The work is focused on the investigation of synthesis and structure of crystalline coordination networks by combining first a row transition metal ion with one anionic and one neutral bridging ligand. In the field of crystalline coordination networks, the goal is to synthesize porous 3D crystalline coordination networks with molecular sized cavities. The materials are characterized by XRD and TGA. It is important to understand the structural topologies to develop practical applications, such as gas storage, gas separation, and catalysis. The bi- and tetra-dentate flexible imidazole ligands, 9,10-bis(imidazol-1-ylmethyl)anthracene (Chapter 2) and 1, 2, 4, 5-tetrakis(imidazol-1ylmethyl)benzene (Chapter 3), are synthesized and used as linkers to construct 1D, 2D, and 3D crystalline coordination networks with cobalt(II) or zinc(II) cations and H3BTC anions under solvothermal conditions. Two 1D chain networks, [M(HBTC²⁻)(C₂₂H₁₈N₄)(H₂O)₂]•H₂O, are constructed from M(Zn(II) or Co(II)), H₃BTC, and 9,10-bis(imidazol-1-ylmethyl)anthracene (Compound 2.1 and 2.2). These two 1D zigzag chains are linked into infinite 2D sheets by inter-chain π•••π stacking and hydrogen bonding. ⁺ Two 2D and one 3D cobalt(II) coordination networks are constructed from the tetradentate imidazole ligand and H3BTC. Compound 3.1 has a 2D corrugated sheet structure that is linked by inter-layer π•••π stacking and hydrogen bonding. Compound 3.2 has a 2D sheet structure. These sheets are interconnected by hydrogen bonds at the free acid group of the HBTC²⁻ ligand. Compound 3.3 forms a two fold interpenetrated 3D network structure. Void spaces in the structure are filled with six water molecules. Six 3D cobalt (II) coordination networks are constructed with bidentate rigid imidazole containing neutral ligands, 1,4-bis(imidazol-1-yl)benzene(L1), 1,4-bis(imidazol-1-yl)naphthalene(L2), and 9,10-bis(imidazol-1-yl)anthracene(L3), and H₂BDC or H₃BTC anion (Chapter 4). In 4.1-4.3, L1-L3 affects on degree of interpenetrations constructed with H₂BDC ligand. In 4.1 and 4.2 are interpenetrating 3D networks with no accessible void space. In 4.3, void spaces of 3D networks are filled with 2D sheets. Compounds 4.4-4.6 are prepared by different concentrations of starting materials and different solvents. In 4.4-4.6, L3 serves as a pillar building block to construct 3D networks by applying with H₃BTC ligand. The solvent exchange experiment for 4.4 is further discussed. / Ph. D.

A busca pelo aprimoramento de materiais nanocristalinos baseia-se na variação do processo de síntese e na alteração de sua estrutura através da inserção de defeitos na estrutura cristalina. O processo de dopagem tem sido considerado de fundamental importância para estabilizar determinadas fases ou faces cristalinas. Por outro lado, o uso de uma metodologia de síntese versátil como a síntese hidrotérmica e solvotérmica mostra-se como uma proposta interessante para obter materiais já produzidos por técnicas convencionais, mas que apresentam propriedades diferenciadas. Nesse trabalho, verificou-se o efeito do método de síntese utilizado e da adição de íons dopantes como Mg+2 e Ni+2 nas propriedades morfológicas e estruturais do composto titanato de cálcio (CaTiO3) que foi preparado através dos métodos hidrotérmico e solvotérmico. Através das técnicas de difração de raios X e microscopia eletrônica de varredura, foi verificado o efeito dos parâmetros de síntese (tempo e temperatura) e dos materiais precursores nas propriedades estruturais e microestruturais das amostras. Na avaliação de fotoatividade realizada (fotodegradação do corante rodamina B) foi observado que os compostos sintetizados pelo método hidrotérmico com os precursores oxisulfato de titânio e cloreto de cálcio apresentaram melhor atividade fotocatalítica que os compostos sintetizados pelo método solvotérmico (solvente PEG-200). / The search for the improvement of nanocrystalline materials is based on the variation of the synthesis process and the modification of its structure through the insertion of defects in its crystalline structure. The doping process has been considered of fundamental importance to stabilize certain crystalline phases or faces of nanomaterials. On the other hand, the use of a versatile synthesis methodology such as hydrothermal and solvothermal methods is an interesting proposal to obtain materials already produced by conventional techniques, but with different properties. In this work, the effect of the synthesis method and the addition of dopant ions such as Mg+2 and Ni+2 on the morphological and structural properties of the calcium titanate (CaTiO3) compound was verified, which was prepared by hydrothermal and solvothermal methods. The effect of the synthesis parameters (time and temperature) and the precursor materials on the structural and microstructural properties of the samples were verified by means of the X-ray diffraction and scanning electron microscopy techniques. It was observed that the compounds synthesized by the hydrothermal method with the titanium oxysulfate and calcium chloride precursors presented better photocatalytic activity than the compounds synthesized by the solvothermal method (solvent PEG-200).

