Magister Scientiae - MSc / With an increase in the amount of harmful carbon emissions in the atmosphere as well as a decrease in the availability of fossil fuels, there is a relatively high demand for alternate energy devices. Solar cells have become an alternative option in aid of leading the way for clean energy; however these devices are relatively expensive and have an efficiency that is relatively low in comparison to that of fossil fuelled energy. As a result the cost of the solar cell needs to be reduced by reducing the amount of silicon used in order to compete with fossil fuelled devices; however this decrease would lead to a decrease in efficiency. In recent years silver nanoparticles have been extensively researched as a result of its extraordinary optical, electrical, catalytic, magnetic and antibacterial properties. As a result of these properties, the nanoparticles may be applied to many research areas such as photovoltaics, catalysis and medical fields. The optical properties of silver nanoparticles may thus be exploited in order to increase absorption and in turn the efficiency of the solar cell devices. This study focuses on the optimization of the polyol synthesis to possibly obtain uniformly dispersed silver nanoparticles. The silver nanoparticles would then be incorporated onto amorphous silicon thin films, deposited by hot wire chemical vapour deposition, by spraying a suspension of the silver nanoparticles onto the thin films. The silver nanoparticles were viii characterized by Ultra Violet Visible Spectroscopy (UV-VIS), High Resolution Transmission Electron Microscopy, X-ray Diffraction, and Thermogravimetric Analysis. The thin films with the incorporated silver nanoparticles were characterized by UV-VIS, and High Resolution Scanning Electron Microscopy. It was shown that silver nanoparticles with various morphologies were produced by the polyol synthesis and may be used to enhance light trapping of thin film photovoltaic devices.

Les nanoparticules, outils d'innovation dans le domaine biomédical, promettent des avantages significatifs, notamment au niveau du diagnostic et du traitement. Les nanoparticules d'or de forme anisotrope, nanobâtonnets, nanoprismes etc. présentent une absorption de la lumière dans le domaine du proche infrarouge, ce qui s'accompagne d'une augmentation locale de la température. Cet échauffement local provoqué par les nanoparticules d'or est exploité dans des thérapies, comme l'hyperthermie photo-assistée. Quant aux nanoparticules de fer, ce sont leurs propriétés magnétiques qui sont visées. Elles sont principalement mises à profit dans l'imagerie médicale, les nanoparticules de fer étant de bons agents de contraste pour l'IRM. Au cours de cette thèse nous nous somme intéressés d'une part à la synthèse de nanoparticules d'or de forme anisotrope sans utilisation, en tant qu'agent structurant, d'un tensioactif cationique, redouté pour sa toxicité. Pour cela la méthode polyol a été utilisée. En fonction des conditions de synthèse des plaquettes ou des cubes d'une taille sans précédent (ca. 21-50 nm) pour cette méthode ont été obtenus. Leur fonctionnalisation par des polymères de type PEG a été ensuite réalisée. D'autre part des nanoparticules de fer zero-valent de ca. 13 nm ont été élaborées en utilisant une approche organométallique dans le but de conserver une aimantation élevée nécessaire pour les applications envisagées. Nous avons réussi leur transfert dans l'eau, tout en conservant un cœur de fer zéro-valent de ca. 10 nm et donc une forte aimantation, grâce à des ligands comportant un groupement d'ancrage à la surface de nanoparticules type acide phosphonique. Des mesures préliminaires de leur relaxivité transversale ont été réalisées, ouvrant des perspectives très prometteuses en tant qu'agent de contraste en IRM. / Nanoparticles, tools of innovation in the biomedical field, promise significant advantages, notably in terms of diagnostic and therapy. Gold nanoparticles of anisotropic shape, nanorods, nanoprisms, etc. exhibit light absorption in the near-infrared region, which is accompanied by a local increase in temperature. This local warm-up is used in therapies, such as photo-assisted hyperthermia. In the case of iron nanoparticles, their magnetic properties are of interest for applications. They are mainly used in medical imaging, iron nanoparticles being good contrast agents for MRI. In this thesis, we have been interested in the synthesis of gold nanoparticles of anisotropic shapes free of cationic surfactants as structuring agent, because of their toxicity. As alternative the polyol method has been used. Depending on the synthesis conditions, platelets or cubes with an unprecedented size (ca. 21-50 nm) for this king of synthetic method have been obtained. On the other hand, zero-valent iron nanoparticles of ca. 13 nm have been developed using an organometallic approach in order to obtain nanoparticles with a high magnetization, necessary for the envisaged applications. We have succeeded in transferring iron nanoparticles into water, while conserving a zero-valent iron core of ca.10 nm and therefore a strong magnetization, thanks to ligands bearing a phosphonic acid head group in order to anchor them to the surface of the nanoparticles. Preliminary measurements of their transversal relaxivity have been carried out, opening up promising prospects as contrast agent for MRI.

