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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.
151

Nanostructured Porous High Surface Area Ceramics for Catalytic Applications

Krawiec, Piotr 30 January 2007 (has links) (PDF)
In the present work new methods were developed for preparation of novel nanosized and nanostructured ceramic materials. Ordered mesoporous silica SBA-15 was found to be useful as a hard template for the nanocasting of silicon carbide and allowed the preparation of high temperature stable mesoporous silicon carbide ceramics. Chemical vapor infiltration of SBA-15 with dimethyldichlorosilane at elevated temperatures yields SiC/SBA-15 nanocomposites. The subsequent HF treatment of those composites resulted in silica removal and preparation of mesoporous silicon carbide with surface areas between 410 and 830 m2g-1 and high mesopore volume (up to 0.9 cm3g-1). The pore size (between 3 and 7nm in diameter) and surface area of mesoporous silicon carbide were controlled by adjusting the infiltration conditions (time, atmosphere). The mesoporous silicon carbide prepared via this method showed high structural thermal stability at 1300 oC, exceeding that of the SBA-15 template. However, the ordering on the mesoscopic scale was low. Nevertheless, highly ordered mesoporous silicon carbide materials were obtained via polymer melt infiltration in SBA-15. The low molecular weight polycarbosilane used as a preceramic precursor was converted at 1300 oC to silicon carbide inside the SBA-15, and after subsequent silica removal by HF, a highly ordered mesoporous material was obtained. Ordered mesoporous silicon carbide prepared by the methods reported here, may be an interesting material as a support due to its high temperature stability, chemical inertness, high thermal conductivity and semiconductor properties. In contrast to the nanocasting approach, based on the complete pore filling, also a new in-situ procedure for the preparation of finely dispersed metal and metal oxide particles inside ordered mesoporous silica was developed. A swelling agent (toluene) was used to deliver a hydrophobic platinum precursor into the surfactant micelles before addition of silica source. Such an in-situ method resulted in very high platinum incorporation (80-100%), not achieved for any other in-situ preparation procedures. Additionally, the presence of platinum allowed to decrease the template removal temperatures. Moreover, the method was also extended to other metal or metal oxide/ordered mesoporous silica systems. This may be especially interesting for the preparation of ordered mesoporous materials with low melting points, where typically the structure collapses during the high temperature calcinations process. The in-situ synthesized V2O5/MCM-41 materials were used to prepare VN/MCM-41 composites via nitridation in ammonia at 800oC. This method allowed to prepare highly dispersed, X-ray amorphous vanadium nitride species, with high activity in the propane dehydrogenation. Compared to nitridation of supported vanadium oxide prepared via the ex-situ procedure, in-situ synthesized materials showed similar catalytic activity, in spite of having significantly lower vanadium loading. As an alternative for the preparation of supported nitride materials, a novel preparation procedure of bulk not supported nanocrystalline vanadium nitride with high surface area was presented. Instead of pure oxide powder (which was typically used in the preparation of high surface area vanadium nitride catalysts), a macroporous amine intercalated V2O5 was used as the starting material. The obtained nitride consisted of small crystallites and had a surface area up to 198 m2g-1. Moreover, this foam-derived VN showed significantly improved activity as a catalyst in propane dehydrogenation. This novel preparation method could also be extended to other systems such as ternary VMoxNy nitrides.
152

ETUDE STRUCTURALE ET DYNAMIQUE DE SOLUTIONS DE SUCRE CONFINEES

Lelong, Gérald 02 February 2007 (has links) (PDF)
Bien que le rôle actif des sucres soit connu dans la stabilisation des membranes cellulaires lors de fortes déshydratations, il s'avère que les processus à l'origine de cette protection ne sont pas encore bien compris. Néanmoins, la très grande affinité de l'eau pour le sucre, comme en témoigne la formation de très nombreuses liaisons hydrogène, est semble-t-il responsable en partie de cette propriété exceptionnelle. L'étude expérimentale de la dynamique des molécules de sucre et d'eau permettra ainsi de quantifier l'importance de ces interactions. <br /> Dans ce travail, nous nous sommes principalement intéressés à des solutions de mono- et disaccharides (glucose, fructose et tréhalose). La diffusion quasi-élastique des neutrons a permis de mesurer, à l'échelle de la picoseconde, la dynamique de l'eau et du sucre en solution et sous confinement dans des matériaux poreux présentant un mimétisme d'échelle avec le vivant. Les deux matrices sélectionnées, c'est-à-dire un gel de silice aqueux et des nanosphères de silice mésoporeuse de type MCM-41, qui présentent des diamètres de pores de 18 et 3 nm respectivement, ont été caractérisées grâce à un large panel de techniques expérimentales (SANS, MET, MEB, Spectroscopie Raman, BET, DRX). L'effet du confinement sur la dynamique et sur les transitions de phase solide-liquide a ainsi pu être exploré, ainsi que l'effet protecteur des sucres grâce à une étude de déshydratation in-situ suivie par diffusion des neutrons aux petits angles.
153

