Cette étude concerne la valorisation du dioxyde de carbone par le procédé de méthanation. Elle vise à mettre au point des catalyseurs efficaces pour cette réaction. L'espèce active est le nickel métallique. Différents supports ont été étudiés tels que SiO₂, Al₂O₃, MgO, Y₂O₃ et CeO₂. Ces catalyseurs ont été préparés par la méthode d'imprégnation à sec. Dans un premier temps, les différents catalyseurs ont été caractérisés par différentes techniques physico-chimiques dont la Diffraction des Rayons X (DRX), la Réduction en Température Programmée (RTP-H₂), la Désorption en Température Programmée (DTP-CO₂), l'Adsorption d'Azote (méthode BET) et la Chimisorption d'Hydrogène. Dans un deuxième temps, les différents catalyseurs ainsi préparés ont été testés dans la réaction de méthanation du CO₂. Le catalyseur Ni/CeO₂ présente les meilleures performances catalytiques, parmi les systèmes étudiés. L'ajout du ruthénium améliore l'activité catalytique et la stabilité des catalyseurs. Le catalyseur Ru(0,5%)-Ni(5%)/CeO₂ est le plus performant, il présente une bonne activité catalytique et une bonne stabilité même pour une pression de 10 bar. Ceci le rend plus avantageux pour une application industrielle. / This study concerns the valorization of carbon dioxide by the methanation process. It aims to develop effectiv catalysts for this reaction. The active species is metallic nickel. Different supports have been studied such as SiO₂, Al₂O₃, MgO, Y₂O₃ and CeO₂. These catalysts were prepared by the dry impregnation method. Initially, the different catalysts were characterized by different physicochemical techniques including X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR-H₂), Temperature Programmed Desorption (TPD-CO₂), nitrogen adsorption (BET method) and hydrogen chemisorption. In a second step, the various catalysts thus prepared were tested in the CO₂ methanation reaction. The Ni/CeO₂ catalysts has the best catalytic performance, among the systems studied. The addition of ruthenium improves the catalytic activity and the stability of the catalysts. The catalyst Ru(0.5%)-Ni(5%)/CeO₂ is the most efficient, it has good catalytic activity and good stability even as a pressure of 10 bar. This makes it advantageous for an industrial application.

This work is studying the layers of cerium oxide (doped with platinum) prepa- red by magnetron sputtering on different types of substrates. Attention is focused mainly on modes of growth and morfology of (Pt−)CeO2 layers. The study was carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The specimens (lamellas) were created by using focused ion beam (FIB) with respect to transparency for electron beam and material contrast. The emphasis was on elimination of redeposition and minimize the amorphous layer of lamella. Representation of elements was determined by energy-dispersive spectroscopy (EDX) and electron-energy loss spectroscopy (EELS). 1

This work reports on physical properties of a novel CeCo0.715Si2.285 compound. The compound crystallizes in the I-4m2 space group structure with extremely elongated unit cell (a = 4.13˚A , c = 32.84˚A) containing BaAl4 structural patterns. In zero magnetic field it orders antiferromagnetically at TN = 10.0K. Under application of magnetic field along the c-axis it manifests numerous magnetic transitions in small fields (B < 0.5T), resembling the so-called 'devil's staircase' behaviour (e.g. CeSb, CeCoGe3). The magnetization is almost constant from 1T up to 45T for H||c but considerably reduced (0.3µB/Ce) with respect to the free Ce3+ ion. For fields applied along the a-axis typical behaviour for a hard axis in a material with uniaxial anisotropy is observed. The performed single crystal neutron diffraction experiment did not allow complete determination of magnetic structure. 1

>Magister Scientiae - MSc / The industrial safety requirements and environmental pollution have created a high demand to develop gas sensors to monitor combustible and toxic gases. As per specifications of World Health Organization (WHO) and Occupational Safety and Health Administration (OSHA), lengthy exposure to these gases lead to death which can be avoided with early detection. Semiconductor metal oxide (SMO) has been utilized as sensor for several decades. In recent years, there have been extensive investigations of nanoscale semiconductor gas sensor.

Cerium oxide nanoparticles (nanoceria) have recently been shown to protect cells against oxidative stress in both cell culture and animal models. Nanoceria has been shown to exhibit superoxide dismutase (SOD) activity using a ferricytochrome C assay, and this mimetic activity that has been postulated to be responsible for cellular protection by nanoceria. The nature of nanoceria's antioxidant properties, specifically what physical characteristics make nanoceria effective at scavenging superoxide anion, is poorly understood. In this study electron paramagnetic resonance (EPR) analysis confirms the reactivity of nanoceria as an SOD mimetic. X-ray photoelectron spectroscopy (XPS) and UV-visible analyses of nanoceria treated with hydrogen peroxide demonstrate that a decrease in the Ce 3+/4+ ratio correlates directly with a loss of SOD mimetic activity. These results strongly suggest that the surface oxidation state of nanoceria plays an integral role in the SOD mimetic activity of nanoceria and that ability of nanoceria to scavenge superoxide is directly related to cerium(III) concentrations at the surface of the particle.