Submitted by Liliane Ferreira (ljuvencia30@gmail.com) on 2018-09-19T15:25:10Z No. of bitstreams: 2 Tese - Thiago Eduardo Pereira Alves - 2018.pdf: 6446029 bytes, checksum: 608f540fa5df66d012459688ced998d9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-09-20T11:36:11Z (GMT) No. of bitstreams: 2 Tese - Thiago Eduardo Pereira Alves - 2018.pdf: 6446029 bytes, checksum: 608f540fa5df66d012459688ced998d9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-09-20T11:36:11Z (GMT). No. of bitstreams: 2 Tese - Thiago Eduardo Pereira Alves - 2018.pdf: 6446029 bytes, checksum: 608f540fa5df66d012459688ced998d9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-07-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / n this study we investigated the structural, optical band-gap, and magnetic properties of CoFe2-xYxO4 ) nanoparticles (NPs) synthesized using a combustion reaction method without the need for subsequent heat treatment or the calcing process. The particle size measured from X-ray diffraction (XRD) patterns and transmission electron microscope (TEM) images confirms the nanostructural character in the range of 16–36 nm. The optical band-gap (Eg) values increase with the Y3+ ion concentration being 3.30 and 3.58 eV for x = 0,00 and x = 0,04, respectively. The presence of yttrium in the cobalt ferrite (Y-doped cobalt ferrite) structure affects the magnetic properties. For instance, the saturation magnetization, MS and remanent magnetization, Mr, decrease from 69 emu.g-1 to 33 and 28 to 12 emu.g-1 for x = 0,00 and x = 0.04, respectively. On the other hand the coercivity, Hc, increases from 1100 to 1900 Oe for x = 0,00 and x = 0,04 at room temperature. Also we found that MS, Mr, and Hc decreased with increasing temperature up to 773 K. The cubic magnetocrystalline constant, K1, determined by using the ‘‘law of approach’’ (LA) to saturation decreases with Y3+ ion concentration and temperature. K1 values for x = 0,00 (x = 0,04) were 3,3 x 106 erg.cm-3 (2,0 x 106 erg.cm-3) e 0,4 x 106 erg.cm-3 (0,3 x 106 erg.cm-3) at 300 K and 773 K, respectively. The results were discussed in terms of inter-particle interactions induced by thermal fluctuations, and Co2+ ion distribution over tetrahedral and octahedral sites of the spinel structure due to Y3+ ion substitution. Also, in the present work, zinc oxide (ZnO) nanoparticles were prepared by the polyol method which consist of zinc acetate acetate and sodium acetate in propylene glycol solution with control over the hydrolysis reaction time and subjecting to the variation of reaction parameters, as ratio of hydrolysis (th) and ratio of acetate (ta). It was observed that the reaction time of the hydrolysis and the addition of ions had a strong effect on the morphology and size of the ZnO particles. For example, transmission electron microscopy (TEM) images revealed that the ZnO samples were synthesized for short time of RH (10 min) and long time (300 min) in small rods and in elongated rod forms, respectively. On the other hand, using only zinc acetate reagent, as the ZnO samples crystallized into a coarse spherical shape. These differences can be attributed to the polarization of the acetate and the propylene glycol, i.e., the greater amount of deficits present in the preferred growth solution of the ZnO crystals. In addition, the HR time does not change changes in the optical band gap. For example, values ​​controlled by the Kubelka-Munk model decreased from 3.31 eV to 3.28 eV for the short HR time and the long HR time, respectively. This can be explained in terms of defects and is due to the change in particle sizes. X-ray diffraction patterns (XRDs) revealed that all the units crystallized the typical wurtzite structure of ZnO. However, the relative intensity of the diffraction peak (002) of the ZnO samples was synthesized with zinc acetate