A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.

O presente trabalho trata da preparação e da caracterização de sistemas contendo tetrassulfoftalocianinas de Co(II) (CoPcTs) e Fe(III) (FePcTs) intercaladas ou somente adsorvidas externamente em matrizes de hidróxidos duplos lamelares (HDLs). Foram sintetizados materiais com composições variadas e empregando-se diferentes métodos de síntese visando, principalmente, o isolamento de materiais com microporosidade intracristalina e/ou com um baixo grau de agregação da ftalocianina. Técnicas de caracterização textural (difração de raios-X e medidas de área superficial) e espectroscópicas (vibracional na região do infravermelho, eletrônica no UV/visível, ressonância paramagnética eletrônica e absorção de raios-X), além das análises elementar (C, H, N e metais) e termogravimétrica foram utilizadas para a caracterização dos sólidos sintetizados. Avaliaram-se os materiais como catalisadores na reação de oxidação do 2,6-di-terc-butilfenol e do catecol, utilizando O2ou H2O2 como oxidantes. Nos materiais isolados contendo a CoPcTs intercalada em HDLs com composição MgxAl (x = 2, 3 e 4) e ZnxAl (x = 4 e 5), a ftalocianina está orientada perpendicularmente às lamelas do HDL, independentemente do método de síntese e da composição dos HDLs utilizados. Adicionalmente, constatou-se que a CoPcTs intercalada está altamente agregada e que os materiais não possuem microporosidade. Porém, a diminuição da densidade de carga do HDL provoca uma pequena diminuição na agregação da CoPcTs. Sob determinada condição sintética, a CoPcTs intercalada nos HDLs ZnxAl sofre o processo de enxertia através dos grupos sulfônicos. Quando testados como catalisadores na oxidação do 2,6-di-terc-butilfenol, os materiais contendo a CoPcTs intercalada e enxertada apresentaram reatividade inexpressiva, que pode ser devida ao acesso restrito do substrato ao sítio ativo na região interlamelar. Estudos de adsorção da FePcTs em HDLs MgxAl na forma carbonato, investigados por espectroscopia eletrônica UV/Visível in situ, mostraram uma elevada tendência de agregação da ftalocianina na superfície dos HDLs. Os espectros eletrônicos indicaram também que diferentes espécies derivadas da FePcTs são formadas durante o processo de adsorção nos HDLs e que a densidade de carga influencia o tipo de espécie adsorvida: há predominância de um dímero do tipo µ-oxo nos HDLs Mg2Al e Mg3Al e do dímero (FePcTs)2 no HDL Mg4Al. Os espectros de absorção de raios-X (XANES) da FePcTs adsorvida nos HDLs MgxAl mostraram que as espécies adsorvidas apresentam geometria piramidal de base quadrada (C4v) e/ou octaédrica (Oh), corroborando com os dados de espectroscopia no UV/Visível. Já os espectros de ressonância paramagnética eletrônica mostraram que a ftalocianina de Fe(III) quando adsorvida nos HDLs gera uma mistura de espécies com configuração de baixo spin e alto spin e, também, elevada distorção rômbica. A FePcTs adsorvida nos HDLs MgxAl apresentou estabilidade e reatividade catalítica superior quando comparada com a ftalocianina livre na oxidação dos fenóis. A ftalocianina adsorvida na superfície externa do HDL deve favorecer o acesso do substrato ao sítio ativo. Uma correlação entre os estudos de adsorção e os resultados dos testes catalíticos mostrou que a espécie dimérica do tipo µ-oxo pode ser a espécie mais ativa na oxidação dos fenóis. Nestes sistemas, as camadas positivas do HDL devem provocar um enfraquecimento da ligação O-H do fenol, facilitando a sua desprotonação (uma das etapas do mecanismo de oxidação). Este último efeito pareceu atuante, pois foram observadas reatividades