3O4 is also important due to its potential usage in the material science, physics and chemistry fields. Co3O4 has been studied extensively due to low cost, low toxicity, the most naturally abundant, high surface area, good redox, easily tunable surface and structural properties. These significant properties enable Co3O4 fruitful for developing variety of nanodevices. Co3O4 nanostructures have been focused considerably in the past decade due to their high electro-chemical performance, which is essential for developing highly sensitive sensor devices. I started my work with the synthesis of ZnO nanostructures with a focus to improve the amount of harvested energy by utilizing oxygen plasma treatment. Then I grow ZnO nanorods on different flexible substrates, in order to observe the effect of substrate on the amount of harvested energy. After that I worked on understanding the mechanism and causes of variation in the resulting output potential generated from ZnO nanorods. My next target belongs to an innovative approach in which AFM tip decorated with ZnO nanorods was utilized to improve the output energy. Then I investigated Co3O4 nanostructures though the effect of anions and utilized one of the nanostructure to develop a fast and reliable pH sensor. Finally to take the advantage of higher degree of redox chemistry of NiCo0O4 compared to the single phase of nickel oxide and cobalt oxide, a sensitive glucose sensor is developed by immobilizing glucose oxidase. However, there were problems with the mechanical robustness, lifetime, output stability and environmental adaptability of such devices, therefore more work is going on to find out new ways and means in order to improve the performance of fabricated nanogenerators and sensors.

Les travaux de recherche actuels menés dans le domaine des supercondensateurs s'orientent vers l'augmentation des densités d'énergie, notamment via le développement de supercondensateurs hybrides "oxydes de métaux de transition / carbones activés". Dans ce contexte, les présents travaux avaient pour objectif d'évaluer les propriétés d'oxydes de cobalt nanométriques en tant que matériaux d'électrode positive pour supercondensateur hybride.Ces oxydes de cobalt, de structure spinelle, sont préparés par précipitation de nitrate de cobalt en milieu basique (T < 90 °C). Ils possèdent une formule chimique du type HxLiyCo3-δO4*zH2O et présentent une bonne conductivité électronique grâce à la présence d'ions H+, Li+ et Co4+. Les analyses par DRX, ATG, RMN et les mesures de conductivité électroniques ont mis en évidence une réorganisation de la structure spinelle de ces matériaux sous l'effet d'un traitement thermique, conduisant à une augmentation du rapport Co4+/Co3+ ainsi qu'à une amélioration des propriétés de transport électrique. L'association d'une conductivité électronique élevée et d'une forte surface spécifique confère à ces oxydes des performances prometteuses en tant que matériaux d'électrode.L'étude des propriétés électrochimiques a montré la présence de deux modes de stockage des charges, l'un électrostatique (double couche électrochimique) et l'autre faradique via l'oxydation et la réduction du cobalt. Elle a également permis de déterminer la signature électrochimique de ces oxydes (capacité, fenêtre de potentiels), prérequis indispensable à leur intégration dans une cellule complète. Finalement, un supercondensateur hybride "oxyde de cobalt / carbone activé" a été assemblé et équilibré, donnant lieu à des performances attractives (61,6 F/g sur 1,60 V).