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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
141

The role of water properties and specific ion effects on the evolution of silica nanoconfinement / Le rôle des propriétés de l'eau et des effets spécifiques des ions sur l'évolution du nanoconfinement de la silice

Baum, Markus 09 November 2018 (has links)
Dans cette thèse, les propriétés de l'eau en présence d'ions dans des nanoconfinement à base de silice ont été étudiées. L'objectif principal est de relier ces propriétés à l'évolution des matériaux mésoporeux de silice dans les solutions aqueuses. Pour atteindre cet objectif, nous avons utilisé une approche originale consistant à remplir avec des solutions électrolytiques comportant des ions ayant des propriétés kosmotropes différentes, XCl2 (X = Ba, Ca, Mg) des systèmes modèles tels que deux surfaces de silice parallèles et planes espacées de 3 et 5 nm (nanocanaux) et des silices à mesoporosité ordonnée comme les silices SBA-15 (6 nm de taille pores et murs des pores microporeux) et MCM-41 (3 nm de taille de pores et murs des pores denses).Les résultats obtenus indiquent que la cinétique de remplissage des nanocanaux dépend de la taille du confinement, de la nature des ions et de la solubilité des sels associés aux électrolytes. Dans certains cas, le remplissage incomplet des nanocanaux peut s'expliquer par une diminution de la dynamique de l'eau associée à l’atteinte de la saturation vis-à-vis des sels XCl2 dans la couche interfaciale. La possible précipitation de phases XCl2 pourrait permettre d’expliquer le bouchage de certains nanocanaux. Par la suite, les propriétés de l'eau dans des nanoconfinement concave de silice tels que les cylindres ont également été étudiées. La structure de l’eau en présence d’ions et sa dynamique à l’échelle de la picoseconde caractérisées respectivement par FTIR-ATR et diffusion quasi élastique des neutrons, ont été analysées. Les résultats suggèrent que les propriétés structurales et dynamiques de l'eau sont fortement influencées par la taille du confinement, le caractère kosmotrope des ions et l'excès d'ions dans la couche interfaciale.Enfin, nous avons déterminé l’évolution des deux silices mésoporeuses dans des solutions électrolytiques par diffusion des rayons X aux petits angles. Pour une taille de pore de 3 nm et des murs de pores denses (MCM-41), une dynamique de l’eau lente à une échelle picoseconde conduit probablement à une sursaturation des ions dans la couche interfaciale et donc à une reprécipitation des sels XCl2 et / ou de la silice plus stable. Dans ce cas, l'évolution du MCM-41 est induite par un processus de dissolution-recondensation / précipitation. Dans les plus grands mésopores du SBA-15, en raison de la microporosité dans la paroi des pores, le processus d'altération est différent. Dès le début, une couche d'altération se forme et la taille des pores augmente jusqu'à saturation de la silice. Par la suite, un processus de recondensation / précipitation similaire à celui observé dans la MCM-41 se produit dans la microporosité. Ces deux types d'évolutions en silice pourraient persister jusqu'à l'obtention d'une phase de silice thermodynamiquement stable. / In this study, we investigated the water properties in the presence of ions in silica nanoconfinement. The main objective is to relate these water properties to the evolution of silica mesoporous materials in aqueous solutions. To reach this goal, we used an original approach, consisting in the use of electrolyte solutions having ions with various kosmotropic property XCl2 (X = Ba, Ca, Mg) confined in model systems such as two parallel and plane silica surfaces spaced of 3 and 5 nm (nanochannels) and highly ordered mesoporous silica materials represented by SBA-15 (6 nm pore size and microporous pore wall) and MCM-41 (3 nm pore size and dense pore wall).The obtained results indicate that the filling kinetics in nanochannels is driven by the size of the confinement, the nature of ions and the salt solubility of electrolytes. In some cases, the incomplete filling of the nanochannels may be explained by a decrease of water dynamics associated to the saturation of XCl2 salts into the interfacial layer. The possible precipitation of XCl2 phases may explain an incomplete filling by a nanochannels clogging.Thereafter, the water properties in nanoconfinement made of silica concave surface such as cylinders were studied. The water structure and dynamics at a picosecond scale in presence of ions were respecteively characterized by infrared spectroscopy and quasi-elastic neutron scattering. The results suggest that the structural and dynamical water properties are strongly affected by the size of the confinement, the kosmotropic properties of ions and the surface ion excess in the interfacial layer.Finally, we characterized the evolution of the two mesoporous silica in electrolyte solutions using in-situ small-angle X-ray scattering. For 3 nm pore size and dense pore wall (MCM-41), the slow dynamics at a picosecond scale probably lead to a supersaturation of ions in the interfacial layer and thus, to a reprecipitation of XCl2 salts and/or silica phases. In that case, the evolution of the MCM-41 is driven by a dissolution-recondesation/precipitation process. In the bigger mesopores of SBA-15, due to the microporosity in the pore wall, the alteration process is different. During a first stage, an alteration layer is formed and the pore size increases until the silica saturation. Afterwards, a similar recondensation/precipitation process as observed in MCM-41 occurs into the microporosity. These two types silica evolutions could persist until the formation of a thermodynamic stable silica phase.
142

