Investigating the structure-property relationships of solid state materials can help improve many of the materials we use each day in life. It can also lead to the discovery of materials with interesting and unforeseen properties. In this work the structure property relationships of newly discovered layered oxypnictide phases are presented and discussed. There has generally been worldwide interest in layered oxypnictide materials following the discovery of superconductivity up to 55 K for iron arsenides such as LnFeAsO[subscript 1-x]F[subscript x] (where Ln = Lanthanoid). This work presents efforts to understand the structure and physical property changes which occur to LnFeAsO materials when Fe is replaced with Rh or Ir and when As is replaced with Sb. As part of this work the solid solution between LaFeAsO and LaRhAsO was examined and superconductivity is observed for low Rh content with a maximum critical temperature of 16 K. LnRhAsO and LnIrAsO compositions are found to be metallic; however Ce based compositions display a resistivity temperature dependence which is typical of Kondo lattice materials. At low temperatures a sudden drop in resistivity occurs for both CeRhAsO and CeIrAsO compositions and this drop coincides with an antiferromagnetic transition. The Kondo scattering temperatures and magnetic transition temperatures observed for these materials can be rationalized by considering the expected difference in N(E[subscript F])J parameters between them, where N(E[subscript F]) is the density of states at the Fermi level and J represents the exchange interaction between the Ce 4f¹ electrons and the conduction electrons. In addition to studying these 4d and 5d substituted systems the LaFeSbO compositional system was investigated. While LaFeSbO has not been successfully synthesized the transition metal free layered oxypnictide composition La₂SbO₂ was discovered and its structural and physical properties have been examined along with the properties of La₂BiO₂. Density functional theory was used to calculate the heats of formation for competing phases within the LaFeSbO system, in order to better understand the stability of LaFeSbO and why it has not yet been observed. The materials La₂SbO₂ and La₂BiO₂ were investigated for the presence of oxygen vacancies using powder neutron diffraction. Structure refinement reveals that there is significant disorder within the a-b plane for Sb compositions. / Graduation date: 2012

L'utilisation de l'équation de Dirac/Weyl conduit à une simplification conceptuelle dans une description de la structure de la bande dans les solides à faible échelle d'énergie. En particulier, les excitations d'électrons-trous peuvent être considérées comme analogues au cas relativiste tel que conductivité optique linéaire, le suppression de backscattering ou la manifestation des arcs de Fermi et la chiralité des particules. En outre, la phase semi-métallique est également un élément crucial pour la classification des matériaux. La taille de le gap est affectée qualitativement par le type de dispersion d'énergie par un croisement continu des bandes linéaires à paraboliques. Cela peut être compris comme une limite classique ou ultra-relativiste du mouvement d'une particule massive.La spectroscopie infrarouge de la transformation de Fourier est une technique unique pour étudier les excitations optiques dans une large gamme d'énergies et représente en combinaison avec le champ magnétique élevé un outil puissant pour sondage de la structure électronique et surmonte le principal obstacle des systèmes sans gap qui est un dopage fort en raison de désordre structurel.La première partie du travail est consacrée à l'arséniure de cadmium, où nous élaborons une approche de distinction qualitative entre les systèmes Dirac et Kane qui ont été utilisés pour prouver sur la base de la réponse magnéto-optique observée la réalisation du modèle Kane presque sans gap avec une similitude frappante avec HgCdTe, en contradiction avec l'existence de cônes purement Dirac. La magnéto-réflectivité dans un champ magnétique à champ élevé la résonance cyclotron caractéristiques par un radical-B dépendance avec un comportement particulier dans la limite quantique. En revanche, la magnéto-transmission montrait des transitions de niveau Landau qui doit être interprétées que comme un type plat-à-cône afin de préserver une cohérence totale du modèle. Les cônes de Dirac prédits par la théorie sont susceptibles de coexister dans le modèle de Kane sous la forme d'une sous-structure décrite par le modèle de Bodnar qui se rapproche de la structure cristalline complexe par une simple cellule antifluorite qui permet d'utiliser la théorie du k.p classique.Dans la deuxième partie, nous nous concentrons sur le bismuth comme