and was higher than the sensations from zinc acetate as sodium acetate. That is, an indication of direction should be directed toward the preferential growth of the crystals. Therefore, the morphology of the ZnO samples can be adapted using the polyol method, just as the physical properties are important for some technological applications. / Neste trabalho, foram investigadas as propriedades estruturais, ópticas e magnéticas de nanopartículas de CoFe2-xYxO4 ) sintetizadas pelo método de reação de combustão sem tratamento térmico subsequente ou o processo de calcinação. Os tamanhos de partícula medidos a partir de padrões de difração de raios X (DRX) e imagens de microscopia eletrônica de transmissão (MET) confirmam nanoestruturas na faixa de 16-36 nm. Os valores de bandas ópticas (Eg) aumentam com a concentração de íons Y+3 sendo 3,30 e 3,58 eV para x = 0,00 e x = 0,04, respectivamente. A dopagem com ítrio na ferrita de cobalto afeta as propriedades magnéticas. Por exemplo, a magnetização de saturação (MS) e a magnetização remanescente (Mr), diminuem de 69 emu.g-1 para 33 e 28 para 12 emu.g-1 para x = 0,00 e x = 0,04, respectivamente. Por outro lado, a coercividade (HC), aumenta de 1100 para 1900 Oe para x = 0,00 e x = 0,04 à temperatura ambiente. Também foidescoberto que MS, Mr e HC diminuem com o aumento da temperatura até 773 K. A constante de anisotropia magnetocristalina (K1), determinada usando a lei de approach para magnetizações próximas à saturação diminuem com a concentração do íon Y3 + e com a temperatura. Os valores de K1 para x = 0,00 e (x = 0,04) foram 3,3 x 106 erg.cm-3 (2,0 x 106 erg.cm-3) e 0,4 x 106 erg.cm-3 (0,3 x 106 erg.cm-3) a 300 K e 773 K, respectivamente. Os resultados foram discutidos em termos de interações entre partículas induzidas por flutuações térmicas e distribuição dos íons Co2+ nos sítios tetraédricos e octaédricos da estrutura espinélio, principalmente devido à substituição iônica pelo Y3+. Também neste trabalho preparou-se nanopartículas de óxido de zinco (ZnO) pelo método do poliol utilizando acetato de zinco e acetato de sódio em solução de propileno glicol com controle sobre o tempo de reação da hidrólise (RH) e submetendo à variação de parâmetros reacionais, como razão de hidrólise (th) e razão de contra íons acetatos (ta). Observou-se que o tempo de reação da hidrólise e a adição de íons acetato tiveram um forte efeito na morfologia e tamanho das partículas de ZnO. Por exemplo, imagens de microscopia eletrônica de transmissão (MET) revelaram que as amostras de ZnO sintetizadas por tempo curto de RH (10 min) e tempo de RH longo (300 min) cristalizaram em pequenos bastões e em formas de bastões alongados, respectivamente. Por outro lado, utilizando apenas reagente de acetato de zinco, as amostras de ZnO cristalizaram numa forma aproximadamente esférica. Essas diferenças podem ser atribuídas à relação da polarização do acetato e do propileno glicol, isto é, a maior quantidade de acetato presente na solução afeta o crescimento preferencial orientado dos cristais de ZnO. Além disso, o tempo de RH causou alterações no gap de banda óptica (Eg) das amostras. Por exemplo, os valores determinados pelo modelo de Kubelka-Munk diminuíram de 3,31 eV para 3,28 eV para os tempos, curto e longo de RH, respectivamente. Isto pode ser explicado em termos de defeitos estruturais e principalmente devido à diferença entre os tamanhos de partículas. Os padrões de difração de raios X (DRX) revelaram que todas as amostras cristalizaram na estrutura típica de wurtzita de ZnO. Contudo, a intensidade relativa do pico de difração (002) das amostras de ZnO sintetizadas apenas com acetato de zinco foi superior àqueles sintetizados utilizando tanto acetato de zinco como acetato de sódio. Isto indica de que o eixo c deve ser a direção de crescimento preferencial dos cristais. Portanto, a morfologia das amostras de ZnO pode ser adaptada usando o método poliol, assim as propriedades físicas que são importantes para algumas aplicações tecnológicas, poderiam ser controladas.