Inférence exacte simulée et techniques d'estimation dans les modèles VAR et VARMA avec applications macroéconomiques

Jouini, Tarek January 2008 (has links)
Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal
154

Overview of business models for Web 2.0 communities

Hoegg, Roman, Martignoni, Robert, Meckel, Miriam, Stanoevska-Slabeva, Katarina 11 April 2014 (has links) (PDF)
A new type of communities is gaining momentum on the web and is reshaping online communication and collaboration patterns and the way how information is consumed and produced [Gros04, Kolb06]. Examples of such communities are Wikipedia, MySpace, OpenBC, YouTube, Folksonomies, numerous Weblogs and others. In literature different terms can be found to denote the emerging and growing new phenomenon: social software [Bäch06] or peer production [Scho05]. In the year 2005, Tim O'Reilly popularized the term Web 2.0 [O'Reil05]. While the first two terms can be applied also to earlier, already established forms of online communities (for an overview see [Stan02]), the term Web 2.0 is mostly applied to emphasize the differences of emerging communities compared to earlier forms of online communities, encompassing various perspectives - technology, attitude, philosophy. (...)
155

Molecular Order and Dynamics in Nanostructured Materials by Solid-State NMR

Kharkov, Boris January 2015 (has links)
Organic-inorganic nanostructured composites are nowadays integrated in the field of material science and technology. They are used as advanced materials directly or as precursors to novel composites with potential applications in optics, mechanics, energy, catalysis and medicine. Many properties of these complex materials depend on conformational rearrangements in their inherently dynamic organic parts. The focus of this thesis is on the study of the molecular mobility in ordered nanostructured composites and lyotropic mesophases and also on the development of relevant solid-state NMR methodologies. In this work, a number of new experimental approaches were proposed for dipolar NMR spectroscopy for characterizing molecular dynamics with atomic-level resolution in complex solids and liquids. A new acquisition scheme for two-dimensional dipolar spectroscopy has been developed in order to expand the spectral window in the indirect dimension while using limited radio-frequency power. Selective decoupling of spin-1 nuclei for sign-sensitive determination of the heteronuclear dipolar coupling has been described. A new dipolar recoupling technique for rotating samples has been developed to achieve high dipolar resolution in a wide range of dipolar coupling strength. The experimental techniques developed herein are capable of delivering detailed model-independent information on molecular motional parameters that can be directly compared in different composites and their bulk analogs. Solid-state NMR has been applied to study the local molecular dynamics of surfactant molecules in nanostructured organic-inorganic composites of different morphologies. On the basis of the experimental profiles of local order parameters, physical motional models for the confined surfactant molecules were put forward. In layered materials, a number of motional modes of surfactant molecules were observed depending on sample composition. These modes ranged from essentially immobilized rigid states to highly flexible and anisotropically tumbling states. In ordered hexagonal silica, highly dynamic conformationally disordered chains with restricted motion of the segments close to the head group have been found. The results presented in this thesis provide a step towards the comprehensive characterization of the molecular states and understanding the great variability of the molecular assemblies in advanced nanostructured organic−inorganic composite materials. / <p>QC 20150225</p>
156

Synthesis and Characterization of Ordered Mesoporous Silica with Controlled Macroscopic Morphology for Membrane Applications

