Magnetite (Fe3O4) is a commonly found in the environment and can form via several pathways, including biotic and abiotic reduction of Fe3+ oxides and the oxidation of Fe2+ and Fe0. Despite extensive research, the redox behavior of magnetite is poorly understood. In previous work, the extent and kinetics of contaminant reduction by magnetite varied by several orders of magnitude between studies, two fundamentally different models are used to explain magnetite oxidation (i.e., core-shell diffusion and redox-driven), and reported reduction potentials vary by almost 1 V. In other fields of science (e.g., physics), magnetite stoichiometry (x = Fe2+/Fe3+) is a commonly measured property, however, in environmental studies, the stoichiometry is rarely measured. The stoichiometry of magnetite can range from 0.5 (stoichiometric) to 0 (completely oxidized), with intermediate values (0 < x < 0.5) referred to as nonstoichiometric or partially oxidized magnetite. To determine the relationship between magnetite stoichiometry and contaminant fate, the reduction rates of three substituted nitrobenzenes (ArNO2) were measured. The kinetic rates varied over five orders of magnitude as the particle stoichiometry increased from x = 0.31 to 0.50. Apparent 15N kinetic isotope effects (15N-AKIE) values for ArNO2 were greater than unity for all magnetite stoichiometries investigated, and indicated that mass transfer processes are not controlling the reaction rate. To determine if the reaction kinetics were redox-driven, magnetite open circuit potentials (EOCP) were measured. EOCP values were linearly related to the stoichiometry, with more stoichiometric magnetite having a lower potential, in good agreement with redox-driven models. The reaction of aqueous Fe2+ and magnetite was investigated. Similar to previous findings for other Fe3+ oxides, the formation of a stable sorbed Fe2+ species was not observed; instead, the sorbed Fe2+ underwent interfacial electron transfer to form a partially oxidized magnetite phase, which was accompanied by reduction of the underlying magnetite. The lack of a stable sorbed Fe2+ species on magnetite indicated that the traditional surface complexation model was incorrect; instead, the uptake of Fe2+ by magnetite appeared to be limited by the whole particle (i.e., the sorbed and underlying phases combined) reaching a stoichiometry of 0.5.

O sistema soda-cal-sílica se destaca na ciência e tecnologia de vidros, pois encontra enorme gama de aplicações, desde os tradicionais vidros de janela até biomateriais. Mesmo assim, a cinética de transformação de fases e em particular a cinética de cristalização de vidros não é bem conhecida em diversas regiões de composições nesse sistema clássico, dentre elas a do binário combeíta-devitrita (Na2O.2CaO.3SiO2 &#8211; Na2O.3CaO.6SiO2). Neste trabalho, a cinética de cristalização de vidros de várias composições no sistema combeíta-devitrita foi investigada por técnicas de microscopia ótica. A partir da determinação experimental das taxas de nucleação e crescimento, e do time-lag para nucleação, as energias interfaciais sólido-líquido super-resfriado para núcleos de tamanho crítico foram estimadas, assim como as difusividades para cada vidro. As temperaturas de transição vítrea, do início (onset) do pico de cristalização, liquidus e de transformação polimórfica da combeíta foram determinadas por Calorimetria Exploratória Diferencial em função da composição do vidro matriz. A taxa de nucleação da combeíta (fase cristalina primária) foi estimada em função da temperatura pelo \"método do desenvolvimento\" ou método de Tamman, em que primeiro realiza-se um tratamento térmico de nucleação de cristais e depois um tratamento para o crescimento dos mesmos até um tamanho mensurável ao microscópio óptico, para vidros de composições 100, 75 e 66,7 % em mol de combeíta. Observou-se um decréscimo da taxa de nucleação com a variação da composição, à medida que a mesma se distancia da combeíta estequiométrica e aproxima-se da composição eutética, devido a mudanças termodinâmicas e cinéticas, tais como o aumento da energia interfacial sólido-vidro e a diminuição da cinética de difusão, respectivamente. Também observou-se a mudança de composição da combeíta cristalizada e do vidro residual através da variação das temperaturas de transformação polimórfica e de transição vítrea, respectivamente, determinadas por DSC. Os resultados obtidos sobre a cinética de cristalização de vidros não-estequiométricos são originais e relevantes para o projeto da microestrutura de novos materiais vitrocerâmicos. / The soda-lime-silica system excels in glass science and technology due its wide range of applications, from traditional window glass to biomaterials. Nevertheless, the kinetics of phase transformation and in particular the glasses crystallization kinetics is not well known in several regions of compositions in this classical system, among them the combeite-devitrite joint (Na2O.2CaO.3SiO2-Na2O.3CaO.6SiO2). In this work, the kinetics of glass crystallization of several compositions in the combeite-devitrite joint was investigated by optical microscopy techniques. From the experimental determination of nucleation and growth rates, and time-lag for nucleation, the solid-supercooled liquid interfacial energies for critical-sized nuclei were estimated as well as the diffusivity for each glass. The glass transition, onset of crystallization peak, liquidus and combeite polymorphic transformation temperatures were determined by Differential Scanning Calorimetry as a function of matrix glass composition. The nucleation rate of the combeite (primary crystalline phase) was estimated as a function of temperature by the \"development method\" or by the method of Tammann, in which first a heat treatment for nucleation of the crystals is performed and then a treatment for growth up to one measurable size by optical microscope, for glasses of compositions 100, 75 and 66.7% mol of combeite. A decrease was observed in the nucleation rate with the variation of the composition as it distances from the stoichiometric combeite and approaches the eutectic composition due to thermodynamic and kinetic changes, such as the increase of the solid-glass interfacial energy and the decrease in diffusion kinetics, respectively. The change in composition of crystallized combeite and residual glass was also observed by the change of the polymorphic transformation and glass transition temperatures, respectively, determined by DSC. The results obtained on the crystallization kinetics of non-stoichiometric glasses are original and relevant for the design of the microstructure of new glass-ceramic materials.