Funcionalização de sílicas mesoporosas com benzotiazol-2-tiol e 3-mercaptopropiltrimetoxisilano para aplicações em eletroanalítica / Funcionalization of mesoporous silica with 2-bezothiazolethiol and 3-mercaptopropyltrimetoxysilane for electronalytical application

Cesarino, Ivana 11 September 2009 (has links)
Sílicas mesoporosas foram funcionalizadas pela imobilização de substâncias orgânicas ligadas covalentemente aos grupos silanol da superfície da sílica. A sílica SBA-15 nanoestruturada foi funcionalizada por pós-síntese com benzotiazol-2-tiol e filmes de sílica modificados com 3-mercaptopropiltrimetoxisilano foram obtidos por funcionalização direta. A caracterização destes materiais foi realizada por espectroscopia no infravermelho, difração de raios X, termogravimetria, análise elementar, ressonância magnética nuclear, microscopia de força atômica e microscopia eletrônica de varredura. Eletrodos compósitos grafite-poliuretana e pasta de carbono modificados com sílica SBA-15 organofuncionalizada com benzotiazol-2-tiol (BTPSBA) e eletrodo carbono vítreo modificado com filme de sílica tiol-funcionalizado foram preparados e avaliados quanto ao seu desempenho em relação à determinação voltamétrica de metais pesados em amostras de água natural e cachaça. Parâmetros que afetam a corrente de pico voltamétrica foram otimizados e cádmio(II) apresentou uma resposta linear no intervalo de 1,0 a 10,0 x 10-6 mol L-1 com limite de detecção de 4,5 x 10-7 mol L-1 usando o eletrodo de pasta de carbono modificado com BTPSBA e voltametria de redissolução anódica de pulso diferencial (DPASV). Cd(II) foi adicionado em amostras de águas naturais e determinado com recuperação média de 96,4% em concentrações da ordem de 10-6 mol L-1. Este mesmo eletrodo, também foi avaliado na determinação de chumbo, cobre e mercúrio em amostras de água natural e cachaça por DPASV. Curvas analíticas foram lineares nos intervalos de concentração de 3,0 a 70,0 x 10-7 mol L-1 de (Pb2+), 8,0 a 100,0 x 10-7 mol L-1 de (Cu2+) e 2,0 a 10,0 x 10-6 mol L-1 de (Hg2+), com limites de detecção de 4,0 x 10-8 mol L-1 (Pb2+), 2,0 x 10-7 mol L-1 (Cu2+) e 4,0 x 10-7 mol L-1 (Hg2+). Os resultados indicaram que o eletrodo de pasta de carbono modificado com BTPSBA é sensível e efetivo na determinação de Pb2+, Cu2+ e Hg2+ nas amostras analisadas. O eletrodo compósito grafite-poliuretana modificado com BTPSBA foi avaliado na detecção de cádmio, chumbo, cobre e mercúrio, utilizando voltametria de redissolução anódica de pulso diferencial e onda quadrada (SWASV). Usando SWASV e 5 min de tempo de acumulação, respostas lineares foram obtidas nas faixas de concentrações de 1,0 x 10-7 a 1,0 x 10-6 mol L-1 (Cd2+), 7,0 a 90,0 nmol L-1 (Pb2+), 5,0 x 10-8 a 9,0 x 10-7 mol L-1 (Cu2+) e 1,0 x 10-8 a 1,0 x 10-7 mol L-1 (Hg2+), com limites de detecção de 29,0 nmol L-1 (Cd2+), 0,8 nmol L-1 (Pb2+), 8,0 nmol L-1 (Cu2+) e 0,9 nmol L-1 (Hg2+). O eletrodo modificado foi testado com sucesso na determinação simultânea de Cd2+, Pb2+, Cu2+ e Hg2+ em amostras de água natural. Hg(II) também foi determinado em amostras de água natural usando o eletrodo carbono vítreo modificado com filme de sílica tiol-funcionalizado e foi observado um limite de detecção de 4,3 nmol L-1, usando 15 min de pré-concentração. Hg(II) foi determinado com recuperação entre 97,0 e 101,4% em concentrações da ordem de 10-8 mol L-1. Os resultados mostraram que o eletrodo é seletivo e