January 2011 (has links)
abstract: Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can be fabricated as top-layers on macroporous supports or as embedded membranes in a dense matrix. The first part of the work deals with the hydrothermal synthesis and water-vapor/oxygen separation properties of supported MCM-48 and a new Al-MCM-48 type membrane for potential use in air conditioning systems. Knudsen-type permeation is observed in these membranes. The combined effect of capillary condensation and the aluminosilicate matrix resulted in the highest separation factor (142) in Al-MCM-48 membranes, with a water vapor permeance of 6×10-8mol/m2&#61655;Pa&#61655;s. The second part focuses on synthesis of embedded mesoporous silica membranes with helically ordered pores by a novel Counter Diffusion Self-Assembly (CDSA) method. This method is an extension of the interfacial synthesis method for fiber synthesis using tetrabutylorthosilicate (TBOS) and cetyltrimethylammonium bromide (CTAB) as the silica source and surfactant respectively. The initial part of this study determined the effect of TBOS height and humidity on fiber formation. From this study, the range of TBOS heights for best microscopic and macroscopic ordering were established. Next, the CDSA method was used to successfully synthesize membranes, which were characterized to have good support plugging and an ordered pore structure. Factors that influence membrane synthesis and plug microstructure were determined. SEM studies revealed the presence of gaps between the plugs and support pores, which occur due to shrinking of the plug on drying. Development of a novel liquid deposition method to seal these defects constituted the last part of this work. Post sealing, excess silica was removed by etching with hydrofluoric acid. Membrane quality was evaluated at each step using SEM and gas permeation measurements. After surfactant removal by liquid extraction, the membranes exhibited an O2 permeance of 1.65x10-6mol/m2.Pa.s and He/O2 selectivity of 3.30. The successful synthesis of this membrane is an exciting new development in the area of ordered mesoporous membrane technology. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011
157

Preparação dos catalisadores MoO3/MCM-41 e MoO3/SBA-15 com fontes alternativas de sílica destinados à reação de transesterificação do óleo de soja.