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / A utilizaÃÃo de resÃduos agroindustriais como matÃria-prima para obtenÃÃo de produtos com maior valor agregado tem recebido grande destaque no campo cientÃfico nos Ãltimos anos. Esses materiais sÃo descartados no ambiente, conduzindo a prejuÃzos ambientais de grandes proporÃÃes ou, quando utilizados, nÃo sÃo empregados de forma plena e sustentÃvel. O Brasil se destaca na produÃÃo agrÃcola mundial de diversos produtos, sendo a regiÃo nordeste a maior produtora nacional de caju, incluindo assim o paÃs em uma situaÃÃo de destaque global em relaÃÃo a esse cultivo. No processamento, retira-se a amÃndoa do caju, que em geral à exportada com excelente preÃo de mercado, e extrai-se o suco, restando uma considerÃvel quantidade de bagaÃo. Esse componente, por sua vez, possui preÃo comercial irrisÃrio podendo ser utilizado na adubaÃÃo e em complemento a alimentaÃÃo animal. O bagaÃo do caju (BC) à rico em celulose (17,73%) e hemicelulose (19,22%), o que o torna um material lignocelulÃsico apto para obtenÃÃo de diversos aÃÃcares fermentescÃveis, especialmente a glicose e a xilose. Esses carboidratos podem ser assimilados por micro-organismos originando, por meio da via biotecnolÃgica, diversos bioprodutos, como por exemplo o xilitol. Essa substÃncia à um poliol com importÃncia alimentÃcia, farmacÃutica e odontolÃgica obtida a partir da D-xilose. Sua produÃÃo industrial ocorre a partir da hidrogenaÃÃo, catalisada pela presenÃa de ligas metÃlicas, da D-xilose, sob condiÃÃes de elevadas temperaturas e pressÃes, o que eleva o custo do processo. Diversos micro-organismos, principalmente leveduras, sÃo reportados por sua capacidade em produzir xilitol a partir de resÃduos lignocelulÃsicos. Dessa maneira, o objetivo desse trabalho foi realizar um estudo pioneiro a respeito da empregabilidade do BC como substrato para a produÃÃo de xilitol por fermentaÃÃo microbiana. A primeira etapa da pesquisa avaliou a produÃÃo de xilitol em meios sintÃticos, compostos por xilose (MX) ou xilose e glicose (MXG), por trÃs leveduras: Candida tropicalis, Kluyveromyces marxianus CCA510 e Kluyveromyces marxianus ATCC36907. As trÃs leveduras foram capazes de produzir xilitol nos meios sintÃticos e C. tropicalis e K. marxianus CCA510 foram selecionadas pelo seu melhor desempenho para os experimentos seguintes. A segunda etapa do trabalho consistiu em avaliar a produÃÃo de xilitol a partir do hidrolisado hemicelulÃsico de bagaÃo de caju (HBC). O hidrolisado foi obtido submetendo-se o BC, apÃs prÃvia lavagem, secagem e padronizaÃÃo de tamanho, a hidrÃlise Ãcida com H2SO4 0,6 mol.L-1, alcanÃando concentraÃÃo de glicose e xilose de 12,09 g.L-1 e 19,02 g.L-1, respectivamente. O HBC foi concentrado por evaporaÃÃo e tratado com dois tipos de carvÃo ativado (em grÃnulos e em pÃ), observando-se que o carvÃo em pà foi mais eficiente para eliminaÃÃo de inibidores do processo microbiana (como Ãcido acÃtico, fÃrmico e compostos fenÃlicos). Por Ãltimo, avaliou-se a influÃncia da suplementaÃÃo do HBC com diferentes fontes de nitrogÃnio (ureia, sulfato de amÃnio e extrato de levedura) para a produÃÃo de xilitol. Concluiu-se que a ureia foi capaz de melhorar o crescimento em biomassa dos micro-organismos testados, contudo, nenhuma das fontes de nitrogÃnio foi significativas para o incremento da produÃÃo de xilitol. Diante do estudo, pode-se concluir que o HBC pode ser matÃria-prima potencial para a produÃÃo biotecnolÃgica de xilitol pelas leveduras empregadas e que tratamentos de destoxificaÃÃo e suplementaÃÃo nutricional podem ser levados em consideraÃÃo para melhoria do processo.