crescentes dos catalisadores à medida que se aumentava a densidade de carga do HDL. Estes resultados indicaram que existe um efeito cooperativo nos HDLs MgxAl contendo a FePcTs adsorvida, mostrando que o HDL não atua como um suporte inerte nos processos estudados. / The present work describes the preparation and characterization of materials containing Co(II) and Fe(III) tetrasulfonated phthalocyanines (CoPcTs and FePcTs, respectively) intercalated or adsorbed on layered double hydroxides (LDHs). Different compositions and synthetic methods were used to isolate materials with microporosity and/or the phthalocyanine in a low aggregation degree. X-ray diffraction analysis, surface area measurements, spectroscopic techniques (infrared, UV/visible and X-ray absorption), elemental analysis and thermogravimetry were used to characterize the solids. The materials were tested as catalysts in the 2,6-di-terc-butilfenol and catechol oxidation, using O2 or H2O2 as oxidants. In the materials prepared by intercalation of the CoPcTs in MgxAl (x = 2, 3 and 4) and ZnxAl (x = 4 and 5) LDHs, the phthalocyanine is perpendicularly orientated related to the LDH layers, regardless of synthetic method or LDH composition used. In addition, it was observed that the intercalated phthalocyanine is aggregated and the solids do not have microporous. However, the aggregation degree of the phthalocyanine is slightly lower when the LDH charge density decreases. Under a particular synthetic conditions the CoPcTs intercalated in the LDH ZnxAl is grafted through the sulfonic groups. Catalytic tests uisng this material in the 2,6-di-terc-butilfenol oxidation showed a neglectful reactivity, which confirms the aggregation of the intercalated CoPcTs, thus avoiding that the substrate accesses the reactive center. In an adsorption study carried by monitoring in situ the FePcTs UV/Vis electronic spectra during its addition to LDH suspensions, a strong tendency of aggregation was observed for the FePcTs. In addition, different FePcTs species are formed during the adsorption process on the LDHs, which is influenced by the LDH charge density: the µ-oxo complex is the main species adsorbed on the Mg2Al and Mg3Al LDHs, whereas for Mg4Al the non oxo-bridged dimeric complex prevailed. X-ray absorption spectra (XANES) of the adsorbed FePcTs on the MgxAl LDHs showed that the species present a square-pyramidal (C4v) and/or an octahedral (Oh) symmetry, in agreement with the UV/visible spectroscopic data. EPR spectra of these samples showed that the FePcTs adsorbed on the LDHs leads to a mixture of Fe(III) high and low spin species along with a strong rhombic distortion. The FePcTs adsorbed on the MgxAl LDHs showed an enhanced catalytic activity and longevity in the phenols oxidation compared to the homogeneous counterpart. The phthalocyanine on the LDH external surfaces allows the access of the substrate to the reactive metal center. A correlation between the adsorption study and the catalytic tests pointed that the FePcTs µ-oxo complex may be the active species in the oxidation of phenols. Furthermore, the positive charge of LDH layers may weaken the O-H bonding in the phenol molecules making them more easily ionized (one step of the phenol oxidation mechanism). This feature seems to be effective because higher activities of the catalysts were observed along with increasing charge density of the LDHs. These results indicated that a cooperative effect takes place in the materials containing the FePcTs adsorbed on the MgxAl LDHs, showing that LDH do not act as an inert support in the studied catalytic reactions.