isolant topologique 3D archétype. Nous étudions une condition particulière obéie pour le BHZ-hamiltonien qui apporte des propriétés intriguantes comme une relation inhabituelle de spin gap et la résonance du cyclotron, l'épinglage spécifique entre les fancharts des sous-groupes Landau ou les g-facteurs compensés dans les bandes de conduction et de valence. Les mesures de photoluminescence ont montré une émission directgap, ce qui donne un nouvel aperçu de la structure largement acceptée à partir des données ARPES, où la “chameau structure” de la bande de valence doit être expliquée dans le confinement de surface et le point de Dirac de l'état de surface doit être repositionné par rapport aux bandes en bulk. La réponse magnéto-optique peut être pleinement expliquée dans une image classique du paramagnétisme de Pauli comme un simple effet d'occupation. Un tel comportement se manifeste dans la transmission en tant que fractionnement progressif du bord d'absorption interbande avec une saturation successive due à la polarisation spin partielle ou totale des électrons. Le dichroïsme relatif entraîne également une forte rotation de Faraday linéaire décrite par un modèle simple de la constante Verdet qui ne dépend pas sur le niveau de Fermi. / The use of the Dirac/Weyl equation leads to a conceptual simplification in a description of the band structure in solids at low energy scales. In particular, electron-hole excitations can be regarded as an analogue to the relativistic case with several expected phenomena to be observed in the condensed systems such as a suppressed back-scattering, linear optical conductivity or the manifestation of the Fermi arcs and particle's chirality. Moreover, the semimetallic phase also symbolizes a boundary between the trivial and topological insulators and thus play a crucial role for the material classification. The size of the gap qualitatively affects the type of the energy dispersion by a continuous crossover from the linear to parabolic bands. This fact can be easily understood as a classical or ultra-relativistic limit of the motion of a free massive particle.Infrared Fourier transform spectroscopy is a unique technique for studying optical excitations in a wide range of energies and it represents in combination with the high magnetic field a powerful tool for probing electronic structure and overcomes the main obstacle of the gapless systems that is a strong doping due to the structural disorder.The first part of the work is devoted to cadmium arsenide, where we elaborate an approach to qualitatively distinguish between the Dirac and Kane systems that was used to prove on the basis of the observed magneto-optical response the realization of the nearly gapless Kane model with a striking similarity to HgCdTe, contradicting the existence of purely Dirac cones. The magneto-reflectivity revealed a strong splitting of the plasma edge that turns into the cyclotron resonance characteristic by a squareroot-of-B dependence in the high magnetic field with a particular behaviour in the quantum limit independent on the initial Fermi level. In contrast, the magneto-transmission revealed interband Landau level transitions that could be only interpreted as a flat-to-cone type in order to preserve a full consistency of the model. The Dirac cones predicted by theory are feasible to coexist within the Kane model in the form of a substructure described by the Bodnar model that approximates the complex crystal structure by a simple antifluorite cell, which allows to use the conventional k.p-theory.In the second part, we focus on bismuth selenide entitled as an archetypal 3D topological insulator. We study a peculiar condition fulfilled for the BHZ-hamiltonian that brings intriguing properties such as an unusual relation of the spin gap and cyclotron resonance, the specific pinning between fancharts of Landau subsets or the compensated g-factors of the conduction and valence bands. The photoluminescence measurements showed a direct-gap emission, that gives a new insight to the widely accepted structure from ARPES data, where the declared camel-back structure of the valence band needs to be explained within the surface confinement and the Dirac point of the surface state should be repositioned with respect to the bulk bands. The magneto-optical response can be fully explained in a classical picture of the Pauli paramagnetism as a purely occupational effect. Such behaviour is evinced in the transmission as a gradual splitting of the interband absorption edge with a successive saturation due to the partial or total spin polarization of electrons. The related dichroism drives also a strong linear Faraday rotation described by a simple model of the Verdet constant that depends only on the Fermi level.