Four novel high performance soft thermoplastic polyurethane elastomers utilizing methylene bis(4-cyclohexylisocyanate) as a hard segment, 1,4 butanediol as a chain extender and modified low crystallinity carbonate copolymer as a soft segment were synthesized. The samples were characterized by infrared spectroscopy (FTIR), tensile, elongation, hardness, abrasion resistance and atomic force microscopy (AFM). SAXS data shows evidence of an interdomain "center-to-center" distance of 45Å. DSC traces show evidence of one glass transition temperature and a weak melting region. DMA analysis reveals a low temperature secondary relaxation and the glass to rubber transition followed by a rubbery plateau. All samples demonstrated the ability to maintain excellent physical and mechanical properties in hardness below 70 Shore A. Thermoplastic polyurethanes in this study do not possess surface tackiness usually observed in soft polyurethanes. Biocompatability testing showed no toxicity of these samples as indicated by USP Class VI, MEM Elution Cytotoxicity and Hemolysis toxicology reports. This novel type of polyurethane material targets growing markets of biocompatible polymers and can be utilized as peristaltic pump tubing, balloon catheters, enteral feeding tubes and medical equipment gaskets and seals. Polyimides are a family of engineering polymers with temperature stability, high polarity and solvent resistance. These high-performance materials are used in aerospace applications, in the production of semi-dry battery binders, and in a host of other high temperature demanding situations. However, their glass transition and melt temperatures are characteristically very high and close to one another, making them difficult to melt process and limiting them to thin film formulations from their polyamic acid precursors. Here, a new series of thermoplastic polyether-polyimides (PE-PIs) are synthesized by incorporating a polyetherdiamine monomer to reduce rigidity and break up an otherwise fully aromatic backbone as seen with most conventional polyimides. It will be shown that control of the stoichiometric ratio between the aromatic 4,4'-methylenebis(2,6-dimethylaniline) and aliphatic polyetherdiamines relative to PMDA (pyromellitic dianhydride), along with the molecular weight of the polyetheramine, can be used to tune the Tg to best balance between temperature performance and processability.

Die molekularen Tantal-Komplexe [TaCl4(NMe2)(OEt2)], [TaCl4(NEt2)(OEt2)], [TaCl3(NEt2)(OiPr)]2, [TaCl4(NEt2)]2, [TaCl3(NEt2)2]2, sowie die Pentachloroetherate [MCl5(OEt2)] (M=Nb, Ta) wurden synthetisiert und ihre Kristallstruktur aufgeklärt. Bei der Zersetzung der Chloridetherate in die korrespondierenden Oxidtrichloride, konnte die vermutete Abspaltung von Ethylchlorid bestätigt werden. Bei den Untersuchungen zur Leistungsfähigkeit der Polyol-Route wurden binäre und ternäre Sulfide, welche sich nicht im wäßrigen System fällen lassen, synthetisiert. Die Sulfide der Gruppe 10 konnten erstmals unter den milden Reaktionsbedingungen der Polyol-Route erhalten werden. Im Falle der untersuchten ternären Cuprosulfide von Indium, Zinn und Antimon, konnte gezeigt werden, daß diese durch die Präparation mittels Polyol-Route zunächst kubisch mit ungeordnetem Kationenteilgitter kristallisieren. Durch eine anschließende thermische Behandlung bei 623 K wurden diese in die tetragonal geordneten Modifikationen überführt. Bei der polyol-vermittelten Synthese binärer und ternärer Selenide wurde erstmals Selenoharnstoff erfolgreich eingesetzt. Hiermit konnte im Zuge der Synthese eine homogene, molekulare Lösung erhalten werden, bei der eine optimale Durchmischung der anionischen und kationischen Edukte gewährleistet ist. Das ternäre Mischoxid LaTaO4 wurde erfolgreich mit Hilfe der Polyol-Route hergestellt und in einem Wirbelschichtreaktor zu La2Ta2O5N2 umgesetzt. Dafür wurde eine neue Anlage entwickelt. Es konnte gezeigt werden, daß die Präparation von Tantaloxidnitriden im Wirbelschichtreaktor mit einem geringeren Ammoniak-Verbrauch als bei der bisherigen Prozeßführung möglich ist.

