The demand for efficient and clean fuel alternatives has been increasing in recent years and is expected to become more pronounced in the future. Utilization of hydrogen as a fuel is one of the most promising energy resources due to its easy production, abundance, regeneration and not creation of greenhouse gases during its combustion. Although gaseous hydrogen has a very high energy content per unit weight, its volumetric energy density is rather low. The large scale use of hydrogen as a fuel crucially depends on the development of compact hydrogen storage materials with a high mass content of hydrogen relative to total mass and to volume. Certain metals and alloys are capable of reversibly absorbing large amounts of hydrogen to form metal hydrides. They exhibit the highest volumetric densities of hydrogen and are very promising for hydrogen storage because of their efficiency, cost and safety. Some of the metal hydride families can also be used in hydrogen compressors. The objective of this work is to investigate the synthesis and characterization behavior of intermetallic alloys (ZrMn2, ZrNi) for hydrogen compression and of complex hydrides (Zn(BH4)2 ) for on-board hydrogen storage. An overview of hydrogen as a fuel and its storage means is provided, synthesis and characterization methods of metal hydrides are presented and the effect of mechanical milling and the catalytic doping of metal/complex hydrides are investigated in detail. The hydrogen storage alloys (hydrides) are extensively characterized using various analytical tools such as: XRD, SEM, EDS, TCD, FTIR and GC/MS. The thermal (heat flow and weight loss) and volumetric (storage capacity, kinetics, cycle life, etc) analysis have been carried out via DSC/TGA and high pressure PCT apparatus. Finally conclusions and recommendations for future work are provided to improve the absorption/desorption cycle of hydrogen storage in the compounds under investigation.

Bi2Rh3Se2 have been known as a charge-density-wave (CDW) superconductor, where the superconducting critical temperature Tc and the CDW phase transition are about 0.7 K and 250 K, respectively. Since there has no definite proof that the anomaly at around 250 K comes from charge-density-wave, we wished to provide another evidence to study whether the superconductor had the properties of CDW by electric resistivity measurements applied different pressures. Bi2Rh3Se2 was prepared by using the solid state reaction method and heating in the quartz tube. After the sample was synthesized, the quality was identified by XRD, MPMS, and specific heat probe. With the confirmation of the above-mentioned measurements, we can determine the sample¡¦s quality is good. Furthermore, temperature-dependent resistivity (2-340 K) under pressure (up to 22.23 kbar) on the ternary superconductor Bi2Rh3Se2 are performed to study the possible coexistence of CDW and superconductivity. Interestingly, the resistive anomaly occurred at Ts~250 K, is shifted to higher temperature with increasing pressure. This experimental finding is not consistent with a traditional CDW transition. Moreover, the temperature-dependent Transmission Electron Microscopy (TEM) electron diffraction is evident a structural phase transition from space group ¡§C1 2/m 1¡¨ (Ts > 250 K) to ¡§P1 2/m 1¡¨ (Ts < 250 K). Finally, We do the Co doping to make sure the effects of chemical pressure on this phase transition. The results are opposite to imposed by physical pressure that the transition is shift to lower temperature with more Co inside the sample.

Cerium oxide has been used extensively for various applications over the past two decades. The use of cerium oxide nanoparticles is beneficial in present applications and can open avenues for future applications. The present study utilizes the microemulsion technique to synthesize uniformly distributed cerium oxide nanoparticles. The same technique was also used to synthesize cerium oxide nanoparticles doped with trivalent elements (La and Nd). The fundamental study of cerium oxide nanoparticles identified variations in properties as a function of particle size and also due to doping with trivalent elements (La and Nd). It was found that the lattice parameter of cerium oxide nanoparticles increases with decrease in particle size. Also Raman allowed mode shift to lower energies and the peak at 464 cm-1 becomes broader and asymmetric. The size dependent changes in cerium oxide were correlated to increase in oxygen vacancy concentration in the cerium oxide lattice. The doping of cerium oxide nanoparticles with trivalent elements introduces more oxygen vacancies and expands the cerium oxide lattice further (in addition to the lattice expansion due to the size effect). The lattice expansion is greater for La-doped cerium oxide nanoparticles compared to Nd-doping due to the larger ionic radius of La compared to Nd, the lattice expansion is directly proportional to the dopant concentration. The synthesized cerium oxide nanoparticles were used to develop an electrochemical biosensor of hydrogen peroxide (H2O2). The sensor was useful to detect H2O2 concentrations as low as 1µM in water. Also the preliminary testing of the sensor on tomato stem and leaf extracts indicated that the sensor can be used in practical applications such as plant physiological studies etc. The nanomolar concentrations of cerium oxide nanoparticles were also found to be useful in decreasing ROS (reactive oxygen species) mediated cellular damages in various in vitro cell cultures. Cerium oxide nanoparticles reduced the cellular damages to the normal breast epithelial cell line (CRL 8798) induced by X-rays and to the Keratinocyte cell line induced by UV irradiation. Cerium oxide nanoparticles were also found to be neuroprotective to adult rat spinal cord and retinal neurons. We propose that cerium oxide nanoparticles act as free radical scavenger (via redox reactions on its surface) to decrease the ROS induced cellular damages. Additionally, UV-visible spectroscopic studies indicated that cerium oxide nanoparticles possess auto-regenerative property by switching its oxidation state between Ce3+ and Ce4+. The auto-regenerative antioxidant property of these nanoparticles appears to be a key component in all the biological applications discussed in the present study.

Cette thèse porte sur l’étude de couches minces ferroélectriques à base de BaTiO3 déposées par pulvérisation cathodique. Ces matériaux permettent par exemple de réaliser des condensateurs accordables ou encore des mémoires non-volatiles pour le stockage d’informations. Cependant, leurs propriétés diélectriques sont considérablement dégradées par des effets extrinsèques d’interfaces; film/substrat ou encore film/électrode. Dans ce contexte, la spectroscopie de photoémission (XPS) a été utilisée pour quantifier les états électroniques et chimiques de ces interfaces avec une approche in-situ. L’étude sur la formation du contact film/électrode a permis de mesurer la hauteur de barrière de Schottky partiellement responsable des caractéristiques capacités – tensions des couches. Des phénomènes de ségrégation ont été mis en évidence révélant une profonde instabilité de la stoechiométrie de surface. Enfin, la conséquence d’un dopage au niobium dans les couches minces de BaTiO3 est discutée du point de vue des modes de compensation, de la solubilité du dopant et des propriétés diélectriques. / The aim of this work was to better understand the surface and interface properties of sputtered ferroelectric BaTiO3 thin films. They are typically used as dielectrics in integrated capacitors, electromechanical sensors and so. This thesis studies the chemical and electronic structures of the interface of BaTiO3 in order to understand basic mechanisms of contact formation with the substrate and the electrode like the Schottky barrier height. Furthermore, the surface stoichiometry of such films has been investigated under different thermal preparation revealing significant instability through segregation phenomenon. Finally, the doping effect with niobium is studied regarding compensation mode, dopant solubility and dielectric properties. The experimental setup allows for in-situ analysis of surface and interface properties using photoelectron spectroscopy.