Transparent ceramics are used in a variety of applications such as protective visors, thermo-graphic lens, night vision devices and windowpane of an armed vehicle, missile domes and in aircrafts. Yttrium Aluminium Garnet (YAG, Y3Al5O12) exhibits uniform index of refraction without birefringence owing to its cubic crystal structure and offers a range of optical and mechanical properties that makes it suitable for transparent applications.

A busca pelo aprimoramento de materiais nanocristalinos baseia-se na variação do processo de síntese e na alteração de sua estrutura através da inserção de defeitos na estrutura cristalina. O processo de dopagem tem sido considerado de fundamental importância para estabilizar determinadas fases ou faces cristalinas. Por outro lado, o uso de uma metodologia de síntese versátil como a síntese hidrotérmica e solvotérmica mostra-se como uma proposta interessante para obter materiais já produzidos por técnicas convencionais, mas que apresentam propriedades diferenciadas. Nesse trabalho, verificou-se o efeito do método de síntese utilizado e da adição de íons dopantes como Mg+2 e Ni+2 nas propriedades morfológicas e estruturais do composto titanato de cálcio (CaTiO3) que foi preparado através dos métodos hidrotérmico e solvotérmico. Através das técnicas de difração de raios X e microscopia eletrônica de varredura, foi verificado o efeito dos parâmetros de síntese (tempo e temperatura) e dos materiais precursores nas propriedades estruturais e microestruturais das amostras. Na avaliação de fotoatividade realizada (fotodegradação do corante rodamina B) foi observado que os compostos sintetizados pelo método hidrotérmico com os precursores oxisulfato de titânio e cloreto de cálcio apresentaram melhor atividade fotocatalítica que os compostos sintetizados pelo método solvotérmico (solvente PEG-200). / The search for the improvement of nanocrystalline materials is based on the variation of the synthesis process and the modification of its structure through the insertion of defects in its crystalline structure. The doping process has been considered of fundamental importance to stabilize certain crystalline phases or faces of nanomaterials. On the other hand, the use of a versatile synthesis methodology such as hydrothermal and solvothermal methods is an interesting proposal to obtain materials already produced by conventional techniques, but with different properties. In this work, the effect of the synthesis method and the addition of dopant ions such as Mg+2 and Ni+2 on the morphological and structural properties of the calcium titanate (CaTiO3) compound was verified, which was prepared by hydrothermal and solvothermal methods. The effect of the synthesis parameters (time and temperature) and the precursor materials on the structural and microstructural properties of the samples were verified by means of the X-ray diffraction and scanning electron microscopy techniques. It was observed that the compounds synthesized by the hydrothermal method with the titanium oxysulfate and calcium chloride precursors presented better photocatalytic activity than the compounds synthesized by the solvothermal method (solvent PEG-200).

