952 resultados para Al-MCM-41 applications
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Ta2O5-SiO2 catalysts were prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) and tantalum (V) ethoxide as the sources of silicon and tantalum, and two families of quaternary ammonium salts, [CnH(2n+1)(CH3)(3)N]Br (n = 14, 16, 18) and [(CnH(2n+1))(4)N]Br (n = 10, 12, 16, 18) as surfactants. The catalysts were compared for the selective suffoxidation of 4,6-dimethyl-2-thiomethylpyrimidine using peroxide as an oxidising agent in a range of ionic liquids and organic solvents. The sol-gel catalysts were also compared with tantalum on MCM-41 prepared by grafting. The catalysts were characterized from adsorption-desorption isotherms of N-2, XRD patterns, small-angle X-ray scattering, IR spectra from adsorbed pyridine and CDCl3, XPS spectra, and Si-29 magic angle spinning (MAS) NNIR experiments. The effect of recycling on the catalyst leaching and selectivity/activity was also studied. High activities and selectivities were found in [NTf2](-) based ionic liquids and organic solvents with good recyclability of the catalyst. Tantalum was found in the solution after reaction; however, this was determined to be due to entrapment of catalyst particulates, as opposed to leaching of the active metal. (c) 2005 Elsevier Inc. All rights reserved.
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Novel drug delivery systems (DDS) to improve the pharmacokinetic profile of hydrophobic drugs following oral administration are an area of keen interest in drug research. An ideal DDS should not adversely affect drug activity, be capable of delivering a therapeutic dose of drug, and allow homogenous drug loading and drug release. Mesoporous silica has been proposed for this application, with ibuprofen employed as the model drug. It was hypothesised that mesoporous silica MCM-41 is capable of delivering a pharmacologically therapeutic dose of ibuprofen. Ibuprofen-loaded MCM-41 can be prepared reproducibly at a drug to carrier ratio of 30% (wt/wt). The release profile was seen to be 90% within 2 h. Initial assessment of COX-1 inhibitory activity suggests the absence of adverse effects attributable to drug-carrier interaction. The results of this study provide further evidence in support of the proposed use of mesoporous silica in drug delivery.
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Copper containing MCM-41 materials can be used to both store gaseous nitric oxide and to catalytically produce nitric oxide from nitrite. The active species for the reaction is copper (I). Addition of cysteine to the solution in contact with the material has different effects depending on how much Cu(I) is present. This is a new method of extending the lifetime of gas delivery from a gas storage material.
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Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.
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A presente dissertação teve como objectivo a síntese, caracterização e estudo das propriedades luminescentes de complexos livres e/ou imobilizados no material mesoporoso MCM-41. Na primeira parte estudaram-se complexos do tipo, Eu(NTA)3L2, onde NTA corresponte ao β-dicetonato 1-(2-naftoil)-3,3,3-trifluoro-acetonato, e L2 aos ligandos bidentados de azoto derivados do pirazolilpiridina e L aos ligandos monodentados (etil-4-piridilacetato, água, piridina e metilfenilsulfóxido). Alguns destes ligandos foram imobilizados e/ou impregnados no MCM-41, tendo-se posteriormente complexado o fragmento Eu(NTA)3. Na segunda parte estudou-se o efeito do contra-ião no complexo C[Eu(NTA)4], usando os catiões (C): tetrabutilamónio [NBu4]+, 1-butil-3-metilimidazolilo [C4mim]+ e 1-butil-3-metilpiridínio [C4mpy]+. O anião [Eu(NTA)4]- foi imobilizado no MCM-41 derivatizado com grupos 1-propil-3-metilimidazolilo. Todos os complexos preparados foram caracterizados pelas técnicas de análise elementar, termogravimetria, espectroscopias vibracionais (Infravermelho e Raman) e de ressonância magnética nuclear, e os materiais preparados foram adicionalmente analisados por difracção de raios-X de pós e ressonância magnética nuclear de estado sólido. Foram também estudadas as propriedades fotoluminescentes dos compostos, e para facilitar a análise dos resultados, nalguns casos foram preparados e caracterizados os compostos análogos de gadolínio.
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Ordered mesoporous silicas with a channel structure of well-defined geometries and dimensions at nanometer scale are excellent candidates to host intercalation reactions. In recent years, our research group has shown that mesoporous silicas of the M41S class combined with metallocene complexes give rise to excellent supported catalysts for ethylene polymerisation. Due to the support characteristics, the reaction is allowed to occur in the channels and in this way hybrid organic-inorganic materials can be prepared within a large range of nanofiller concentration. These HDPE/MCM-41 nanocomposites exhibit an improved mechanical performance and an easier degradability due to the additional role of MCM-41 as a promoter for PE degradation.