Ce travail est consacré à la synthèse de phases d’Hydroxydes Doubles Lamellaire (HDL) [NiAl-CO32-] à morphologies contrôlées et à l’étude de la relation entre leurs propriétés structurales / microstructurales et leurs propriétés électrochimiques. Les phases HDL sont préparées par un nouveau procédé de synthèse, basé sur un traitement hydrothermal en présence d’acides aminés. Nous avons mis en évidence l’influence de plusieurs paramètres de synthèse tels que la quantité d’acide aminé, la concentration de sels métalliques, le pH du milieu ainsi que la température et le temps du traitement hydrothermal ou encore la nature de l’acide aminé. Trois phases présentant différents degrés de cristallinité et différentes morphologies et représentatives des échantillons synthétisés, ont été plus particulièrement étudiées. Leur structure et microstructure ont été déterminées par affinement Rietveld en utilisant des données de diffraction des rayons X à haute résolution enregistrées au synchrotron. Ces résultats de DRX combinés avec les observations en microscopie électronique à transmission (MET) indiquent que l'élargissement des raies de diffraction 00l est principalement dû à des effets de taille, tandis que les effets, à la fois de taille et de micro-contrainte contribuent à l’élargissement anisotrope des autres réflexions hkl. Les micro-contraintes sont attribuées à un phénomène d’interstratification (CO32-/SO42-) et d’intercroissance de deux polytypes 2H1 et 3R1, confirmés et quantifiés à l’aide du logiciel DIFFaX. L’étude des propriétés électrochimiques de ces phases par voltammétrie cyclique a permis de montrer que la présence du motif d’empilement 2H1 induit une nette augmentation du signal électrochimique. / This work is devoted to the synthesis of NiAl-CO32- Layered Double Hydroxide phases (LDH) with controlled morphology and to the study of the relationship between the structural / microstructural and electrochemical properties. The LDH phases are prepared by a new synthetic method, based on the hydrothermal synthesis in presence of amino acids. We have highlighted the influence of various synthetic parameters such as the amount of amino acid, the concentration of metal salts, the pH of the medium, the temperature and time of hydrothermal treatment as well as the amino acid nature. Three phases of different degrees of crystallinity and different morphologies, representative of synthesized samples were particularly studied. Their structures and microstructures were determined by Rietveld refinement using high-resolution synchrotron powder X-ray diffraction (XRD) data. These XRD results combined with transmission electron microscopy (TEM) observations indicate that the broadening of 00l diffraction lines is mainly due to size effects, while both size and micro-strain effects contribute to the anisotropic broadening of the other hkl reflections. The micro-strain are attributed to an interstratification phenomena (CO32-/SO42-) and intergrowth between rhombohedral 3R1 and hexagonal 2H1 polytypes, confirmed and quantified using the software DIFFaX. The electrochemical properties of these phases are also studied by cyclic voltammetry showing that the presence of the 2H1 stacking motifs results in a net increase of the electrochemical signal.

A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-10T12:37:20Z No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T15:04:53Z (GMT) No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) / Made available in DSpace on 2017-05-17T15:04:53Z (GMT). No. of bitstreams: 1 deysegomesdacosta.pdf: 10386782 bytes, checksum: a18ce8ca7fd4c235c246f70bc4f6f946 (MD5) Previous issue date: 2011-07-29 / Os hidróxidos duplos lamelares (HDL) ou compostos tipo-hidrotalcita vêm sendo muito estudados devido a suas inúmeras aplicações. No campo da catálise, estes compostos podem atuar como catalisadores, suportes para catalisadores ou precursores de catalisadores. É sabido que a morfologia do suporte tem grande influência sobre a dispersão, a atividade e a seletividade apresentada pelo catalisador. Nestes caso, o conhecimento detalhado dos efeitos do suporte e dos sítios catalíticos exigem a compreensão da estrutura do HDL. Entretanto, por causa da desordem estrutural, muitas vezes inerente ao material, torna-se a determinação completa da estrutura, via difração de raios X, raramente possível. As bandas largas presentes na análise do IV, fazem a atribuição das mesmas ambígua. Devido à complexidade dos HDL e à dificuldade de se adquirir ou