sensível na determinação de mercúrio. Em todos os casos, a sílica SBA-15 organofuncionalizada com benzotiazol-2-tiol e o filme de sílica tiol-funcionalizado mostraram ser bons modificadores, melhorando a sensibilidade dos eletrodos. / Mesoporous silicas were functionalised by immobilisation of organic substances covalently bonded to the silanol groups on the silica surface. SBA-15 nanostructured silica was functionalised by post-synthesis with 2-benzothiazolethiol and silica films modified with 3-mercaptopropyltrimethoxysilane were obtained by direct functionalisation. The characterization of these materials was performed by IR spectroscopy, X-ray diffraction, thermogravimetry, elemental analysis, nuclear magnetic resonance, atomic force microscopy and scanning electron microscopy. Composite graphite- polyurethane and carbon paste electrodes modified with SBA-15 silica organofunctionalised with 2-benzothiazolethiol (BTPSBA) and glassy carbon electrode modified with silica film thiol-functionalised were prepared and evaluated in relation to their performance in voltammetric determination of heavy metals in natural water and sugar cane spirit samples. Parameters affecting the voltammetric peak current were optimized and cadmium(II) showed a linear response in the range from 1.0 to 10.0 x 10-6 mol L-1 with detection limit of 4.5 x 10-7 mol L-1, using the carbon paste electrode modified with BTPSBA and differential pulse anodic stripping voltammetry (DPASV). Cd(II) spiked in a natural water sample was determined with 96.4% mean recovery at µmol L-1 level. The same electrode was also evaluated in the determination of lead, copper and mercury in natural water and sugar cane spirit samples by DPASV. Analytical curves were linear in concentration ranges from 3.0 to 70.0 x 10-7 mol L-1 (Pb2+), 8.0 to 100.0 x 10-7 mol L-1 (Cu2+) and 2.0 to 10.0 x 10-6 mol L-1 (Hg2+), with detection limits of 4.0 x10-8 mol L-1 (Pb2+), 2.0 x 10-7 mol L-1 (Cu2+) and 4.0 x 10-7 mol L-1 (Hg2+). The results indicated that the carbon paste electrode modified with BTPSBA is sensitive and effective in the simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analyzed samples. The graphite-polyurethane composite electrode modified with BTPSBA was evaluated in the simultaneous detection of cadmium, lead, copper and mercury, using differential pulse and square wave anodic stripping voltammetry (SWASV). Using SWASV and 5 min accumulation time, the linear response ranges were 1.0 x 10-7 to 1.0 x 10-6 mol L-1 (Cd2+), 7.0 x 10-9 to 90.0 nmol L-1 (Pb2+), 5.0 x 10-8 to 9.0 x 10-7 mol L-1 (Cu2+) and 1.0 x 10-8 to 1.0 x 10-7 mol L-1 (Hg2+), with detection limits of 29.0 nmol L-1 (Cd2+), 0.8 nmol L-1 (Pb2+), 8.0 nmol L-1 (Cu2+) and 0.9 nmol L-1 (Hg2+). The modified electrode was tested successfully in the determination of Cd2+, Pb2+, Cu2+ and Hg2+ in natural water samples. Hg(II) was also determined in natural water samples using glassy carbon electrode modified with silica film thiol-functionalised and observed a detection limit of 4.3 nmol L-1, using 15 min of pre-concentration time. Hg(II) was determined between 97.0 and 101.4% mean recovery at 10-8 mol L-1 level. The results indicate that this electrode is selective and sensitive for the Hg(II) determination. In all cases, silica SBA-15 organofunctionalised with 2-benzothiazolethiol and silica film thiol-functionalised improved the sensitivity of the electrodes.
143