PAULA, Gustavo Medeiros de. 19 October 2018 (has links)
Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-19T13:06:58Z No. of bitstreams: 1 GUSTAVO MEDEIROS DE PAULA - DISSERTAÇÃO (PPGEQ) 2017.pdf: 3627178 bytes, checksum: f30200badddb75701ea0fec49346e30e (MD5) / Made available in DSpace on 2018-10-19T13:06:58Z (GMT). No. of bitstreams: 1 GUSTAVO MEDEIROS DE PAULA - DISSERTAÇÃO (PPGEQ) 2017.pdf: 3627178 bytes, checksum: f30200badddb75701ea0fec49346e30e (MD5) Previous issue date: 2017-03-30 / Capes / Este trabalho teve como objetivo sintetizar as peneiras moleculares MCM-41 e SBA-15, utilizando fontes alternativas de sílica, e preparar os catalisadores MoO3/MCM-41 e MoO3/SBA-15 e avaliar seu potencial catalítico na reação de transesterificação de óleo de soja para produção de biodiesel. As peneiras moleculares MCM-41 e SBA-15 foram sintetizadas empregando TEOS, argila chocolate B, cinzas de casca de arroz e pó de vidro como fontes de sílica. As fontes alternativas de sílica foram previamente dissolvidas em solução de NaOH (1 mol.L-1) a 100ºC por 6 horas. Em seguida, as misturas foram filtradas, e os filtrados contendo sílica dissolvida foram armazenados para posterior utilização nas sínteses das peneiras moleculares. As sínteses da MCM-41 ocorreram em duas etapas, o envelhecimento térmico ocorreu a 28 ºC por 2 horas e as sínteses hidrotérmicas ocorreram a 150 ºC por 96 horas. As sínteses da SBA-15 foram realizadas em duas etapas, o envelhecimento térmico ocorreu a 35 ºC por 24 horas e as sínteses hidrotérmicas ocorreram a 100 ºC por 48 horas. Os produtos das sínteses foram, lavados com água destilada e secos a 60 ºC por 24 horas. A deposição do MoO3 sobre os suportes MCM-41 e SBA-15 foi realizada por meio de impregnação úmida utilizando-se solução aquosa de Heptamolibdato de Amónio (0,1 mol.L-1), seguida de calcinação. As matérias-primas, assim como as peneiras moleculares e os catalisadores foram caracterizadas por Difração de raios X (DRX), Espectroscopia de Fluorescência de Raios X por Energia Dispersiva (FRX-ED), Microscopia eletrônica de Varredura (MEV) e Espectroscopia na Região de Infravermelho por Transformada de Fourier (FTIR). Os catalisadores foram avaliados na reação de transesterificação do óleo de soja com etanol em reator batelada sem agitação, com temperatura de 100 ºC durante 3 horas. Os resultados de DRX e FRX-ED das fontes de sílica mostram que todas são compostas por sílica amorfa e cristalina, evidenciando o potencial dos materiais. Os resultados de DRX, MEV e FTIR das peneiras moleculares mostraram a eficácia dos processos de síntese da MCM-41 e SBA-15 e dos catalisadores MoO3/MCM-41 e MoO3/SBA-15 com todas as fontes de sílica. Os biodieseis obtidos foram caracterizados utilizando técnicas de determinação de massa específica, viscosidade cinemática e índice de acidez. Os produtos gerados evidenciaram o poder catalítico dos catalisadores, porém revelaram que as condições reacionais empregadas são insuficientes para produção de biodiesel B100. / The study aimed to synthesize the MCM-41 and SBA-15 molecular sieves, using alternative silica sources, and to prepare the MoO3/MCM-41 and MoO3/SBA-15 catalysts and to evaluate their catalytic potential in the transesterification reaction of soybean for biodiesel production. The MCM-41 and SBA-15 molecular sieves were synthesized using TEOS, chocolate B clay, rice husk ash and glass powder as silica sources. The molecular sieves were synthesized using a hydrothermal method. Alternative silica sources were previously dissolved in NaOH solution (1 mol.L-1), filtered and the filtrates containing silica in the liquid phase were stored for further use in the molecular sieve synthesis. The MCM-41 synthesis occurred in two steps, the thermal ageing occurred at 28 °C for 2 hours and the hydrothermal synthesis occurred at 150 °C for 96 hours. The SBA-15 synthesis occurred in two steps, the thermal ageing occurred at 35 °C for 24 hours and the hydrothermal synthesis occurred at 100 °C for 48 hours. The synthesis products were washed with distilled water, filtered, dried at 60 °C for 24 hours and calcined at 550 °C for 7 hours.The MoO3 deposition on MCM-41 and SBA-15 support was performed by means of wetness impregnation using an aqueous solution of 0,1 mol.L-1 Ammonium Heptamolybdate. After the impregnation process, the material was subjected to calcination. The samples were characterized by X-ray diffraction (XRD), Energy Dispersive X-Ray Fluorescence Spectroscopy (ED-XRF), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). The catalysts were evaluated in the transesterification reaction of soybean oil with ethanol in a batch reactor without stirring at 100 ° C for 3 hours. The results of XRD and ED-XRF of the silica sources show that all are composed of amorphous and crystalline silica, evidencing the potential of the materials. The results of XRD, SEM and FTIR of the molecular sieves showed the efficiency of the synthesis of MCM-41 and SBA-15 and MoO3/MCM-41 and MoO3/SBA-15 catalysts with all silica sources. The biodiesel were characterized using techniques for determining specific mass, kinematic viscosity and acid index. The products generated evidenced the catalytic power of the catalysts, but revealed that the reaction conditions employed are insufficient for the production of B100 biodiesel.
158

Síntese da zeólita MCM-22 a partir de sistema reacional contendo sódio e potássio e desenvolvimento de catalisadores ácidos com topologia MWW modificada.