interpretar os resultados experimentais, foi proposto um modelo para simular as características estruturais dos compostos tipo-hidrotalcita com o politipo 3R1, usando condições periódicas de contorno e cálculos ab initio dentro da teoria do funcional da densidade (DFT). As informações estruturais da hidrotalcita, obtidas experimentalmente, foram usadas para verificar a validade do modelo teórico. Os resultados mostraram boas concordâncias com os padrões de raios X do pó experimentais. O espectro na região do infravermelho, a entalpia e energia livre de Gibbs, também foram calculadas. Os cálculos de frequências vibracionais mostraram que as moléculas de água intercaladas são altamente organizadas devido às fortes interações intermoleculares com outras moléculas de água, com ânions interlamelares e com as hidroxilas das lamelas. A presença destas interações é refletida na presença do estiramento O-H das moléculas de água deslocadas para baixas frequências. A perda da degenerescência dos modos vibracionais v3 e do v4 foi observada, indicando a redução da simetria do íon carbonato. As modificações termodinâmicas e estruturais resultantes da substituição do íon presente no HDL Zn-Al-Cl também formam analisadas. O íon Cl- do HDL precursor foi trocado por uma série de ânions como o F-, Br-, OH-, NO3-, ClO4-, CO32- e SO42-. Os resultados mostraram que a intercalação do HDL com diferentes íons, afeta o gap de energia e a basicidade da lamela tipo-brucita. A entalpia e a energia livre de Gibbs, a densidade de estados (DOS) e a densidade de estados projetada (PDOS) foram avaliadas para todos os HDL. / The layered double hydroxide (LDH) or hydrotalcite-like compounds have been widely studied due to many applications they have. In catalysis field these compounds can act as catalyst, catalyst support or precursor for supports and catalysts. It is well known that the support morphology has larger influence on the dispersion, activity and selectivity of catalysts. In this case, detailed knowledge about support effects and catalytic sites requires understanding the LDH structure. However, because of the inherent structural disorder, complete structure determination using X-ray diffraction is rarely possible. The IR analysis present broad bands, which makes their assignment ambiguous. Due to the complexity of the LDH and the difficult of acquiring experimental data, we proposed a model to simulate structural features of the hydrotalcite-like compounds with 3R1 polytypes using periodic boundary conditions and ab initio density functional theory (DFT) calculations. The structural information of hydrotalcite from experiments were used to verify the validity of theoretical model. Our results showed good agreements to the powder X-ray patterns. The infrared spectroscopy, enthalpy and Gibbs free energy, also was calculated. The IR calculations showed that intercalated water molecules are highly ordered due the strong intermolecular interactions with other water molecules, interlayer anions and layer hydroxyls. These interaction is reflected by the presence of downshift vibrational frequencies of OH-stretching of interlayer water. The loss of degeneracy of the v3 and v4 vibrational modes are observed, indicating the reduction of the carbonate anion symmetry. The thermodynamic and structural modifications derived from anion exchange on a LDH containing Zn-Al-Cl was also analyzed. The Cl- ion to the LDH precursor was exchanged for a series of anions as F-, Br-, OH-, NO3-, ClO4-, CO32- and SO42-. The resulted show that intercalation of LDH with different anions affect their gap energy and basicity of brucite-like layer. The enthalpy and Gibbs free energy, density of charge, density of state (DOS) and projected density of state (PDOS) were evaluated for all substituted materials.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-07-21T12:20:27Z No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-09T13:15:43Z (GMT) No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) / Made available in DSpace on 2017-08-09T13:15:43Z (GMT). No. of bitstreams: 1 sergiorodriguestavaresfilho.pdf: 2771047 bytes, checksum: 581bb53472b98a51c16297f55b6c9259 (MD5) Previous issue date: 2013-07-25 / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / Muitos compostos lamelares, como os hidróxidos duplos lamelares e os hidroxissais lamelares, vem ganhando cada vez mais atenção devido às suas inúmeras aplicabilidades no ramo de catálise, troca iônica e precursores para óxidos. Os dois compostos estudados