Sistemas porosos de zircônia e céria / Zirconia-Ceria Porous Systems

Bacani, Rebeca 16 December 2009 (has links)
Neste trabalho foram desenvolvidas sínteses de ZrO2-x%CeO2, baseadas na preparação da sílica mesoporosa ordenada SBA-15, utilizando um molde de co-polímero tribloco Pluronic P-123, diversos precursores de zircônio e cério e diferentes métodos. Os métodos de síntese testados foram com: precursores a base de cloreto hidratado (com x=50, 70 e 90), precursores a base de cloreto anidro (x=50 e 90), precursores a base de nitrato (x=90), solução supersaturada de nitrato (x=90), do tipo híbrido com Zr, Ce e Si (com 10%mol de Si e x=90), paliçada de Si (com 10 e 30%mol de Si e x=90) e paliçada de Si com temperatura de síntese de 40°C (com 30%mol de Si e x=90). Visando obter paredes compostas por fase cristalina única e grande área supercial, para futuras aplicações em catálise. Os compósitos polímero/(zircônio-cério) sintetizados a partir de cloretos formam uma estrutura lamelar organizada, que se transforma num sistema poroso desordenado após a calcinação para a retirada do molde. O processo de decomposição/remoção do molde até 540°C produz mudanças de fase nos precursores a base dos metais utilizados, além das transformações morfológicas. Para uma concentração de 90% de CeO2 obtém-se um material poroso com paredes homogêneas de estrutura fcc e de maior estabilidade mecânica. Os valores de área supercial e volume de poros dependem fundamentalmente do método de preparação do material e independem da concentração de CeO2. Aumentos signicativos da área supercial (~100m²/g) e do volume de poros (~0,4cm³/g) são obtidos a partir da introdução de sílica nesses sistemas. Foram alcançados área supercial aproximadamente 6 vezes maior e tamanho de cristalito ~4 vezes superior à do material similar nanocristalino preparado por gel-combustão. Esses valores também são iguais aos reportados para os melhores materiais porosos a base de zircônia-céria, preparados por outros métodos, encontrados na literatura. / In this work synthesis of ZrO2-x%CeO2 were developed, based on the formation of ordered mesoporous silica SBA-15, using the triblock co-polymer Pluronic P-123 as template, different precursors of zirconium and cerium and dierent methods. The tested synthesis methods were with: hydrated chloride precursors (with x=50, 70 and 90), anhydrous chloride precursors (x=50 and 90), nitrate precursors (x=90), supersaturated nitrate solution (x=90), hybrid type with Zr, Ce and Si (with 10%mol of Si and x=90), Si palisade (with 10 and 30%mol of Si, and x=90) and Si palisade with synthesis temperature of 40°C (with 30%mol of Si and x=90). Aiming to obtain crystalline single phase walls and large supercial area, for future applications in catalysis. The composites polymer/zirconium-cerium synthesized from chloride precursors formed an organized lamellar structure, which transforms into a disordered porous system after the calcination to remove the template. The template decomposition/removal up to 540°C produces phase transformations in the metallic precursors, besides morphological changes. A CeO2 content of 90% resulted in a porous material with homogeneous walls of fcc structure and better mechanical stability. The values of supercial area and pore volume depend mostly on the preparation method rather than the CeO2 concentration. Signicant increases on supercial area (~100m²/g) and pore volume (~0.4cm³/g) were obtained with the introduction of silica into the material. Supercial area ~6 times larger and crystallite size ~4 times superior to a nanocrystalline similar material, made by gel-combustion were attained. These figures are also equal to the ones reported for the best porous zirconia-ceria materials, prepared by other routes, found in the literature.
144

Mesoporous materials for optical applications and plasmon-fluorophore interactions. / 介孔材料的光學應用和表面等離子體-熒光分子之間相互作用 / CUHK electronic theses & dissertations collection / Mesoporous materials for optical applications and plasmon-fluorophore interactions. / Jie kong cai liao de guang xue ying yong he biao mian deng li zi ti - ying guang fen zi zhi jian xiang hu zuo yong