QUINTELA, Paulo Henrique Leite. 16 April 2018 (has links)
Submitted by Dilene Paulo (dilene.fatima@ufcg.edu.br) on 2018-04-16T15:00:45Z No. of bitstreams: 1 PAULO HENRIQUE LEITE QUINTELA - TESE (PPGEQ) 2016.pdf: 3975153 bytes, checksum: 257f1154ea4502e70913fe7937bf8a3f (MD5) / Made available in DSpace on 2018-04-16T15:00:45Z (GMT). No. of bitstreams: 1 PAULO HENRIQUE LEITE QUINTELA - TESE (PPGEQ) 2016.pdf: 3975153 bytes, checksum: 257f1154ea4502e70913fe7937bf8a3f (MD5) Previous issue date: 2016 / Capes / A MCM-22 é uma zeólita com estrutura porosa identificada pelo código MWW, cuja cristalização ocorre mediante a formação de um precursor lamelar. Embora a síntese da MCM-22 tenha sido extensivamente investigada, alguns parâmetros importantes para sua obtenção ainda não foram sistematicamente estudados. Neste contexto, o presente trabalho teve como objetivos avaliar a influência da fonte de alumínio e da presença dos cátions sódio e potássio na mistura reacional sobre a cristalização da MCM-22 e desenvolver catalisadores ácidos com topologia MWW modificada a partir da dessilicação da MCM-22 e da deslaminação do precursor lamelar. O método hidrotérmico foi utilizado para sintetizar a referida zeólita, variando-se a fonte de alumínio (hidróxido de alumínio, aluminato de sódio e pseudoboemita) e a quantidade relativa de sódio e potássio presente na mistura reacional, em condições estáticas. O processo de dessilicação foi efetuado utilizando soluções de hidróxido de sódio com diferentes concentrações, enquanto a deslaminação foi realizada via intumescimento do precursor lamelar e posterior esfoliação por sonicação. A acidez dos catalisadores foi avaliada por dessorção termoprogramada de amônia. Os resultados de DRX revelaram que entre as fontes de alumínio utilizadas o hidróxido de alumínio foi mais eficaz para sintetizar a MCM-22 nas condições experimentais empregadas, e que a presença simultânea de sódio e potássio na mistura reacional aumentou a cristalinidade e a taxa de cristalização da zeólita,quando o potássio correspondeu a 45% do total de metais alcalinos em base molar. As micrografias das amostras de MCM-22 mostraram que a morfologia e o tamanho das partículas foram afetados pelas diferentes proporções entre sódio e potássio avaliadas. As análises de DRX, adsorção física de N2 e MEV dos materiais dessilicados e deslaminados evidenciaram a sensibilidade da topologia MWW a tratamentos alcalinos e que o processo de esfoliação das monocamadas do precursor lamelar não ocorreu de forma integral. Os catalisadores ácidos com estruturas modificadas pelos processos de dessilicação e deslaminação apresentaram menor acidez e sítios ácidos mais fracos quando comparados à MCM-22 sem alterações estruturais, sendo a maior redução observada para o catalisador parcialmente esfoliado. / MCM-22 is a zeolite with a porous structure identified by the MWW code, which crystallization occurs through the formation of a lamellar precursor. Although the MCM-22 synthesis has been extensively investigated, some important parameters for its preparation have not yet been systematically studied. In this context, the present work aimed to evaluate the influence of the aluminum source and the presence of sodium and potassium cations in the reaction mixture on the MCM-22 crystallization and develop acid catalysts with MWW topology modified by MCM-22 desilication and delamination of its lamellar precursor. The hydrothermal method was used to synthesize the said zeolite, varying the aluminum source (aluminum hydroxide, sodium aluminate, and pseudoboehmite) and the relative amount of sodium and potassium present in the reaction mixture, under static conditions. The desilication process was conducted using sodium hydroxide solutions with different concentrations, whereas delamination was performed by swelling of the lamellar precursor and subsequent exfoliation by sonication. The catalysts acidity were evaluated by ammonia thermal programmed desorption. The XRD results showed that among the aluminum sources used the aluminum hydroxide was more effective to synthesize MCM-22 under the experimental conditions employed, and that the simultaneous presence of sodium and potassium in the reaction mixture increased zeolite crystallinity and crystallization rate, when potassium corresponded to 45% of the total alkali metal on a molar basis. The micrographs of MCM-22 samples showed that the morphology and particle size were affected by the different ratios between sodium and potassium evaluated. The XRD, N2 physical adsorption and SEM analyses of the desilicated and delaminated materials evidenced the MWW topology sensitivity to alkaline treatments and that the lamellar precursor monolayers exfoliation process did not occur integrally. The acid catalysts with structures modified by desilication and delamination processes presented lower acidity and weaker acid sites compared to the MCM-22 without structural changes, with the greatest reduction being observed in the partially exfoliated catalyst.
159

Utilização de um novo material mesoporoso funcionalizado PABA-MCM-41 na remoção de hidrocarbonetos policíclicos aromáticos (HPAs)