aqui possuem sítios octaédricos e tetraédricos de zinco, sendo classificados por Louër et al. como hidroxissais do tipo II. O hidroxicloreto de zinco (Zn5(OH)8Cl2.H2O) é romboédrico e possui ocorrência natural sendo designado como simonkolleite. Enquanto que o hidroxinitrato de zinco diidratado (Zn5(OH)8(NO3)2.2H2O) é monoclínico e não possui ocorrência natural. Seus nitratos não se encontram coordenados aos zincos tetraédricos, como é o caso do composto Zn5(OH)8Cl2.H2O. Ao invés disso, suas moléculas de água se encontram coordenadas nos tetraedros e, para balancear a carga positiva das lamelas, esses nitratos se encontram na região interlamelar. Esses dois hidroxissais e uma modificação do hidroxinitrato de zinco com moléculas de amônia coordenadas aos tetraedros (BENARD, 1995) foram estudados por simulação computacional. O pacote Quantum ESPRESSO, baseado na Teoria do Funcional da Densidade (DFT – Density Functional Theory) com funções de onda planas e condições periódicas de contorno foi utilizado para a condução dos cálculos. As moléculas de água foram retiradas das estruturas hidratadas otimizadas e essas foram reotimizadas. Todos os dados experimentais foram comparados com os dados retirados das estruturas simuladas e um bom acordo foi obtido. A estrutura simulada do composto desidratado de Zn5(OH)8(NO3)2.2H2O não correspondeu à estrutura obtida pelo processo de calcinação, como foi visto pela análise termodinâmica do processo de desidratação. Porém, pôde ser concluído que essa estrutura corresponde ao mínimo local, pela ausência de frequências imaginárias. Cálculos de pós-processamento puderam ser conduzidos para uma análise das interações existentes nos compostos e das espécies químicas presentes neles. Os cloretos e os nitratos de ambos os compostos se mostraram equivalentes quimicamente, como foi visto pelo cálculo de pDOS (projected Density of States). As hidroxilas das células unitárias puderam também ser classificadas em dois grupos a partir de suas semelhanças químicas. Pôde-se concluir também com esse trabalho que o modelo de diminuição da célula unitária (DEYSE, 2012) foi capaz de diminuir os custos computacionais e prever certas propriedades dos compostos estudados. / Many layered compounds, like the double hydroxides and the hydroxide salts, have been gaining attention lately due to their various applicabilities in catalysis, anionic exchange and oxide precursors. The studied compounds here have octahedral and tetrahedral sites, which have been classified as type-2 hydroxide salts by Louër et al. Zinc hydroxide chloride monohydrate (Zn5(OH)8Cl2.H2O) is rhombohedric and is found in the nature as a mineral so-called simonkolleite. Whereas zinc hydroxide nitrate dihydrate (Zn5(OH)8(NO3)2.2H2O) is monoclinic and does not have natural occurrence. Their nitrates are not coordinated to the tetrahedral zincs, whereas the chlorides of Zn5(OH)8Cl2.H2O are grafted to the tetrahedral zincs. Their water molecules are grafted to the tetrahedrons and, in order to balance the charges, the nitrates are located in the interlayer region. Those hydroxide salts and a modification of the zinc hydroxide nitrate with ammonia molecules grafted to the tetrahedros (BENARD, 1995) have been studied by computational simulation. The Quantum ESPRESSO package based in the Density Functional Theory (DFT) with waveplanes and periodic boundary conditions was used for the calculations. The water molecules were removed from the optimized hydrate structures and, later on, those were re-optmized. All the experimental data were compared with the ones obtained by simulated structures and a good agreement was shown. The simulated dehydrate structure of Zn5(OH)8(NO3)2.2H2O did not correspond to the structure obtained by calcination, as it was shown by the thermodynamical analysis of the calcination process. However, it was concluded that this structure corresponds to a local minimum due to the lack of imaginary frequencies. Post-processing calculations were conducted in order to analyze the compounds' interactions and the chemical species. The chlorides and nitrates of both compounds were chemically equivalents, as it was shown by the pDOS calculations (projected Density of States). The hydroxyls of the unit cells could be classified in two groups based on their chemical equivalence. It could also be concluded with this work that the unit cell reduction method (DEYSE, 2012) was able to reduce the computational costs and to predict certain properties of the studied compounds.