January 2011 (has links)
Zhao, Lei = 介孔材料的光學應用和表面等離子體-熒光分子之間相互作用 / 趙磊. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese. / Zhao, Lei = Jie kong cai liao de guang xue ying yong he biao mian deng li zi ti - ying guang fen zi zhi jian xiang hu zuo yong / Zhao Lei.
145

Medical Implant Applications of Mesoporous Silica Films

Geite, Patrik January 2019 (has links)
A literature review of medical implant applications of mesoporous silica films was written, highlighting the advantages and limitations of different film synthesis methods. Both films synthesized through the EISA sol-gel method and particulate films, including those synthesized through the direct growth method, were reviewed and discussed. All films were found to have their strengths and weaknesses, however, the films synthesized through the direct growth method was found to be the most promising type for coating implants. In addition to the literature review, copper-doped mesoporous silica films were synthesized on titanium grade 2 substrates. SEM shows that particles grown on all the films and EDX elemental analysis confirms the presence of copper in the material. Nitrogen physisorption measurements show that particles with incorporated copper have a higher specific surface area, and pore volume compared to un-doped particles. No copper content could be confirmed through FTIR. The particles grown on titanium substrates were more rod-like compared to the ones grown on the silicon substrates as control.
146

Designer 3D magnetic mesostructures

Mueller, Andre January 2012 (has links)
Micro Hall probe magnetometry has been used to investigate the magnetisation of various electrodeposited microcrystals. Superconducting tin crystals of almost perfect square cuboid shapes exhibit a strong size dependence of the supercooling of the superconducting state and, for the smallest accessible crystals, the crossover to the mesoscopic regime can be readily explored close to their critical temperatures. Experimental results are in good agreement with Ginzburg-Landau simulations using the exact experimental parameters. Electroplating of the tin cores with another material provides unique core-shell structures of either two superconductors (S-S’: tin-lead) or of a superconducting core, covered with a ferromagnetic shell (S-F: tin/lead-nickel). The critical parameters of the tin core in Sn-Pb core-shell crystals are considerably enhanced and superconductivity in the tin core is detected up to 1:16 TSn c . Little-Parks oscillations in the shell can be analysed to reveal the extent of the superconducting sheath and hence can be utilised to measure the range of the proximity effect close to the critical temperature of the shell. In S-F core-shell structures, field cancellation effects govern the overall behaviour. Under certain conditions it was possible to switch the overall magnetic response from para(ferro-)magnetic to diamagnetic and back at finite applied fields. Micromagnetic simulations qualitatively reproduce the experimentally observed effects. Applications for the core-shell structures include magnetic guidance or memory devices.
147

Films mesoporeux photocatalytiques de tio2 non dope et dope par differents metaux : elaboration, caracterisation et etude des proprietes photocatalytiques / Non-doped and metal-doped photocatalytic tio2 mesoporous thin films : elaboration, characterisation and photocatalytic properties

Semlali, Sanaa 19 December 2013 (has links)
L’objet de cette thèse est le développement et l’étude de la photoréactivité de TiO2, absorbant dans le visible et ayant des propriétés autonettoyantes et de dépollution de l’eau et de l‘air. Dans ce contexte, des films d’épaisseur controlée et mésostructurés de TiO2 non dopés et dopés par différents métaux (platine, vanadium et tungstène) , ont été synthétisés par voie sol-gel combinée au procédé d'auto-assemblage induit par évaporation. Les propriétés structurales et optiques ainsi que la composition chimique de la surface des films ont été caractérisées par de nombreuses techniques de caractérisation telles que DRX, GISAXS, TEM, MEB ellipsoporosimétrie, DRUV et XPS. Une étude complète des propriétés photocatalytiques des films à base de TiO2 aux interfaces solide-solide, solide-liquide et solide-gaz a été réalisée en utilisant respectivement les tests avec de l’acide stéarique, du bleu de méthylène et de l’acétone. Durant cette étude, nous avons montré qu’un contrôle adapté de l’épaisseur des films, de la nature et de la quantité du dopant peut améliorer l’activité photocatalytique jusqu’à un facteur de 16 par rapport à des films non dopés. Des tests préliminaires de piégeage chimiques des radicaux OH• par l’acide téréphtalique sous irradiation UV ont montré qu’il existait une bonne corrélation entre la photoréactivité et la génération des radicaux OH•. / The aim of this thesis is the development and study of photocatalytic properties of visible light photoactive mesoporous TiO2-based films to act as self-cleaning, and purification systems applied to air and water. Pure and doped mesoporous titania films with different metals as Pt, V and W were prepared by sol-gel method combined with evaporation induced self-assembly process at different thicknesses. Structural, optical properties and chemical composition of these films were characterized by XRD, GISAXS, TEM, SEM, ellipsoporosimetry , DRUV and XPS. In order to better characterize and compare the efficiency of these films at solid-solid, liquid-solid and air-solid interfaces, several tests were used: mineralization of stearic acid, photobleaching of methylene blue and photooxidation of acetone. In this study, it is shown how a suitable control of the film thickness, the nature and amount of the dopant can improve the photocatalytic activity up to a factor of 16 relative to un-doped films. Preliminary results on the OH• radicals production using terephtalic acid as a chemical probe showed good correlation between photoreactivity and generation of these radicals.
148