No description available.

Intermetallic compounds are highly investigated, as they combine or enhance the properties of their constituting elements or even bring forth new properties. Especially at the nanoscale, these features can be exploited in heterogeneous catalysis.[1] Various methods have been developed so far to synthesize intermetallic particles, each with its own benefits and drawbacks. A facile procedure is the polyol process, which was first introduced by the group of FIÉVET and FIGLARZ in 1989. Here, the polyol serves a threefold purpose. First, it serves as the primary solvent. With respect to metal salts, it displays a solvation behavior similar to water due to the chelating properties. Second, the polyol can act as a surface-capping agent, which prevents agglomeration, resulting in finely dispersed particles. Third and last, the main attribute of the polyol is its reductive property, which increases with temperature, enabling the reduction of multiple metal cations. Compared to other synthetic routes, the polyol process can be performed with cheap starting materials, such as metal salts or oxides. The utilization of a laboratory microwave can further improve the process. A homogeneous heat distribution and contactless heating diminish side reactions. Additionally, the extreme heating rates foster homogeneous nucleation, resulting in a uniform product. Furthermore, the precise control over the temperature profile enables good reproducibility, making this setup ideal for efficient syntheses as well as investigations of reaction pathways. In this PhD thesis, formation mechanisms of Bi-M particles (M = Ni, Ir, Rh; ) were elucidated, revealing different mechanisms depending on the metal combination as well as various intermediates. Additionally, the influence of reaction parameters, such as metal precursor, anion, and pH value was investigated. In the case of BiNi particle formation, a successive reduction of bismuth and nickel cations was observed. Bismuth cations are reduced first producing bismuth particles, which act as nucleation sites for the subsequent nickel reduction. The particles grow on the surface of the bismuth core resulting in a core-shell structure. Diffusion of nickel results in Bi3Ni and eventually BiNi after full depletion of the nickel shell. The choice of nickel precursor substantially influences the required reaction time. Nickel acetate requires the shortest reaction time, whereas nickel nitrate necessitates drastically longer reaction times due to a decreased reductivity. Nickel chloride is not reducible in neat ethylene glycol due to the formation of a stable dinuclear nickel complex in solution. The overall formation kinetics are substantially promoted by increasing the pH value or temperature, leading to a higher reduction strength or improved diffusion dynamics, respectively. The study of Bi2Ir particle formation revealed a two-stage scenario. First, the starting materials are partially co-reduced to the new intermetallic suboxide Bi4Ir2O. In a second step, at higher temperatures, the suboxide is fully reduced to Bi2Ir. So far, only the combination of bismuth nitrate and iridium acetate results in the suboxide, whereas the introduction of chloride ions, i.e., iridium chloride or potassium hexachloroiridate, merely results in BiOCl and elemental iridium. A structural model of Bi4Ir2O was established based on diffraction data and quantum chemical calculations. Edge-sharing [IrBi6] octahedra form corrugated layers stacked along the c-axis, which are separated by oxide ions. The calculated band structure and DOS suggest metallic behavior within the layers, whereas a band gap was found along the stacking order, thus, making the compound a pseudo 2D metal.The formation of Bi2Rh particles follows a two-step mechanism. For rhodium acetate, the process starts with a direct co-reduction of rhodium and bismuth cations resulting in the formation of BiRh. Increasing the temperature further leads to a gradual transition into Bi2Rh via reduction of residual bismuth cations in solution followed by diffusion. In the case of rhodium nitrate, a bismuth-glycolato complex precipitates, which undergoes a reaction with rhodium at high temperatures. The addition of a base promotes the reactions by lowering the necessary reduction temperatures and preventing the precipitation of the bismuth glycolate. Rhodium chloride does not yield intermetallic phases in the desired purity and yield. These results allowed for a comparison and assessment of reactions in the synthesis of γ-BiPd particles. Similar to the above discussed reactions, chlorides resulted in the formation of BiOCl. An increased pH value was beneficial by preventing precipitation of intermediates, i.e., BiOCl or bismuth glycolates, and improved reduction strength.