Ces travaux de thèse pluridisciplinaires à l‘interface entre biocatalyse et nanomatériaux visent la conception de matériaux biohybrides innovants par assemblage dans des conditions douces de matériaux inorganiques de type hydroxydes doubles lamellaires (HDL) avec des enzymes. La première partie de ce mémoire est consacrée à la caractérisation des interactions physico-chimiques entre les HDL et la fructose-6-phosphate aldolase (FSA) catalysant la formation stéréosélective de liaisons C-C pour conduire à des polyols chiraux. Les structures lamellaires HDL permettent un confinement efficace de systèmes enzymatiques grâce à leur structure bidimensionnelle poreuse, leurs propriétés physico-chimiques favorables à l‘échange ionique et leur biocompatibilité. Différentes stratégies d‘immobilisation de la FSA dans des matrices d‘HDL ont été explorées, le taux d‘immobilisation et l‘activité biocatalytique étant fortement dépendant de la méthode d‘assemblage et de la nature des phases HDL. Le taux d‘immobilisation de l‘enzyme obtenu par coprécipitaton est supérieur à celui obtenu par adsorption. Dans une deuxième partie, un bioréacteur a été élaboré par un assemblage hiérarchisé constitué de la FSA, de nanoplaquettes d‘HDL et de billes de polysaccharide, ce dernier jouant le rôle de matrice macrostructurante. De façon notable, le taux d‘encapsulation de l‘enzyme dans la matrice macroscopique est amélioré lorsque le biocatalyseur est pré-encapsulé dans les nanoplaquettes d‘HDL. Ceci est attribué aux interactions électrostatiques favorables entre les chaînes de polysaccharide et les HDL, facilitant une charge de matière plus importante. L‘efficacité catalytique du bioréacteur obtenu et sa recyclabilité ont été démontrés. Dans la troisième partie de cette thèse, nous décrivons pour la première fois la conception de bionanoréacteurs enzymes@HDL par co-immobilisation de systèmes bi- ou tétra-enzymatiques dans les HDL permettant de réaliser des cascades multienzymatiques biomimétiques. L‘immobilisation des différentes enzymes prises séparément a d‘abord été optimisée afin de déterminer les conditions de co-immobilisation et de réaliser les cascades biocatalytiques en phase hétérogène. Ces bionanoréacteurs, dont nous avons démontré la recyclabilité, ont été appliqués pour la synthèse de sucres phosphorylés de série D. Enfin, une cascade multienzymatique a été conçue de novo en solution aqueuse et optimisée pour synthétiser différents sucres phosphorylés rares de série L. / This multidisciplinary thesis at the biocatalysis/nanomaterial interface perfectly aims at designing innovative biohybrid materials by the assembly of inorganic materials the Layered Double Hydroxides (LDH) with enzymes under mild conditions. The first part of this thesis is devoted to the characterization of physico-chemical interactions between the LDH and the fructose-6-phosphate aldolase (FSA) catalyzing the stereoselective C-C bond formation to provide chiral polyols. LDH structures allow the effective confinement of enzymatic systems thanks to their opened two-dimensional structure as well as their chemical surface properties at the nanoscale and their biocompatibility. The FSA immobilization in different LDH matrices by different methods was studied. Biocatalytic activity is highly dependent on the method of assembling, modulating the final amount of FSA. The retaining activity rate of co-precipitated material was higher than that obtained for the adsorbed enzyme. In a second part, a bionanoreactor was developed based on a hierarchized assembly of FSA, LDH nanoplatelets and polysaccharide beads acting as a macrostructuring matrices. Significantly, the encapsulated enzyme rate in the beads was improved when the biocatalyst was pre-encapsulated in LDH nanoplatelets. This is attributed to favorable electrostatic interactions between the polysaccharide chains and LDH, facilitating a higher catalyst loading. The catalytic efficiency of the prepared bioreactor and its recyclability were demonstrated. In the third part of this thesis, we describe for the first time the design of bionanoreactors ―enzymes@LDH‖ by co-immobilisation of two and four enzymes in LDH allowing biomimetic multienzymatic cascades. We first studied the immobilization of the different enzymes taken separately. Then we worked on the optimization of the biocatalytic cascades in heterogeneous phase. These bionanoreactors, for which we have shown the recyclability, have been applied to the synthesis of D-series phosphorylated sugars. Finally, a multienzymatic cascade was de novo designed in aqueous homogeneous solution. It was optimized for the synthesis of rare L-phosphorylated sugars.