Innovative hydrocarbons recovery and utilization technology using reactor-separation membranes for off-gases emission during crude oil shuttle tanker transportation and natural gas processing

Shehu, Habiba January 2018 (has links)
The increase in greenhouse gas (GHG) concentrations in the atmosphere, as well as the high rate of depletion of hydrocarbon-based resources have become a global concern. A major source of emissions of hydrocarbon vapours occur during loading and offloading operations in crude oil shuttle tanker transportation. The emitted gases have a typical composition of 60 % N2, 10 % CO2, 5% O2, 5 % C3H8, 10% CH4, 5% C2H6 and 5 % higher hydrocarbons. As a result, various methods aimed to add value to GHG to produce valuable fuels and chemical feedstock are being developed. This work incorporates the use of silica, polyurethane/zeolite and y-type zeolite membrane on an alumina support to selectively permeate methane and carbon dioxide from inert gases and higher hydrocarbons. The recovered gas is upgraded by dry reforming reactions employing rhodium/alumina membrane incorporated into a shell and tube reactor. Mixed gas permeation tests have been carried out with the permeate and feed gases sent to the online gas chromatograph (GC) equipped with a mass spectrometry (MS) detector and an automated 6-port gas sampling valve with a 30 mm HP- Plot Q column. The question is what mesoporous membrane can be highly selective for the separation of methane and carbon dioxide from inert gases and higher hydrocarbons, and what is the effect of temperature and feed gas pressure on the conversion of separated gases? Characterisation of the modified membranes was carried out using nitrogen physisorption measurements and showed the hysteresis isotherms corresponding to type IV and V, which is indicative of a mesoporous membrane. The surface area and the pore size were determined using the Barrett, Joyner, Halenda (BJH) desorption method, which showed the silica membrane had a larger surface area (10.69 m2 g-1) compared to zeolite (0.11 m2 g-1) and polyurethane/zeolite membrane (0.31 m2 g-1). Fourier Transform Infrared spectroscopy, Scanning Electron Microscope and Energy Dispersive X-ray Analysis confirmed the asymmetric deposition of silica, polyurethane, rhodium and zeolite crystals in the matrix of the alumina support. Single gas permeation tests showed that the synthesised y-type zeolite membrane at 293 K had a CH4/C3H8 selectivity of 3.11, which is higher than the theoretical value of 1.65. The permeating CH4 and C3H8 flux at 373 K and a pressure of 1 x 105 Pa was 0.31 and 0.11 mol s-1 m-2 respectively proving that zeolite has molecular sieving mechanism for separation of methane and propane. The silica membrane exhibited higher effectiveness for the separation of CO2 than the other membranes. For methane dry reforming using a supported rhodium membrane, an increase of the reaction temperature from 973 K to 1173 K showed an increase in conversion rate of CO2 and CH4 from less than 20% to over 90% while increasing the gas hourly space velocity (GHSV) did not have a noticeable effect. The study revealed the high potential of the zeolite and rhodium membrane for gas separation and dry reforming reactions concept in creating value-added carbon-based products from CO2 and CH4.
149

S?ntese da mordenita a partir da Al-SBA-15 / Synthesis of mordenite from the Al-SBA-15.

