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Structure, Stability, Vibrational, Thermodynamic, And Catalytic Properties Of Metal Nanostructures: Size, Shape, Support, And Adsorbate EffectsBehafarid, Farzad 01 January 2012 (has links)
Recent advances in nanoscience and technology have provided the scientific community with new exciting opportunities to rationally design and fabricate materials at the nanometer scale with drastically different properties as compared to their bulk counterparts. A variety of challenges related to nanoparticle (NP) synthesis and materials characterization have been tackled , allowing us to make more homogenous, well defined, size- and shape-selected NPs, and to probe deeper and more comprehensively into their distinct properties. In this dissertation, a variety of phenomena relevant to nanosized materials are investigated, including the thermal stability of NPs and coarsening phenomena in different environments, the experimental determination of NP shapes, gaining insight into NP-support interactions, epitaxial relationships, and unusual thermodynamic and electronic properties of NPs, including the effect of adsorbates on the electron density of states of small clusters, and the chemical, and structural evolution of NPs under reaction conditions. In chapter 2, a general description of different characterization tools that are used in this dissertation is provided. In chapter 3, the details of two different methods used for NP synthesis, namely inverse micelle encapsulation and physical vapor deposition (PVD) are described. Chapter 4 describes the thermal stability and coarsening behavior of Pt NPs supported on TiO2(110) and γ-Al2O3 as a function of the synthesis method, support pretreatment, and annealing environment. For the Pt/TiO2(110) system, micellesynthesized NPs showed remarkable stability against coarsening for annealing temperatures up to 1060°C in vacuum, in contrast to PVD-grown NPs. When comparing v different annealing environments (H2, O2, H2O), Pt NPs on γ-Al2O3 annealed in O2 were found to be the least affected by coarsening, followed by those heated in H2O vapor. The largest NP growth was observed for the sample annealed in H2. The role of the PtOx species formed under oxidizing conditions will be discussed. In chapter 5, the shape of Pt and Au NPs and their epitaxial relationship with the TiO2(110) support was extracted from scanning tunneling microscopy (STM) measurements. Three main categories of NP shapes were identified, and through shape modeling, the contribution of facets with different orientations was obtained as a function of the number of atoms in each NP. It was also shown that the micellesynthesized Pt and Au NPs have an epitaxial relationship with the support, which is evident from the fact that they always have one symmetry axis parallel to TiO2(110) atomic rows in [001] directions. Chapter 6 describes how the presence of NPs on TiO2(110) surface affects its reconstruction upon high temperature annealing in vacuum. In contrast to NP-free TiO2(110) substrates, long and narrow TiO2 stripes are observed for Pt NP-decorated surfaces. This phenomenon is explained based on the stabilization of TiO2, induced by Pt NPs, which hinders the desorption of oxygen atoms in TiO2 to vacuum. In chapter 7, a systematic investigation of the thermodynamic properties of γ- Al2O3-supported Pt NPs and their evolution with decreasing NP size is presented. A combination of in situ extended x-ray absorption fine structure spectroscopy (EXAFS), ex situ transmission electron microscopy (TEM) measurements, and NP shape modeling is used to obtain the NPs shape, thermal expansion coefficient, and Debye vi temperature. The unusual thermodynamic behavior of these NPs such as their negative thermal expansion and enhanced Debye temperature are discussed in detail. Chapter 8 presents an investigation of the electronic properties of size-controlled γ-Al2O3-supported Pt NPs and their evolution with decreasing NP size and adsorbate (H2) coverage. The hydrogen coverage of Pt NPs at different temperatures was estimated based on XANES data and was found to be influenced by the NP size, and shape. In addition, correlations between the shift in the center of the unoccupied d-band density of states (theory) and energy shifts of the XANES spectra (experiment) upon hydrogen chemisorption as well as upon modification of the NP structure were established. Chapter 9 is dedicated to an operando study, describing the evolution of the structure and oxidation state of ZrO2-supported Pd nanocatalysts during the in-situ selective reduction of NO in H2 via EXAFS and XANES measurements.
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Etude de la croisssance CVD des films minces de 3C-SiC et élaboration du cantilever AFM en 3C-SiC avec pointe Si intégrée / Study of the CVD growth of 3C-SiC thin films and fabrication of 3C-SiC based AFM centilever with integrated Si typeJiao, Sai 12 November 2012 (has links)
Parmi les polytypes les plus connus du carbure de silicium (SiC), le polytype cubique (3C-SiC), est le seul qui peut croitre sur des substrats silicium. L’hétérostructure 3C-SiC/Si est intéressante non seulement pour son faible coût de production mais aussi pour la conception de Systèmes Micro-Electro-Mécaniques (« MEMS »). La valeur élevée du module de Young du 3C-SiC, comparé à celui du silicium, permettrait à des cantilevers submicroniques, fabriqués à partir de films minces de 3C-SiC, de vibrer à ultra-hautes fréquences (>100MHz). Cette haute fréquence de résonance est la clé pour obtenir un système AFM non-contact ultra-sensible et rapide. Cependant, il n’existe pas de cantilever en SiC disponible sur le marché en raison de la difficulté à élaborer des films minces de 3C-SiC de bonne qualité, la technique de synthèse la plus utilisée étant le Dépôt Chimique en phase Vapeur (CVD). La raison première de cette difficulté à obtenir un matériau de bonne qualité réside essentiellement dans l’important désaccord de maille et la différence de dilatation thermique entre le 3C-SiC et Si qui génèrent des défauts cristallins à l’interface et jusqu’à la surface du film de 3C-SiC, la zone la plus défectueuse se localisant auprès de l’interface……. / Among aIl the well known polytypes ofihe silicon carbide (SiC), the cubic polytype (3C-SiC) is the only one that min be grown on silicon substrates. This heterostructure 3C SiC/Si ta interesting not only for its low production cost but also for the design of tise Micro-Electro-Mechanical Systems (MEMS). The high value ofthe Young’s modulis the 3C-SiC, compared to the silicon, allows submicronic cantilevers, fabrmcated from tIse 3C-SiC thin filins, to resonate at ultra-high frequency (>100MHz). The high resonant frequency is the key to obtain s fast, ultra-sensitive non-contact AFM systein.However, there isn’t any SiC cantilevers available on the market because of the difficulty to elaborate gond quality 3C-SiC thin films, with tIse Chemical Vapor Deposition (CVD) technique being tIse most frequently used synthesis technology. Tise first reason of tIse difficulty with the CVD technology to obtain gond quality thin film rests essentially in the important lattice mismatch and the difference in thermal expansion coefficient existing between 3C SiC and Si which generate crystalline defects at the interface and propagating tilI the 3C-SiC filin surface, with the inost defective zone localizing near the interface…….
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