Lithium-ion batteries play a crucial role in portable electronics, but require further innovation for electric vehicle and grid storage applications. To meet this demand, significant emphasis has been placed on developing safe, inexpensive, high energy density cathode materials. LiFePO₄ is a candidate cathode material for electric vehicle and grid storage applications. Vanadium-doped LiFePO₄ cathodes of the form [chemical formula] (0 ≤ x ≤ 0.25) were synthesized here by a facile, low-temperature microwave-assisted solvothermal (MW-ST) method. Such an approach offers manufacturing-energy and cost savings compared to conventional synthesis. Additionally, although [chemical formula] has been synthesized previously by conventional methods, it is shown here that the MW-ST method allows much higher doping levels than can be achieved at conventional temperatures, indicating that metastable phases can be isolated through the low-temperature microwave-assisted synthesis. LiFePO₄ suffers from poor ionic conductivity, but this limitation can be minimized by microwave-assisted synthesis through a tuning of the particle size, allowing for decreased Li⁺ diffusion paths. LiVOPO₄ is another polyanion material with higher energy density than LiFePO₄, but similar ionic conductivity limitations. It has not been previously synthesized by MW-ST. Thus, a MW-ST method was developed here to prepare LiVOPO₄. By varying reaction conditions, three polymorphic modifications of LiVOPO₄ were accessed and the electrochemical performance was optimized. LiVOPO₄ can be further discharged to Li₂VOPO₄, which has been suggested in the literature, but the structural transformation that accompanies this process has not been detailed. To this end, the delithiation process was studied by ex situ XRD measurements to better understand how the second lithium is accommodated. Finally, MW-ST has also been exploited to grow thin films of anatase TiO₂ phase on indium tin oxide (ITO)-coated glass substrates. The microwave field is selectively absorbed by the conductive ITO layer on the glass substrates, leading to ohmic heating. The resulting heated ITO layer acts as a favorable site for nucleation and growth. TiO₂ thin films have widespread applications in the energy and electronics sectors. Such selective microwave-assisted ohmic heating of solid materials within a growth solution represents a promising new avenue for microwave synthesis, which has been minimally explored in the literature. / text

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The ability to encapsulate linear nanoparticle (NP) chains in scrolled nanosheets is an important advance in the formation of nanocomposites.These nanopeapods (NPPs) exhibit interesting properties that may not be achieved by individual entities. Consequently, to fully exploit the potential of NPPs, the fabrication of NPPs must focus on producing composites with unique combinations of morphologically uniform nanomaterials. Various methods can produce NPPs, but expanding these methods to a wide variety of material combinations can be difficult. Recent work in our group has resulted in the in situ formation of peapod-like structures based on chains of cobalt NPs. Building on this initial success, a more versatile approach has been developed that allows for the capture of a series of preformed NPs in NPP composites. In the following chapters, various synthetic approaches for NPPs of various material combinations will be presented and the key roles of various reaction parameters will be discussed. Also, uniform hexaniobate nanoscrolls were fabricated via a solvothermal method induced by heating up a mixture of TBAOH, hexaniobate crystallites, and oleylamine in toluene. The interlayer spacing of the nanoscrolls was easily tuned by varying the relative amount and chain lengths of the primary alkylamines. To fabricate NPPs, as-synthesized NPs were treated with hexaniobate crystallite in organic mixtures via solvothermal method. During solvothermal treatment, exfoliated hexaniobate nanosheets scroll around highly ordered chains of NPs to produce the target NPP structures in high yield. Reaction mixtures were held at an aging temperature for a few hours to fabricate various new NPPs (Fe3O4@hexaniobate, Ag@hexaniobate, Au@hexaniobate, Au-Fe3O4@hexaniobate, TiO2@hexaniobate, CdS@hexaniobate, CdSe@hexaniobate, and ZnS@hexaniobate). This versatile method was