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Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18981号 / 工博第4023号 / 新制||工||1619(附属図書館) / 31932 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 松原 英一郎, 教授 邑瀬 邦明, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd–Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd–Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd–Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd–Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd–Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd–Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd–Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (TC~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)x prepared with this method as compared to V(TCNE)x prepared by hitherto used methods.

<p>In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)_x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (T_C~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)_x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)_x prepared with this method as compared to V(TCNE)_x prepared by hitherto used methods.</p>

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

Orientador: Francisco das Chagas Marques / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T16:01:42Z (GMT). No. of bitstreams: 1 OliveiraJunior_MyrianoHenriquesde_M.pdf: 3252159 bytes, checksum: a130bcbe767628c40a0600e14112a2a4 (MD5) Previous issue date: 2005 / Resumo: Neste trabalho foi preparada uma série de filmes de carbono amorfo pelo processo de IBAD (Ion Beam Assisted Deposition), onde foi utilizado um feixe iônico de Xe com energia fixa para todas as amostras em 1500eV para realizar sputtering em um alvo de grafite e, um segundo feixe de Xe + responsável pelo bombardeio do filme durante o crescimento. Para cada amostra foi utilizada uma energia de bombardeio diferente, de 0 a 400eV. Esse bombardeio, além de gerar uma compactação da matriz induzindo uma pressão na rede (stress intrínseco), faz com que uma certa quantidade de Xe seja incorporada pelo filme. Por medidas de RBS foram observadas concentrações de 3 a 4% desse gás nobre na matriz, que são as concentrações nas quais são observadas formações de aglomerados sólidos desse elemento quando implantado em metais ou semicondutores cristalinos. Por medidas de XAS realizadas com radiação com energias no intervalo que envolve a borda L3 do xenônio foi verificada a formação de tais aglomerados sólidos e, em conjunto com resultados obtidos por simulações computacionais obtivemos um entendimento melhor sobre a estrutura fina na região de XANES dessa borda de absorção. A partir da técnica de SAXS foram encontradas estruturas com dimensões características de cerca de 10 a 25nm de forma achatada. Como os filmes de a-C crescidos por essa técnica são altamente grafíticos, contendo uma concentração de cerca de 90% de ligações do tipo sp 2 essas estruturas parecem ser aglomerados grafíticos, cujas dimensões mostraram-se dependentes da energia de bombardeio utilizada na deposição / Abstract: In this work it was prepared a series of amorphous carbon thin films using the ion beam assisted deposition technique. We used a xenon ion beam in order to sputter a graphite target with a fixed energy of 1500eV for all samples set up. A second ion beam was used as an ion assisting beam during the deposition with different energy for each film but, always in the range of 0 to 400eV. As the bombardment energy is varied the film produced can have a structure more or less compact which implies in a pressure rising along the amorphous net, called intrinsic stress. Another consequence of the bombardment is the xenon incorporation. By RBS measurements it was observed a concentration of about 3 to 4% of this noble gas inside the films, which belong to the same range where is observed a condensation of this element in solid clusters when implanted in crystalline metals or semiconductors. From XAS measurements, with radiation energy within a range involving the Xe L3 absorption edge, those solid clusters formation were observed. With some computational simulations compared to those experimental results we were able to have a better comprehension about XANES fine structure. We used SAXS measurements to try to determine some geometrical parameters beyond those obtained by XAS. As the xenon clusters dimensions are too small (probably of about ten atoms) it is difficult to detect them by this technique with the experimental parameters used but, it was observed some structures that seem to be shaped and have characteristics dimensions varying from 10 to 25nm. What seem to be graphitic planes clusters, once amorphous carbon thin films prepared by IBAD are graphitic-like / Mestrado / Física da Matéria Condensada / Mestre em Física

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity. / Science, Faculty of / Chemistry, Department of / Graduate