Costa, José Arnaldo Santana 23 October 2013 (has links)
This work describes the synthesis and characterization of the mesoporous material MCM-41 and a new functionalized mesoporous material, PABA-MCM-41, for use as adsorbents to remove the PAHs benzo[k]fluoranthene (B[k]F), benzo[a]pyrene (B[a]P), and benzo[b]fluoranthene (B[b]F). Both materials were synthesized using hydrothermal methods. PABA-MCM-41 was synthesized using a hydrothermal/co-condensation technique, with functionalization employing modified 4-aminobenzoic acid. The mesoporous materials were characterized using Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), nitrogen adsorption/desorption, scanning electron microscopy (SEM), and thermogravimetric analysis (TG). Batch adsorption experiments were employed to determine the effects of initial adsorbate concentration, contact time, and temperature on the removal of the PAHs. The co-condensation method was shown to be effective for the synthesis of functionalized PABA-MCM-41. The two mesoporous materials presented the hexagonal mesostructures typical of the M41S family, which were confirmed by the SAXS analyses and by the type IV isotherms with type H1 hysteresis. The materials possessed uniform mesopore size distributions, high surface areas, and were thermally stable. Adsorption tests showed that for both materials, the quantity adsorbed (qe) increased as the initial PAHs concentration was increased, with adsorption equilibrium reached in around 90 minutes. For adsorption by MCM-41, the equilibrium qe values were 12.49, 14.06, and 18.06 ìg g-1 for B[k]F, B[a]P, and B[b]F, respectively, while the corresponding values for the same PAHs were 22.51, 27.24, and 26.58 ìg g-1 when PABA-MCM-41 was used. The experimental kinetic data were fitted using the pseudo-second order model, and the Langmuir isotherm model was able to describe the process of PAH adsorption. At higher temperatures, there were increases in the initial adsorption rate and the kinetic constant for adsorption of the PAHs by PABA-MCM-41. The thermodynamic parameters indicated that the processes are spontaneous, endothermic, and with a tendency towards disorder of the system at the adsorbent/adsorbate interface. Functionalization of MCM-41 increased the efficiency of adsorption of the PAHs by 44.5, 48.4, and 32.0% for B[k]F, B[a]P, and B[b]F, respectively. / Este trabalho descreve a sintese e caracterizacao do material mesoporoso MCM-41 e do novo material mesoporoso funcionalizado PABA-MCM-41 para serem utilizados como materiais adsorventes na remocao dos HPAs benzo[k]fluoranteno (B[k]F), benzo[a]pireno (B[a]P) e benzo[b]fluoranteno (B[b]F). Os dois materiais foram sintetizados pelo metodo hidrotermal, sendo que PABA-MCM-41 foi sintetizado pelo metodo hidrotermal/co-condensacao, o qual foi funcionalizado pelo acido 4-aminobenzoico modificado. Os materiais mesoporosos sintetizados foram caracterizados por espectroscopia na regiao do infravermelho por transformada de Fourier (FTIR), espalhamento de raios-X a baixo angulo (SAXS), adsorcao/dessorcao de N2, microscopia eletronica de varredura (MEV) e analise termogravimetrica (TG). Os experimentos de adsorcao em batelada foram utilizados para determinar os efeitos da concentracao inicial do adsorbato, tempo de contato e temperatura na remocao dos HPAs B[k]F, B[a]P e B[b]F. O metodo da co-condensacao mostrou-se eficiente na sintese do material mesoporoso funcionalizado PABA-MCM-41. Os dois materiais mesoporosos apresentaram mesoestruturas hexagonais tipicas da familia M41S, as quais foram confirmadas por SAXS, com isotermas do tipo IV e histerese do tipo H1. Tambem, apresentaram distribuicao uniforme do tamanho de mesoporos, alta area superficial e estabilidade termica. Os ensaios de adsorcao mostraram que ocorreu um aumento da quantidade adsorvida (qe) com o aumento da concentracao inicial dos HPAs, isto para os dois materiais mesoporosos utilizados, sendo que o equilibrio de adsorcao foi alcancado em cerca de 90 minutos. Os valores de qe obtidos no equilibrio foram de 12,49; 14,06 e 18,06 Êg g-1, respectivamente, na adsorcao do B[k]F, B[a]P e B[b]F pelo MCM-41 e de 22,51; 27,24 e 26,58 Êg g-1, respectivamente, na adsorcao dos mesmos pelo PABA-MCM-41. Os dados cineticos experimentais se ajustaram melhor ao modelo cinetico de pseudo-segunda ordem e o modelo de isoterma de Langmuir descreveu melhor o processo de adsorcao dos HPAs pelo MCM-41 e PABA-MCM-41. Foi verificado que em temperaturas mais altas houve um aumento na taxa inicial de adsorcao e na constante cinetica de adsorcao dos HPAs pelo PABA-MCM-41. Os parametros termodinamicos indicaram que o processo e espontaneo, endotermico e com uma tendencia para desordem do sistema na interface adsorvente/adsorbato. Com a funcionalizacao do MCM-41 foi verificado um aumento na eficiencia de adsorcao dos HPAs de 44,5; 48,4 e 32,0 %, respectivamente para o B[k]F, B[a]P e B[b]F.
160