first developed for the fabrication of magnetic peapod nanocomposites with preformed nanoparticles (NPs). This approach is effectively demonstrated on a series of ferrite NPs (≤ 14 nm) where Fe3O4@hexaniobate NPPs are rapidly (~ 6 h) generated in high yield. When NP samples with different sizes are reacted, clear evidence for size selectivity is seen. Magnetic dipolar interactions between ferrite NPs within the Fe3O4@hexaniobate samples leads to a significant rise in coercivity, increasing almost four-fold relative to free particles. Other magnetic ferrites NPPs, MFe2O4@hexaniobate (M = Mn, Co, Ni), can also be prepared. This synthetic approach to nanopeapods is quite versatile and should be readily extendable to other, non-ferrite NPs or NP combinations so that cooperative properties can be exploited while the integrity of the NP assemblies is maintained. Further, this approach demonstrated selectivity by encapsulating NPs according to their size. The use of polydispersed NP systems is also possible and in this case, evidence for size and shape selectivity was observed. This behavior is significant in that it could be exploited in the purification of inhomogeneous NP samples. Other composite materials containing silver and gold NPs are accessible. Partially filled Fe3O4@hexaniobate NPPs were used as templates for the in situ growth of gold to produce the bi-functional Au- Fe3O4@hexaniobate NPPs. Encapsulation of Ag and Au NP chains with a hexaniobate nanoscroll was shifted the surface plasmon resonance to higher wavelengths. In these composites NPs can be incorporated to form NPP structures, decorated on nanosheets before scrolling, or attached to the surfaces of the nanoscrolls. The importance of this advancement is the promise it holds for the design and assembly of active nanocomposites. One can create important combinations of nanomaterials for potential applications in a variety of areas including catalysis, solar conversion, thermoelectrics, and multiferroics.

Encapsulation of nanoparticles within hexaniobate nanoscrolls presents interesting advances in the formation of nanocomposites exhibiting unique multi-dimensional properties. Building upon previous successes, facile yet versatile wet-chemical and microwave-irradiation synthetic protocols for the fabrication of a series of hexaniobate composites are presented herein. Solvothermal and, more recently, microwave-assisted methods have been developed that allow for the fabrication of peapod-like structures. During solvothermal treatment, exfoliated hexaniobate nanosheets scroll around highly ordered chains of preformed nanoparticles (NPs) to produce nanopeapods (NPPs). This approach offers versatility and high yields, in addition to the potential for advanced functional device fabrication. For the characterization of these materials, advanced techniques in atomic force microscopy (AFM) were used for investigating the surface of materials at the nanometer scale. Extensive physical, dynamic, and force modulation studies were performed on novel oxide nanocomposites by implementing particular scanning techniques to determine information such as topology, stress-induced behavior at the nanoscale, magnetic behavior, and frictional forces of the nanoscale materials. These composites were then analyzed by topological intermittent contact studies in tapping and contact mode, as well as with derivative techniques of these commonly used scanning probe approaches. In addition to studying surfaces using conventional modes of AFM, the mechanical properties of these nanocomposites were measured via dynamic lateral force modulation (DLFM) and magnetic properties of functionalized magnetic nanosheets were mapped via magnetic sampling modulation (MSM). By utilizing the capabilities of the DLFM imaging mode, elastic properties such as Young’s Modulus were measured from force-distance curves. In addition to this modulation mode, MSM was used to selectively map the vibrating magnetic nanomaterials from a modulated electromagnetic field. The information obtained from these AFM techniques can be helpful in determining the relative structural behavior of these nanocomposites and gauge their use in various applications such as structural engineering of nanoarchitectures as well as studying magnetic characteristics of metal oxide nanocomposites that exhibit characteristics different from their bulk counterparts.