Ce travail de thèse traite de la production d’hydrogène par le procédé de photoélectrocatalyse en utilisant une photoanode à base de nanotubes de TiO2 verticalement alignés. L’utilisation du TiO2 étant limité pour des applications solaires en raison de son large gap, il est nécessaire de le modifier. Deux approches sont proposées pour modifier les nanotubes de TiO2 et leur permettre d’absorber la lumière visible. La première est une modification chimique du TiO2 par co-dopage cationique-anionique (Ta-N) ou (Nb-N). Les cations sont insérés durant la croissance des nanotubes grâce à une approche inédite, et l’azote est inséré durant le traitement thermique. Ceci a pour effet la formation d’orbitales hybrides qui entraîne une réduction du gap et une activité sous lumière visible, tout en permettant une stabilité de la structure. La seconde approche consiste à déposer des nanoparticules d’Ag sur la surface des nanotubes de TiO2. Grâce au contrôle de la morphologie des nanoparticules d’Ag, leur résonnance plasmonique permet de stimuler l’absorption du TiO2 et ainsi d’augmenter son rendement à la fois sous lumière UV et sous lumière visible. / This work is about the production of hydrogen by photoelectrocatalysis using a vertically aligned TiO2 nanotubes based photoanode. Utilization of TiO2 for solar applications is limited due to its large band gap, it has to be modified. Two approaches are proposed for the modification of the TiO2 nanotubes to make them absorb visible light. The first one is the chemical modification of the TiO2 by (Ta-N) or (Nb-N) cationic-anionic co-doping. Cations are inserted during the growth of the nanotubes by a novel approach, and nitrogen is inserted during heat treatment. This leads to the formation of hybrid orbitals resulting in a band gap reduction and of activity under visible light. The second approach consists of the deposition of Ag nanoparticles on the surface of the TiO2 nanotubes. Thanks to the control of the morphology of the Ag nanoparticles, their plasmonic resonance can enhance the absorption of TiO2 and thus increase its activity both under UV and visible light.