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Over time science has provided us with new materials and fabrication techniques making it possible to design and create more complex engineering components for service. If we are to include these materials in damage tolerant design efforts, engineers need to understand when/where degradation will occur in the engineering component. To do so it is imperative that micromechanical studies be conducted to understand the material behavior of the microstructural features including phases, build pattern features, and microstructural imperfections including cracks of new materials to validate any future modeling efforts. This dissertation will discuss the experimental and computational micromechanics of extruded and cast aluminum cerium alloys and selective laser melted 316L stainless steel. In Chapters 2 and 3, micromechanical experiments and computational efforts are carried out on extruded 52:1 Al-8Ce-10Mg alloy. Using in-situ scanning electron microscopy tensile testing microcracking is observed in Al11Ce3 intermetallic after yield in the bulk alloy. In-situ digital image correlation tests observe the load sharing characteristics between the Al(Mg) matrix and the Al11Ce3 intermetallic before and after microcracking. Finally, that failure process is determined to be coalesce of microvoids leading to ductile damage failure. These results are used to create an experimental-computational framework to develop a crystal plasticity finite element model for extruded Al-8Ce-10Mg alloys. The calibrated model is used to perform multiple simulations evaluate the possible effect changes intermetallic content and grain orientation texture have on the mechanical strength of the alloy. The experimental and computational framework are expandable to other material systems not just Al-Ce alloys. In Chapter 4, in-situ scanning electron microscopy tensile testing is used to investigate how the matrix and intermetallic phases contribute to the failure behavior alloy of cast Al-11Ce- 0.4Mg alloy. The in-situ tests shows that after multiple points of crack nucleation, crack coalescence causes the subsequent failure to occur in the Al(Mg) matrix phase of the alloy, as seen by tortuous behavior. The cause of this crack behavior is determined to be due to the high strength match between the matrix and intermetallic phase, strong metallurgical bond between the two phases, and the size effect created by large eutectic colonies created during casting. The results of the experimental work are used to propose a 3D multiscale computational model of cast Al-Ce alloys. In Chapter 5, micromechanical experiments are carried out on SLM 316L Stainless Steel with four different sets of varied processing parameters. Discontinuous yielding is observed in the lowest energy density sample caused by the strong [110] texture, optimal for dislocation slip, in the loading direction. The in-situ loading experiments are also able to capture the melt pool track deformation and crack formation that leads to the failure of these samples. This highlights the importance of micromechanical experiments for additive manufactured materials. / Doctor of Philosophy / As time has progressed new materials have been discovered that make it possible to design more complex parts for engineering design. To ensure the safety and reliability of these materials, engineers need to understand when/where damage will occur in a design. Micromechanical studies conducted at magnifications higher than human visible range allow engineers to explore where damage in materials initiates which would otherwise not be detected until after failure. The results of these studies can be used to build and test models of these materials. This dissertation will discuss the micromechanical studies of extruded and cast aluminum cerium alloys and selective laser melted 316L stainless steel. In Chapters 2 and 3, micromechanical experiments and computational techniques are performed on extruded Al-Ce alloys. In Chapter 4, the failure behavior of cast Al-Ce alloys is examined in active tension using scanning electron microscopy. Finally, in Chapter 5, selective laser melted 316L stainless steel is studied and the results highlight the importance of micromechanical experiments for the new age of metal 3D printing.

A serious challenge in photocatalytic solar fuel production lies in the design of efficient catalysts that are stable, have visible light response and are easy to make. In order to realize this goal, efforts should be focused on designing new photocatalysts that have such properties to drive the field forward towards commercialization. Metal-Organic Frameworks (MOFs) are a class of crystalline and porous materials that offer tunable and diverse structural and electronic properties that can be exploited for enhanced photocatalytic solar fuels production. This thesis focuses on the utilization and characterization of a 3-D MOF photocatalyst with metal-oxo chain and pyrene-based ligand as secondary building units. Specifically, through hydrothermal synthesis technique, we constructed a bimetallic cerium/titanium MOF that exhibits excellent and stable photoactivity for visible-light driven hydrogen generation. The incorporation of two redox active metals of CeIII /CeIV and TiIII/TiIV in an oxo-chain connected by a photosensitizing organic ligand resulted in a strong ligand-tometal charge transfer (LMTC), evident by EPR, for efficient reduction of water. A high hydrogen production rate of 49 μmol h-1 was achieved, which is attributed to energetic LMTC and better charge separation. This work expands on MOFs photocatalysis field and open new direction towards designing redox active heterometallic MOFs for solar fuels production.

A comparative study of the electro-oxidation of ethanol and methanol was carried out on a Pt/ceria composite electrode prepared by electro-deposition. Modification of the Pt electrode was realized by co-deposition from a 1.0 mM K₂PtCl₆ solution that also contained a 20 mM suspension of ceria. The electro-catalytic activities and stabilities of the Pt/ceria catalyst towards ethanol electro-oxidation reactions (EOR) and methanol electro-oxidation reactions (MOR) were investigated by potentiodynamic and potentiostatic methods in 0.5 M sulfuric acid and 1.0 M sodium hydroxide solutions at various concentrations of ethanol and methanol. The kinetics of ethanol and methanol on a Pt/ceria composite electrode were measured in 0.5 M sulfuric acid and 1.0 M sodium hydroxide solutions using a rotating disk electrode (RDE). Cyclic voltammetry was employed in temperatures ranging from 15 to 55°C to provide quantitative and qualitative information on the kinetics of alcohol oxidation. The temperature dependence of the electro-catalytic activities afforded the determination of apparent activation energies for ethanol and methanol oxidation.