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A presente dissertação tem como objetivo principal contribuir para um maior conhecimento e compreensão das propriedades catalíticas de sistemas baseados em metais de transição com estado de oxidação elevado. O trabalho desenvolvido englobou a síntese e a caracterização de novos compostos de molibdénio, tendo como ponto de partida a síntese de cis-dioxocomplexos do tipo MoO2Cl2Ln (n = 1 ou 2, conforme ligandos bidentados ou monodentados, respetivamente) a partir dos precursores MoO2Cl2, MoO3 e Na2MoO4 com ligandos como dimetilformamida (DMF), tris(benzimidazolil)metano (HC(bim)3). Os compostos MoO2Cl2(DMF)2 (Capítulo2) e [MoO2Cl(HC(bim)3]Y (Y = Cl, BF4 e PF6) (Capítulo 3) foram testados como precursores catalíticos na epoxidação de olefinas, em fase heterogénea. O primeiro foi imobilizado no suporte MCM-41 enquanto os últimos foram heterogeneizados com recurso a líquidos iónicos - [BMIM]Y e [BMPy]Y (BIM = 1-n-butil-3-metilimidazólio, BMPy = 1-n-butil-3-metilpiridina; Y = BF4 ou PF6), como estratégia alternativa à heterogeneização dos catalisadores homogéneos. Por outro lado, aprofundou-se também a epoxidação de olefinas em fase homogénea e, para isso, sintetizaram-se os compostos Mo(CO)3(HC(pz)3) (HC(pz)3 = tris(1-pirazoli)metano), Mo(CO)3(HC(3,5-Me2pz)3 (HC(3,5-Me2pz)3 = tris(3,5-dimetil-1-pirazolil)metano) (Capítulo 4) e Mo(CO)4(BPM) (BPM = bis(pirazolil)metano) (Capítulo 5) a partir do material de partida Mo(CO)6. A descarbonilação oxidativa destes compostos, com TBHP, originaram estruturas cristalinas do tipo dioxo--oxo, [{MoO2(HC(pz)3)}2(2-O)][Mo6O19] e [{MoO2(HC(3,5-Me2pz)3)}2(2-O)][Mo6O19], e oxodiperoxo, MoO(O2)2(BPM), respetivamente. Obtiveram-se os mesmos produtos in situ durante as respetivas reações catalíticas. Todos os compostos foram utilizados como catalisadores ou pré-catalisadores na epoxidação de olefinas, com bons resultados. Por fim e, tendo em conta o crescente interesse em materiais híbridos orgânicos-inorgânicos baseados em óxidos de molibdénio, sintetizou-se o composto MoO2Cl2(pypzEA) (pypzEA = etil[(3-piridin-2-il)-1H-pirazol-1-il]acetato) o qual, ao reagir com água, originou o material híbrido [Mo2O6(HpypzA)] (HpypzA = [3-(piridin-2-il)-1H-pirazol-1-il]acetato) (Capítulo 6). A estrutura deste último composto foi resolvida por difração de monocristal e de raio-X de pós, em conjunto com a informação proveniente de técnicas como FT-IR, RMN 13C CP/MAS e análise elementar. Este material híbrido apresenta um bom desempenho catalítico quando o TBHP é usado como oxidante e continua estável e a comportar-se como um catalisador heterogéneo mesmo após sofrer testes de reciclagem e de filtração. Ainda durante este estudo constatou-se que a reação oxidativa do material de partida, MoO2Cl2(pypzEA), com TBHP, originou o oxo(diperoxo)complexo MoO(O2)2(pypzEA) e o complexo octamérico [Mo8O24(pypzEA)4] obtido previamente pela descarbonilação oxidativa do Mo(CO)4(pypzEA). Todos os catalisadores ou precursores de espécies ativas foram analisados por técnicas de caracterização comuns (AE, FT-IR, Raman, ATR, 1H RMN) bem como por técnicas de caracterização do estado sólido (EXAFS, DRX de pós e de cristal único, 13C e 29Si RMN CP MAS). Os compostos com propriedades catalíticas e pré-catalíticas promissoras foram estudados nas reações catalíticas de epoxidação de diversas olefinas, nomeadamente, cis-cicloocteno, 1-octeno, trans-2-octeno, -pineno, (R)-(+)-limoneno, estireno, norborneno, entre outras.