Le dioxyde de titane (TiO2) est un matériau polyvalent qui présente des propriétés intéressantes allant de la catalyse au stockage et conversion d'énergie. Afin d'améliorer ses propriétés physico-chimiques, plusieurs approches ont été appliquées telles que, la réduction de la taille des particules, modification de la morphologie, le dopage par d'autres éléments. Dans cette thèse, une nouvelle méthode de synthèse basée sur la chimie de sol-gel est développée en milieu fluoré. Les anions divalents de O2- dans TiO2 anatase sont substitués par anions monovalents de F- et OH-, le déficit de charge négative est compensée par la création simultanée de lacunes cationiques dont la concentration peut être réglés par la température de réaction. La nouvelle famille de matériaux polyanioniques a la composition générale de Ti1-x-y•x+yO2-4(x+y)F4x(OH)4y avec de lacune cationique jusqu’à 22 %. Le matériau considérablement dopé maintient son réseau cristallin original et montre une structure locale unique. Son mécanisme de formation est étudié à l'échelle atomique. Les effets des paramètres de synthèse sur la structure, la morphologie et la composition chimique de la phase obtenue sont étudiés en détail. Lorsqu'il est utilisé comme anode pour batteries aux ions lithium, l'anatase fluorée lacunaire montre des performances supérieures pour le stockage de lithium, surtout à haute régime de charge/décharge. La présence de lacune modifie le mécanisme d'insertion du lithium par rapport à TiO2 anatase stœchiométrique: une réaction de solution solide a été trouvé à la place une réaction diphasique, soulignant l'impact de la modification de la structure sur les propriétés électrochimiques vis-à-vis au Li+. Enfin, le mécanisme d'insertion de sodium dans anatase stœchiométrique et lacunaire est étudié. Des aperçus sans précédent sont acquis pour la réaction d’insertion de Na+. / Titanium dioxide (TiO2) is a multifunctional material and presents promising properties ranging from catalysis to energy storage and conversion. In order to obtain enhanced physico-chemical properties, several approaches were applied such as, reducing particle sizes, modifying morphology, doping with other elements. In this thesis, a new synthesis method based on sol-gel chemistry is developed in fluorinated medium. The divalent O2- in TiO2 anatase is substituted by monovalent F- and OH- anions, the deficiency of negative charge is counterbalanced by the simultaneous formation of cationic Ti4+ vacancies (•) which can be tuned by the reaction temperature. The new family of polyanionic materials has the general composition of Ti1-x-y•x+yO2-4(x+y)F4x(OH)4y with up to 22 % of cationic vacancies. The drastically doped material keeps its original crystalline network and shows unique local structure. Its formation mechanism is investigated at atomic scale. The effects of synthesis parameters on structure, morphology and chemical composition of the resulting phase are studied in details. When used as anode for lithium-ion batteries, the cation-defected fluorinated anatase shows superior lithium storage performance, especially at high charge/discharge rate. The presence of vacancy modifies lithium insertion mechanism compared to stoichiometric TiO2 anatase: a solid solution reaction was found instead a well-known two-phase reaction, highlighting the impact of structure modification on the electrochemical properties vs. Li+. Sodium insertion mechanism into stoichiometric and defective anatase are studied at the last. Unprecedented insights into Na+ insertion reaction are gained.