108 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-08T14:18:11Z No. of bitstreams: 1 Dissertação - Camila Santana Carriço.pdf: 3281348 bytes, checksum: a3b9881e9a61204bb28727d3345e0e1e (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-06T15:31:43Z (GMT) No. of bitstreams: 1 Dissertação - Camila Santana Carriço.pdf: 3281348 bytes, checksum: a3b9881e9a61204bb28727d3345e0e1e (MD5) / Made available in DSpace on 2013-06-06T15:31:43Z (GMT). No. of bitstreams: 1 Dissertação - Camila Santana Carriço.pdf: 3281348 bytes, checksum: a3b9881e9a61204bb28727d3345e0e1e (MD5) Previous issue date: 2012 / CAPES / O aproveitamento do glicerol excedente pela conversão catalítica a produtos de maior valor agregado vem sendo bastante estudado no sentido de dar um destino mais nobre a este coproduto, valorizando a cadeia produtiva do biodiesel. Dentre os processos de conversão catalítica do glicerol destaca-se a sua desidratação a acroleína, um produto de grande interesse da Química Fina, que pode ser utilizada como matéria-prima para a produção de ácido acrílico, polímeros superabsorventes produtos farmacêuticos, entre outros. Os zeólitos são catalisadores bastante ativos para a desidratação do glicerol a acroleína, devido às suas propriedades ácidas e texturais, mas sua principal limitação é a rápida desativação por formação de coque, como resultado da acidez excessiva e dos pequenos diâmetros de poros encontrados nestes materiais. Uma alternativa promissora é o uso de materiais derivados de zeólitos de precursores lamelares, que permitem ajuste das propriedades ácidas e texturais através de processos de pilarização e exfoliação. Neste trabalho, o precursor lamelar de estrutura MWW foi sintetizado nas razões molares SiO2/Al2O3 = 30, 50 e 80, e convertidos ao zeólito MCM-22 por calcinação, ao derivado pilarizado com SiO2, conhecido como MCM-36 e ao derivado exfoliado, denominado ITQ-2. As amostras foram caracterizadas por DRX, FTIR, TG/DTG, análise textural, MEV e TPD-NH3. Os materiais foram avaliados na reação de desidratação do glicerol à acroleína em fase gasosa e os parâmetros reacionais temperatura, tempo de contato (W/F) e concentração de glicerol foram ajustados com o zeólito MCM-22 na razão molar SiO2/Al2O3 = 30. As condições que favoreceram maiores conversões e seletividades foram empregadas para avaliar os materiais MCM-36 e ITQ-2. Os difratogramas de raios-X comprovaram que a síntese dos materiais foi bem sucedida, apresentando os picos característicos da topologia MWW. A análise textural mostra uma diminuição do volume de microporos e um aumento do volume de mesoporos, consistente com os processos de pilarização e exfoliação do precursor lamelar de estrutura MWW. O processo de exfoliação aumenta a acessibilidade aos sítios ácidos, enquanto a pilarização provoca o bloqueio dos sítios ácidos de natureza zeolítica e criação de novos sítios ácidos devidos aos pilares de SiO2. O melhor desempenho do MCM-36 na conversão de glicerol pode ser associado a sua dupla porosidade, a qual não permite que os canais/sítios ativos sejam obstruídos pela formação de resíduos carbonáceos, e consequentemente, permite que este material seja ativo por mais tempo, no entanto apresenta baixa seletividade a acroleína e formação de subprodutos gasosos. O ITQ-2 mostrou-se altamente seletivo a acroleína, resultado da maior densidade de sítios ácidos e maior acessibilidade aos sítios zeolíticos presentes nas semicavidades superficiais das lamelas. Em todos os materiais o aumento da razão molar SiO2/Al2O3 resulta num decréscimo da conversão do glicerol e da seletividade à acroleína. O principal mecanismo de desativação destes materiais é a formação de coque, que pode ser eliminado por tratamento em atmosfera oxidante a 500°C. O ITQ-2 apresentou uma boa recuperação em três ciclos reacionais / Salvador

Os argilominerais são empregados na área farmacêutica e cosmética tanto como excipientes quanto ingredientes ativos. Esses compostos inorgânicos são inertes quimicamente, apresentam estruturas definidas e alta estabilidade térmica, o que contribui para o uso nessas áreas. Atualmente a indústria farmacêutica busca modificações no sistema de entrega de drogas (melhorias no tempo, local e taxa de liberação), objetivando um aumento na estabilidade das drogas e a prevenção e diminuição de efeitos colaterais. Nesse sentido, surge a necessidade de desenvolver novas formulações farmacêuticas, novos métodos de preparação e novos materiais. Considerando o fato dos argilominerais incorporarem espécies diversas entre suas lamelas, é interessante explorar a possibilidade de uso dessas matrizes inorgânicas como carregadores de espécies bioativas. O principal