Obtenção de nanocristais semicondutores de CdTe via síntese in situ em matrizes mesoporosas MCM-41 para aplicação em sensores eletroquímicos na detecção de íons Cu2+ / Obtaining semiconductors nanocrystals CdTe by synthesis in situ into mesoporous of MCM-41 matrix for application electrochemical sensors in the Cu2+ ions detection

Santos, José Carlos dos 05 April 2016 (has links)
Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / CdTe semiconductor nanoparticles have unique optical properties, which can be tunable sizes, due to the quantum confinement effect. In the present work, stable CdTe nanocrystals were grown in the mesoporous environment of thiol-functionalized MCM-41 mesoporous silica from an approach employing 3-mercaptopropionic acid, an efficient capping agent. The obtained materials were characterized by infrared spectroscopy, N2 dessortion/adsorption, UV-Vis emission and absorption spectroscopy, transmission electron microscopy (TEM) and electrochemical characterization; X-ray diffraction (XRD) and thermogravimetric analyses were used to MCM-41 silica. The emission properties of CdTe were found to be dependent on the proportion of mesoporous matrix used in the synthesis, yielding CdTe nanocrystals emitting below the wavelength range usually obtained from aqueous colloidal synthesis. The detection of Cu2+ ions using modified carbon paste electrodes by anodic stripping voltammetry was possible only with samples of CdTe in situ, evidencing the role of the semiconductor as active phase. The most active sample obtained here was exactly that containing the lowest CdTe loading, showing it is possible to reduce the dosage of Cd-containing nanocrystals while improving their properties, which is crucial to concretize applications of CdTe nanocrystals. / Nanopartículas semicondutoras de CdTe possuem propriedades ópticas únicas ajustáveis, que são dependentes de seus tamanhos, devido ao efeito do confinamento quântico. No presente trabalho, nanopartículas estáveis de CdTe foram sintetizadas confinadas em um ambiente mesoporoso de uma sílica MCM-41 funcionalizada com grupos tióis, através do método de funcionalização com o uso do ácido 3-mercaptopropiônico. Os materiais obtidos foram caracterizados por espectroscopia vibracional na região do infravermelho, adsorção/dessorção de nitrogênio, espectroscopias eletrônicas de absorção UV-Vis e emissão, microscopia eletrônica de transmissão (MET) e caracterização eletroquímica; já as caracterizações por difração de raios X (DRX) e análise termogravimétrica foram usadas para sílica MCM-41. As propriedades de emissão do CdTe mostraram relação de dependência da proporção da matriz mesoporosa usada nas sínteses, resultando em emissão abaixo da faixa de comprimento de onda usualmente obtido para CdTe em meio coloidal aquoso. A detecção de íons Cu2+ através de eletrodos de pasta de carbono modificados foi realizada por voltametria de redissolução anódica, a qual apresentou sinal somente para as amostras de CdTe in situ, o que evidenciou o papel do semicondutor como fase ativa do eletrodo. A amostra mais ativa foi aquela que continha a menor proporção CdTe, evidenciando que é possível reduzir a dosagem de Cd2+ nos nanocristais enquanto se aperfeiçoam suas propriedades, o que é crucial do ponto de vista das aplicações de nanocristais de CdTe.

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