The continuous high demand on permanent magnets in industries opened new research plateau to develop alternative magnetic material. The current used permanent magnet materials in the market still suffer from high cost and insufficient magnetic or thermal properties. The central focus of this dissertation work is the optimization of cobalt carbide based nanomaterial by means of modifying polyol synthesis assisted by nucleation agent and systematic statistics using JMP software tool. In most existing literatures, producing cobalt carbide (Co2C or Co3C) lack reproducibility and consistency resulting in nonsolid magnetic properties results. The practical requirements for cobalt carbide to be used as permanent magnet are high coercivity (Hc), high magnetization (Ms), resulting in a high-energy product (HcxMs). Previous literatures have shown coercivities of 1.5 to 2.5 kOe for cobalt carbides under aggressive temperatures conditions (300oC) or after aligning the particles under magnetic field. A statistical guided method performed a sequence of experiments toward producing high coercivities using surface response design. Primarily, the statistical study to optimize cobalt carbide was made by analyzing experimental condition to fulfill high magnetic properties with tuned conditions as much as possible. Therefore, having the advantage for superior control on process variable when shifting cobalt carbide for scale up production in flow chemistry set up using microreaction system (MMRS). The optimization is based upon selecting the most important conditions in polyol reaction to produce cobalt carbide (Co2C or Co3C) and feed JMP software model e.g. reaction temperature, reaction time, and or precursor concentration…etc. These factors called (effects) used to design experiments and generate tables to run minimum experiments. Points of each effect (levels) are selected based on previous knowledge and experience with the synthesis. The output called (response) can be any of the magnetic properties of our interest e.g. magnetization (Ms), coercivity (Hc), or energy magnetic product (HcxMs). In the first model fit of cobalt carbide magnetic was studied in a polyol reaction to increase its magnetic energy product and optimize the experimental conditions. The results disclosed increase in magnetic energy product (6.2 MGOe) when validating the prediction model conditions suggested by JMP: shorter reaction time, and lower precursor concentration conditions at maximum reaction temperature. Finally, to my knowledge studying the effect of the nucleating agent to alter cobalt carbide growth have not been studied so far. Therefore, statistical study design using central composite design (CCD) to investigate the nucleating agent effect of silver nitrite on cobalt carbide coercivity was made. The importance of nucleating agent on coercivity is vigorous to attain and control the growth direction of cobalt carbide nanoparticles. This is due to the shape anisotropy contribution to enhance coercivity unlike weak shape anisotropy attributed to agglomeration of nanoparticles demonstrated in previous studies. Enhancement of coercivity reached 3 kOe with aspect ratio control as a function of silver nitrite concentration under lower reaction temperature. The continuous high demand on permanent magnets in industries opened new research plateau to develop alternative magnetic material. The current used permanent magnet materials in the market still suffer from high cost and insufficient magnetic or thermal properties. The central focus of this dissertation work is the optimization of cobalt carbide based nanomaterial by means of modifying polyol synthesis assisted by nucleation agent and systematic statistics using JMP software tool. In most existing literatures, producing cobalt carbide (Co2C or Co3C) lack reproducibility and consistency resulting in nonsolid magnetic properties results. The practical requirements for cobalt carbide to be used as permanent magnet are high coercivity (Hc), high magnetization (Ms), resulting in a high-energy product (HcxMs). Previous literatures have shown coercivities of 1.5 to 2.5 kOe for cobalt carbides under aggressive temperatures conditions (300oC) or after aligning the particles under magnetic field. A statistical guided method performed a sequence of experiments toward producing high coercivities using surface response design. Primarily, the statistical study to optimize cobalt carbide was made by analyzing experimental condition to fulfill high magnetic properties with tuned conditions as much as possible. Therefore, having the advantage for superior control on process variable when shifting cobalt carbide for scale up production in flow chemistry set up using microreaction system (MMRS). The optimization is based upon selecting the most important conditions in polyol reaction to produce cobalt carbide (Co2C or Co3C) and feed JMP software model e.g. reaction temperature, reaction time, and or precursor concentration…etc. These factors called (effects) used to design experiments and generate tables to run minimum experiments. Points of each effect (levels) are selected based on previous knowledge and experience with the synthesis. The output called (response) can be any of the magnetic properties of our interest e.g. magnetization (Ms), coercivity (Hc), or energy magnetic product (HcxMs). In the first model fit of cobalt carbide magnetic was studied in a polyol reaction to increase its magnetic energy product and optimize the experimental conditions. The results disclosed increase in magnetic energy product (6.2 MGOe) when validating the prediction model conditions suggested by JMP: shorter reaction time, and lower precursor concentration conditions at maximum reaction temperature. Finally, to my knowledge studying the effect of the nucleating agent to alter cobalt carbide growth have not been studied so far. Therefore, statistical study design using central composite design (CCD) to investigate the nucleating agent effect of silver nitrite on cobalt carbide coercivity was made. The importance of nucleating agent on coercivity is vigorous to attain and control the growth direction of cobalt carbide nanoparticles. This is due to the shape anisotropy contribution to enhance coercivity unlike weak shape anisotropy attributed to agglomeration of nanoparticles demonstrated in previous studies. Enhancement of coercivity reached 3 kOe with aspect ratio control as a function of silver nitrite concentration under lower reaction temperature.