objetivo do presente trabalho foi preparar e caracterizar argilas de uso farmacêutico e/ou cosmético intercaladas com espécies que apresentam potencial terapêutico. Para tanto, usou-se duas argilas esmectitas naturais do tipo montmorilonita (Cloisita Sódica e Veegum HS) e uma esmectita sintética do tipo hectorita (Laponita RD). Os aminoácidos L-lisina, L-arginina e L-ornitina, e o dipeptídeo L-carnosina foram imobilizados em argilas catiônicas, por meio de reação de troca iônica. Na preparação dos materiais híbridos, alguns parâmetros experimentais foram avaliados: concentração hidrogeniônica (pH) da suspensão de reação, proporção argila/aminoácido e tempo de reação. As argilas precursoras e os materiais híbridos obtidos foram caracterizados por difratometria de raios X, espectroscopia vibracional na região do infravermelho e Raman, análise termogravimétrica acoplada à espectrometria de massas e análise química de carbono. Os valores de distância interlamelar (d(001)) dos materiais sugerem que a cadeia carbônica das espécies orgânicas se orienta paralelamente em relação às lamelas de baixa densidade de carga dos argilominerais. Nos espectros vibracionais na região do infravermelho há predominância das bandas características da estrutura inorgânica, mas as bandas entre 1800 e 1400 cm-1 relativas aos grupos funcionais do aminoácido permitem inferir sobre o seu grau de protonação no material híbrido. A acidez de Brönsted gerada pela polarização das moléculas de água associadas à argila foi observada para as montmorilonitas empregadas neste estudo. Amostras preparadas em suspensões nas quais o valor do pH era maior que o valor da primeira constante ácida (pKa1) dos aminoácidos apresentam bandas atribuídas ao estiramento C=O de grupo carboxilato protonado. Os espectros Raman foram obtidos apenas para a argila sintética, uma vez que as naturais apresentam luminescência. O espectro Raman da L-carnosina imobilizada em Laponita indica a presença preponderante da espécie zwitteriônica; o deslocamento das bandas atribuídas aos grupos amida e carboxílico do dipeptídeo para região de menor energia sugere a formação de ligações de hidrogênio com os grupos silanol da Laponita. Os resultados de análise termogravimétrica acoplada à espectrometria de massas dos materiais híbridos são distintos daqueles observados para os aminoácidos livres. A temperatura de início de decomposição das espécies orgânicas não é praticamente modificada após imobilização nas argilas, mas os processos térmicos se estendem até regiões de maior temperatura, evidenciando a influência da estrutura inorgânica sobre a decomposição térmica dos aminoácidos. Através dos dados de quantidade de carbono e de água nas amostras, calculou-se a concentração de aminoácidos nos materiais híbridos (massa de aminoácido / 100 gramas de material). As maiores concentrações de aminoácido (entre seis e oito por cento) foram observadas para as amostras de Cloisita e Veegum HS, isoladas em condições nas quais predomina a interação eletrostática entre as lamelas e os aminoácidos com carga positiva. Nas condições experimentais empregadas neste trabalho não foi observada a saturação das argilas com os aminoácidos, ou seja, as cargas das lamelas não foram totalmente neutralizadas pelos íons orgânicos. / Clay minerals are used as excipients or active ingredients in the pharmaceutical and cosmetic fields. These inorganic compounds are chemically inert, have defined structures and high thermal stability, which make them useful for these areas. Currently the pharmaceutical industry seeks modifications in the drug delivery systems (improvements in the time, place and rate of release), aiming an increase in the stability of the drugs and also the prevention and reduction of side effects. In this way, it is a need to develop new pharmaceutical formulations, new preparation methods and new materials. Considering the fact that clay minerals incorporate various species between their layers, it is interesting to explore the possibility of using these inorganic matrices as carriers of bioactive species. The main aim of this work was to prepare and characterize clays of pharmaceutical and/or cosmetic usage intercalated with species of therapeutic potential. Two natural smectite clays of montmorillonite type (Sodium Cloisite and Veegum HS) and one synthetic smectite of hectorite type (Laponita RD) were employed. The amino acids L-lysine, L-arginine and L-ornithine, and the L-carnosine dipeptide were immobilized on cationic clays by ion exchange reaction. Some experimental parameters were evaluated in the preparation of hybrid materials: hydrogen ion concentration (pH) of reaction suspension, clay/amino acid