Dan Beaty (1937-2002) was a prolific composer, pianist, researcher, educator, and writer. His large compositional output included chamber works, choral works, songs, orchestral pieces, electronic music, and keyboard works. Beaty was well versed in traditional Western music as well as the more avant-garde and perplexing idioms of the twentieth century. Beaty's compositions reflect the many fascinating, if not always popular, musical trends of his time. His music encompasses styles from serial to jazz, shows compositional influences from Arnold Schoenberg to Indonesian music, and demonstrates thought-provoking and highly intellectual craftsmanship. This document explores several of Beaty's songs through a discussion of the composer's life and compositional process. Songs included in this document are Three Weeks Songs, October, November, A Sappho Lyric, Love Song, That Night When Joy Began, and War Lyrics. This document was written to accompany the author's DMA Lecture-Recital at the University of North Texas. Unfortunately, Beaty's vocal music was never published and is mostly unknown. One goal of the project was to initiate interest in Beaty's songs. Through this document, Lecture-Recital, and additional performances, considerable strides have been made to bring Beaty's songs to new audiences throughout the United States. In addition, the author has received permission from the Beaty family to publish Dan Beaty's songs.

Monolayer two-dimensional (2D) materials have been regarded as a hot topic in the fields of condensed matter physics, materials science, and chemistry due to their unique physical, chemical, and electronic properties. However, the research on the preparation method and properties understanding of the 2D monolayer are inadequate. In this dissertation, taking 2D nickel-iron layered double hydroxides (NiFe LDHs) and molybdenum disulfide (MoS2) as examples, the practicability of the direct synthesis of NiFe LDHs monolayer and the thermal enhancement catalytic performance of 2D MoS2 monolayer (MoS2 ML) are discussed. First, a one-pot synthetic strategy (bottom-up method) is presented to synthesize 2D NiFe-based LDHs monolayers, including NiFe, Co-, Ru-, doped, and Au-modified NiFe LDHs. The prerequisite and universality of this strategy are investigated and confirmed. The features of LDHs are characterized by advanced technologies. The obtained LDH bulks own a large interlayer spacing up to 8.2 Å, which can be facilely exfoliated into monolayers in water by hand-shaking within 10 s. As a result, the as-prepared NiFe-based LDH monolayers display a good electrocatalytic oxygen evolution reaction (OER) performance. This facile strategy paves the way for designing easily exfoliated LDHs for highly active catalysts and energy conversion devices based on other monolayer LDHs. Second, with gold-modified tape, 2D MoS2 ML is exfoliated from the bulk crystal through a micromechanical exfoliation method (top-down strategy). The thermal effects of MoS2 ML are confirmed by Raman and photoluminescence (PL) spectra. Moreover, an on-chip MoS2 ML hydrogen evolution reaction (HER) reactor is designed and fabricated. The thermal effects generate efficient electron transfer in the MoS2 ML and at the electrolyte-catalyst (MoS2 ML) interface, leading to an enhanced HER performance. Compared to the results obtained at room temperature, the MoS2 ML shows a direct thermal enhanced HER performance at higher temperatures. In summary, the findings and understandings, the direct synthesis and direct thermal enhancement catalytic performance, of 2D monolayers offer a guideline for synthesizing and catalyst application of other 2D monolayers.

Résumé non disponible. / Résumé non disponible.