Le marché de l’éclairage est un marché de masse à diffusion large en pleine mutation face aux nouvelles contraintes environnementales. Il s’inscrit dans une démarche de préservation de l’environnement avec une volonté européenne de voir sa consommation énergétique réduite de 20% d’ici 2020. Les luminophores jouent un rôle prépondérant dans les performances des systèmes d’éclairage utilisant comme sources d’excitations des LEDs bleues ou UV, ou encore un plasma (Xe-Ne), où ils permettent de convertir les photons incidents (VUV, UV ou bleus) en lumière visible. Dans le cadre de cette thèse, nous nous sommes intéressés à la production de lumière blanche. Pour obtenir une couleur la plus proche du blanc idéal et répondant aux mieux au cahier des charges de l’éclairage domestique, une amélioration des performances des luminophores utilisés classiquement est nécessaire. Au cours de ces travaux nous avons porté notre attention sur deux aluminates de formulations Y3Al5O12 dopé Ce3+ (YAG :Ce) et BaMgAl10O17 dopé Eu2+ (BAM :Eu). L’aspect novateur repose d’une part sur la synthèse de ces luminophores sous forme de nanoparticules par des voies de synthèse originales (la voie solvothermale et la combustion assistée par micro-ondes respectivement) et d’autre part sur leur mise en forme (revêtements composites « luminophores/polymère »). Plusieurs techniques expérimentales (DRX, IR, Mössbauer, aimantation, MEB, MET,…) ont été utilisées afin de caractériser leurs propriétés structurales et morphologiques. L’étude des performances optiques de ces luminophores enregistrées sous excitations bleue, UV et/ou VUV nous a permis de mettre en évidence leur utilisation potentielle dans les nouveaux dispositifs d’éclairage : associés à d’autres luminophores (rouge pour le YAG :Ce; rouge et vert pour le BAM :Eu) en proportions adéquates, il est possible de générer de la lumière blanche présentant les propriétés escomptées. / Lighting market is a widespread distribution mass market undergoing radical transformation faced with new environmental restrictions. It fits into an environmental protection approach with a European will to reduce by 20% its energy consumption by 2020. Phosphors play a key role on performances of lighting devices where, combined with LEDs (blue or UV) or plasma (Xe-Ne) excitations, they provide visible light. In this work, we have focused on the generation of white light. In order to obtain a color closest to ideal white and meeting with the specifications of domestic lighting, it is necessary to improve the performances of traditional phosphors. Two aluminates have been investigated: Ce3+ doped Y3Al5O12 (YAG :Ce) and Eu2+ doped BaMgAl10O17 (BAM :Eu). On the one hand, innovation is based on unconventional synthesis methods allowing the preparation of nanostrutured phosphors (solvothermal and microwave induced solution combustion syntheses respectively) and on the other hand on their shaping (composite coatings « phosphors/polymer »). Structural and morphological features have been studied by means of several tools (XRD, IR, Mössbauer, magnetization, SEM, TEM,…). Finally, the optical properties of phosphors recorded upon blue, UV and/or VUV excitations have evidenced that they are suitable for applications in new lighting devices: their combination with other phosphors (red for YAG:Ce; red and green for BAM:Eu) in appropriate proportions allows producing white light with the required specifications.

Les nanomatériaux sont de plus en plus utilisés dans de nombreusesapplications, que cela soit pour la catalyse, la coloration, l’optique, etc. Pour optimiser leurutilisation, il est nécessaire de mieux comprendre les réactions et interactions ayant lieu à ceséchelles. Cette thèse se propose d’essayer d’explorer les liens entre conditions de synthèse,morphologie de particules, et propriétés de celles-ci. En particulier, nous avons opté pourl’étude d’un matériau modèle : l’oxyde de cérium (IV). Les nanoparticules de CeO2 ont étéobtenues par voie de synthèse solvothermale assistée par chauffage micro-ondes. Lesmorphologies des nanoparticules de CeO2 étudiées ont été : les cubes, les octaèdres et lesbâtonnets, et nous avons essayé de fournir une explication à leur obtention par la voie desynthèse utilisée. De l’or a ensuite été déposé en surface des ces nanoparticules de CeO2 etétudié par une combinaison d’études par Microscopie Électronique en Transmission et demodélisations numériques. / Nanomaterials are more and more used in various situations, such as catalysis,color, optics, etc. To optimize their use, it is necessary to better understand reactions andinteractions taking place at these scales. This PhD thesis aims at exploring the links betweensynthesis conditions, particle morphology and their properties. In particular, we chose a tostudy a model-material: cerium (IV) oxide. CeO2 nanoparticles have been obtained bymicrowave-heating assisted solvothermal synthesis. Morphologies obtained and studied havebeen: cubes, octahedrons and rods. We tried to to give an explanation on how these synthesesallowed the formation of such morphologies. Gold has then be deposed on the surface of theseCeO2 nanoparticles, and studied by a combination of Transmission Electron Microscopystudies, and computer modelizations.