Valente, Tain? Dias 17 December 2015 (has links)
Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-01-03T12:20:02Z No. of bitstreams: 1 2015 - Tain? Dias Valente.pdf: 2209049 bytes, checksum: 5c25bcd5878b607ea484c8dbccb59903 (MD5) / Made available in DSpace on 2017-01-03T12:20:02Z (GMT). No. of bitstreams: 1 2015 - Tain? Dias Valente.pdf: 2209049 bytes, checksum: 5c25bcd5878b607ea484c8dbccb59903 (MD5) Previous issue date: 2015-12-17 / In the present dissertation it was conducted the study of the synthesis of mesoporous molecular sieve Al-SBA-15 by direct synthesis in agitated reactor having the following molar ratio: 14 SiO2: 1 Al2O3: 0.235 P123: 1800 H2O. Initially, a study was done to optimize the synthesis of Al-SBA-15. Through this study, it was found that the operating conditions that resulted in the SBA-15 sample with a higher degree of ordering were gel aging time equal to 15 hours at 40 ? C and then at 100 ? C for 8 hours. These optimal conditions were used to perform scaling up to 5 gallon reactor. Samples of Al-SBA-15 were subjected to carbonization in order to fill the pores of SBA-15 with carbonaceous material and prevent the collapse of its structure. The carbonized samples were used as a source of silica for the synthesis of mordenite in dry medium using the transmission technique in the vapor phase (VPT). The purpose of this procedure was to obtain the mordenite having mesopores. For the preparation of the mordenite by VPT, several conditions were used, varying the synthesis time and form of addition of the reactants, presence or absence of an organic driver. The samples were characterized by X-ray and nitrogen adsorption. It was observed that in most of the experiments, there was no formation of mordenite phase. In the experiments in this phase was obtained, there was no significant mesoporosity training. Apparently, the presence of carbonaceous material was not sufficient to preserve the mesoporous structure of SBA-15. Key / No presente trabalho foi realizado o estudo da s?ntese da peneira molecular mesoporosa Al-SBA-15 a partir da s?ntese direta em reator agitado apresentando a seguinte propor??o molar: 14 SiO2: 1 Al2O3: 0,235 P123: 1800 H2O. Inicialmente, foi feito um estudo visando otimizar a s?ntese da Al-SBA-15. Atrav?s deste estudo, foi verificado que as condi??es operacionais que resultaram na amostra de SBA-15 com maior grau de ordenamento foram com tempo de envelhecimento do gel de s?ntese igual a 15 horas a 40?C e depois a 100?C por 8 horas. Estas condi??es otimizadas foram utilizadas para efetuar o aumento de escala para o reator de 5 gal?es. As amostras de Al-SBA-15 foram submetidas a carboniza??o com o objetivo de preencher os poros da SBA-15 com material carbon?ceo e evitar o colapso de sua estrutura. As amostras carbonizadas foram utilizadas como fonte de s?lica para a s?ntese da mordenita em meio seco utilizando a t?cnica de transporte em fase vapor (VPT). O objetivo deste procedimento foi a obten??o de mordenita tendo mesoporos. Para o preparo da mordenita por VPT, v?rias condi??es foram utilizadas, variando o tempo de s?ntese e forma de adi??o dos reagentes, presen?a ou aus?ncia de um direcionador org?nico. As amostras obtidas foram caracterizadas por difra??o de raios X e adsor??o de nitrog?nio. Foi observado que na maioria dos experimentos n?o houve a forma??o da fase mordenita. Nos experimentos em que esta fase foi obtida, n?o foi observada forma??o de mesoporosidade significativa. Aparentemente, a presen?a de material carbon?ceo n?o foi suficiente para preservar a estrutura mesoporosa da SBA-15. Palavras chave:
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Single Molecule Investigation of the Structural Aspects and Mass Transport Dynamics of Mesoporous Silica Nanopores