proportion and reaction time. Pristine clays and hybrid materials were characterized by X-ray diffraction, infrared and Raman vibrational spectroscopies, thermogravimetric analyses coupled to mass spectrometry and chemical analysis of carbon. The materials values of interlayer distance (d(001)) suggest that the carbon chain of the organic species is oriented parallel to the layers of clay minerals. The infrared vibrational spectra are dominated by the inorganic structure bands; however the bands between 1800 and 1400 cm-1 related to the functional groups of the amino acid allow to infer about the protonation degree in the hybrid material. The Brönsted acidity generated by the polarization of water molecules associated with the clay was observed for montmorillonite samples used in this study. Materials prepared in suspensions in which the pH value was greater than the value of the first acid constant (pKa1) show bands assigned to the C=O stretching of protonated carboxylate group. Raman spectra were obtained only for the synthetic clay, since the natural ones luminesce. Raman spectrum of L-carnosine immobilized on Laponita indicates the presence of mostly zwitterionic species; the displacement of bands assigned to amide and carboxylic groups of the dipeptide to the lower energy region suggests the formation of hydrogen bonds with the Laponita silanol groups. The results of thermogravimetric analyses coupled to mass spectrometry of hybrid materials are different from those observed for the free amino acids. The onset temperature of the organic species decomposition is practically unmodified after the immobilization on clays, but thermal processes are postponed up to higher temperature, revealing the inorganic structure influence on the amino acids thermal decomposition. Data on the carbon and water amounts in the samples were used to calculate the concentration of amino acids in the hybrid materials (mass of amino acid / 100 grams of material). The highest concentrations of amino acid (between six and eight percent) was observed for Cloisite and Veegum HS samples, isolated under conditions in which the electrostatic interaction between the layers and the positively charged amino acids are predominant. Under the experimental conditions employed in this study no saturation of clay with amino acids was observed, i.e. the layer charges were not completely neutralized by the organic ions.

No description available.

No description available.

Thermoelectric materials can convert waste heat into electric power and thus provide a way to reduce the dependence on fossil fuels. Our aim is to model the underlying materials properties and, in particular, the transport as controlled by electrons and lattice vibrations. The goal is to develop an understanding of the thermoelectric properties of selected materials at a fundamental level. The structural, electronic, optical, and phononic properties are studied in order to tune the transport, focusing on KxRhO2, NaxRhO2, PtSb2 and Bi2Se3. The investigations are based on density functional theory as implemented in the all electron linearized augmented plane wave plus local orbitals WIEN2k and pseudo potential Quantum-ESPRESSO codes. The thermoelectric properties are derived from Boltzmann transport theory under the constant relaxation time approximation, using the BoltzTraP code. We will discuss first the changes in the electronic band structure under variation of the cation concentration in layered KxRhO2 in the 2H phase and NaxRhO2 in the 3R phase. We will also study the hydrated phase. The deformations of the RhO6 octahedra turn out to govern the thermoelectric properties, where the high Seebeck coefficient results from ”pudding mold" bands. We investigate the thermoelectric properties of electron and hole doped PtSb2, which is not a layered material but shares “pudding mold" bands. PtSb2 has a high Seebeck coefficient at room temperature, which increases significantly under As alloying by bandgap opening and reduction of the lattice thermal conductivity. Bi2Se3 (bulk and thin film) has a larger bandgap then the well-known thermoelectric material Bi2Te3, which is important at high temperature. The structural stability, electronic structure, and transport properties of one to six quintuple layers of Bi2Se3 will be discussed. We also address the effect of strain on a single quintuple layer by phonon band structures. We will analyze the electronic and transport properties of Tl-doped Bi2Se3 under strain, focusing on the giant Rashba spin splitting (Tl doping breaks the inversion symmetry in Bi2Se3) and its dependence on biaxial tensile and compressive strain.

No description available.

A number of different aspects of the chemistry of layered double hydroxides and similar materials have been explored in this thesis. The intercalation chemistry of these compounds, in both aqueous and mixed solutions, has been explored to synthesise over forty new hybrid layered materials by ion-exchange and rehydration-reconstruction methods. The host used include both previously-reported layered hydroxide compounds, and novel host materials synthesised by the extension of heterogeneous reactions of solid oxides. The synthesis of these novel materials provides insights into the factors that control the compatibility of the metal ions that may form hydrotalcite-like structures, in addition to providing compounds that may act as the precursors of catalysts and other functional materials. The new intercalation compounds synthesised show interlayer distances ranging from 7.1Å to 23.6Å, and demonstrate a variety of interlayer alignments as determined by powder X ray diffraction, dependent upon both the metallic content and the degree of hydration of the host compound. The anionic contents of the interlayer regions have been further characterised through infra-red spectroscopy, elemental microanalysis, solid-state NMR and thermogravimetric analysis techniques. The mechanism and kinetics of the release of the intercalated anions from the hosts have been studied in situations approximating their real-world applications, and the degree of release quantified by UV/Visible spectroscopy. Both the rates and mechanisms of anion release have been found to be dependent on the anion, the host, the temperature and the solution into which the anions are released; as such, the release timescales of the anions may be fined tuned through modifications of the host materials. In addition, an explanation has been suggested for the observed change in mechanism observed in instances of release in which the host compound is in only partial contact with the release medium.

The technology of semiconductor-based photocatalytic water splitting to produce hydrogen using solar energy has been considered as one of the most important approaches to solve the world energy crisis. Therefore, the development of the effective semiconductor photocatalysts has undergone considerable research. However, the traditional photocatalysts suffer from the negative effects from rapid charge recombination, which reduces the excited charges by emitting light or generating phonons. Efficient charge separation and fast charge transport, avoiding any bulk/surface recombination, are fundamentally important for photocatalytic hydrogen generation through water splitting. Here, we have introduced assembled layered materials as photocatalyst systems with their unique physicochemical properties to realize the effective charge separation and high photocatalytic activity. Using graphene as a two-dimensional supporting matrix, we have succeeded in selective anchoring of semiconductor and metal nanoparticles as separate catalytically active sites on the graphene surface. The ability of graphene to capture, transfer and store electrons and its potential to serve as a conductive support are demonstrated. The TiO₂ semiconductor/metals nanocrystals-graphene ensemble makes it possible to carry out selective catalytic processes at the separate sites and provides the potentials for applications in water splitting reactions. After demonstrating the positive role of graphene in such photocatalytic system, we then fabricate a simple but highly cooperative ensemble with CdS and MoS₂ nanocrystals dispersed on graphene sheets. It is demonstrated that CdS nanocrystals can also capture visible light energy and facilitate excited electron transfer to MoS₂ (as metal substituent) for catalytic hydrogen production via the 2-D graphene which plays a key role as an efficient electron mediator. Hexagonal multilayer MoS₂ with a layered structure in this system serves to provide active sites for hydrogen evolution by its exposed Mo edges. Hence, multilayer MoS₂ is an ideal cocatalyst of semiconductors for hydrogen generation. This crystalline-layered structure also shows semiconducting properties, however, its characteristic indirect band gap displays a poor light capture and emission ability with excited electrons and holes with different momentum. In contrast, single layer MoS₂ shows a direct band gap behavior. Our studies have clearly shown that single layer MoS₂ prepared with lithium intercalation indeed displays encouraging results in hydrogen evolution due to the direct band gap and quantum confinement effects. In addition, the exfoliated single layer MoS₂ exhibits extraordinary enhanced activity and stability in combination with the Eosin Y sensitized system when compared to those of multilayer MoS₂ and bulk MoS₂ counterparts, which is attributed to the improvement of the density of surface active sites with stronger adsorption for the Eosin Y molecules on the single layer MoS₂. In addition, this multifunctional catalyst on graphene sheet can also create adsorption sites on a defective basal surface of single layer MoS₂ through adsorption of Eosin Y where electron transfer from photoexcited Eosin Y molecule to graphene via the 2-D MoS₂ mainly takes place. Thus, the photo-generated electrons are then effectively transported to the exposed active sites of MoS₂ for the proton reduction to hydrogen molecule. It is believed the above novel assembled molecular layered systems may be applicable for a wide range of catalytic,photocatalytic and electrocatalytic reactions.