Kumarasinghe, Ruwandi January 1900 (has links)
Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This dissertation describes single-molecule tracking (SMT) studies for the quantitative characterization of one-dimensional (1D) solvent-filled surfactant-templated mesoporous silica (STMS) materials and other nanostructured materials, such as double-stranded DNA. SMT permits the simultaneous and quantitative assessment of the nanoscale and microscale morphologies and mass-transport properties of the materials with nanometer-scale spatial resolution. The efficiency and selectivity of catalytic reactions and chemical separations occurring in liquid-filled mesoporous materials are governed by the translational and orientational mobilities and surface interactions of the incorporated reagents and analytes. Polarization dependent SMT results demonstrate that the dye molecules used as probes of materials nanostructure are tightly confined within the one-dimensional (1D) pores of surfactant-templated mesoporous silica films. Spectroscopic single molecule tracking (sSMT) data reveal that the hydrophobic probe dyes are confined within nonpolar regions of the nanomaterials For this dissertation, surfactant templated mesoporous silica films were prepared by the spin coating of acid catalyzed tetramethoxysilane (TMOS)-based silica sols on glass substrates in the presence of Cetyltrimethylammonium bromide (CTAB). Cylindrical CTAB micelles formed during evaporation of the solvent acted as a structure directing template, forming nanometer-sized one-dimensional pores within the silica films. SMT experiments were performed using a wide-field fluorescence microscope that was sufficiently sensitive to allow detection of the fluorescence from individual dye molecules. A series of perylene diimide (PDI) dyes was employed for basic structural characterization of the silica materials. Single molecule fluorescence was recorded in the form of fluorescence videos. These videos revealed the presence of immobile dye molecules, along with those diffusing in one and two dimensions (1D and 2D). The 1D diffusing molecules provided basic evidence for the confinement mass transport of the dye molecules within the silica mesopores. Spectroscopic single molecule tracking (sSMT) studies served as an extension of basic SMT experiments and were employed to determine the location of the molecules. The polarity sensitive dye Nile Red (NR) was employed in these studies. It exhibits 1D diffusion, consistent with its confinement to the cylindrical pores, as was also the case for the PDI dyes. The sSMT data revealed that the majority of NR molecules were found in nonpolar environments having polarities similar to that of n-hexane. Single molecule emission polarization (SMEP) measurements were employed to explore the orientational confinement of the dyes. The results of these experiments demonstrated that the PDI and NR molecules diffuse with their long axes aligned parallel to the long axis of the pores. All of the dyes employed were found to be orientationally confined to ∼1 nm diameter pathways within the pores. The diffusion coefficient for the dyes was also shown to be ∼10^3 -fold smaller than in bulk solution. The results of the NR studies demonstrate that the dye molecules were confined to the hydrophobic cores of the micelles, and provide support for the conclusion that the PDI dyes are similarly confined. These studies afford an enhanced understanding of how nanostructuring of the pore-filling medium in solvent- and surfactant-filled mesoporous materials governs the mass transport and surface interactions of incorporated reagents and analytes. The dependence of molecular confinement on dye charge and structure was also explored in this dissertation. The confined translational and orientational motions of a series of four different PDI dyes diffusing along one dimension (1D) within individual cylindrical silica mesopores were investigated in these studies. Specifically, the motions of cationic and anionic PDI dyes were compared to those of two uncharged PDIs having different alkane tail lengths. All four dyes exhibited populations that were immobile, along with separate populations that diffused in either 1D or 2D. The anionic and cationic PDI dyes exhibited the largest and smallest populations, respectively, of immobile molecules, suggesting that electrostatic interactions between the charged dyes and the cationic surfactant head groups play a significant role in limiting molecular motion. The cationic and anionic PDI dyes also exhibit the largest populations of 2D diffusing molecules, suggesting they may more readily pass between the cylindrical micelles and through the silica pore walls. All four dyes also emit strongly polarized fluorescence as they move in 1D, indicating they are orientationally confined within the nanochannels. Nile Red dye was used to determine the dielectric constant, ε, of nonpolar microenvironments in double-stranded DNA (ds-DNA) single molecules both in aqueous buffer solution and when adsorbed on amine-modified chemical gradient surfaces. The value of ε within the DNA decreased with increasing buffer concentration. Values of ε ∼ 6.75 and ∼3.00 were obtained in 0.1 mM phosphate buffered saline (PBS) and in 10 mM PBS, respectively. Similar effects were observed upon adsorption to chemically graded amine-modified silica surfaces. Under 1 mM buffer, ε was measured to be ∼2.84 and ∼1.90 at the low amine (high silica), and high amine (low silica) ends of the gradient, respectively. An increase in the buffer concentration again led to a decrease in ε, but only at the low amine end. It is concluded that high buffer concentrations and binding to an amine surface cause condensation of the ds-DNA, forming less polar microenvironments within its structure. These results provide important knowledge of the factors governing the polarity of DNA microenvironments to which intercalators bind.

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