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Introducción: el Cáncer de cérvix en Colombia ocupa el primer lugar en mortalidad e incidencia. La mortalidad en el departamento del Meta durante el 2008 llegó a 65 casos, incrementándose en 15 casos con relación al año anterior. De esta cifra Villavicencio reportó 36 casos. Metodología: estudio descriptivo, de pacientes nuevos que reportaron biopsias LEIAG afiliados al régimen contributivo, subsidiado y población pobre no asegurada, en el municipio de Villavicencio durante el año 2008. De 471 registros, 189 biopsias fueron clasificadas LEIAG, datos de 71 pacientes fueron procesados en SPSS15. Resultados: por aseguramiento el 42% pertenece al contributivo, 41% al subsidiado, 12 % a la población pobre no asegurada y 5 % multiafiliados. El 88.7% de LEIAG se presentan entre 30-60 años. El 90.1% no asistió a programas de promoción y prevención. El 84% del contributivo, recibió reporte de citología entre 0-11 días. Contrastando con el 95% de la población pobre no asegurada 20-49 días. El 70.3% recibió reporte de biopsia entre 0 a 19 días. El 43.7% inició relaciones sexuales entre los 12-15 años. El 35.2% ha estado expuesta a fumigaciones. El 38% presentan antecedentes familiares de cáncer, predominando cérvix, seno y estómago. Discusión: riesgos como edad, relaciones sexuales tempranas, exposición a tóxicos, se encuentran en parámetros de literatura revisada. Demanda inducida y procesos de promoción y prevención son factores que deben fortalecer aseguradores, prestadores y ente territorial.
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El ejemplar correspondiente al Documento 41/1 se publicó el año 1978 y el corriespondiente al Documento 41/2 en el año 1980
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Selected silicas were modified with the covalently bound ligand 2,6-bis(benzoxazoyl)pyridine (BBOP), equilibrated with copper(II) nitrate, then challenged with toxic vapour containing HCN (8000 mg m(-3) at 80% relative humidity). The modified SBA-15 material (Cu-BBOP-SBA-15) had an improved breakthrough time for HCN (36 min at a flow rate of 30 cm(3) min(-1)) when compared to the other siliceous materials prepared in this study, equating to a hydrogen cyanide capacity of 58 mg g(-1), which is close to a reference activated carbon adsorbent (24 min at 50 cm(3) min(-1)) that can trap 64 mg g(-1). The enhanced performance observed with Cu-BBOP-SBA-15 has been related to the greater accessibility of the functional groups, arising from the ordered nature of the interconnected porous network and large mesopores of 5.5 nm within the material modified with the Cu(II)-BBOP complex. Modified MCM-41 and MCM-48 materials (Cu-BBOP-MCM-41 and Cu-BBOP-MCM-48) were found to have lower hydrogen cyanide capacities (38 and 32 mg g(-1) respectively) than the Cu-BBOP-SBA-15 material owing to the restricted size of the pores (2.2 and <2 nm respectively). The materials with poor nano-structured ordering were found to have low hydrogen cyanide capacities, between 11 and 19 mg g(-1), most likely owing to limited accessibility of the functional groups. (C) 2004 Elsevier Inc. All rights reserved.
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The synthesis of highly ordered mesoporous tungsteno-silicas in which a high percentage of tungsten is introduced into a silica framework is reported hereafter. Powder XRD and TEM have been used to characterize the materials synthesized at room temperature. The materials are shown to be homogeneous as there is no evidence for any crystalline species other than the silica framework. The pore diameter and the surface area of the materials, evaluated from the nitrogen adsorption isotherms and unit cell parameter indicate a pore diameter of about 2 nm and a surface area of 1400 m(2) g(-1) for a content of 10% tungsten. Catalyzed dehydration of 2-propanol has been investigated and the activity of the materials synthesized is significant, even for low tungsten content W-MCM-41 materials. (C) 2003 Elsevier B.V. All rights reserved.
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The MCM-41 mesoporous synthesis was done using rice hulls ash and chrysotile as natural alternative silica sources. For the using of these sources, chemical and thermic treatments were done in both materials. After chemical and thermic treatments, these materials were employed on the MCM-41 mesoctructures synthesis. The natural materials treated and employed in the synthesis were characterized by several techniques such as X-ray diffraction, N2 adsorption and desorption, scanning electronic microscopy and thermogravimetric analysis. MCM-41 standart samples synthetized with aerosil 200 commercial sílica were used to evaluation. The formed material from rice hulls ash showed values from BET specific area about 468 m².g-1, N2 adsorption and desorption isotherms and loss mass similar to reference materials. The silica from chrysotile calcined and leached was employed to mesoporous materials synthesis. The BET specific area showed values about 700 m².g-1, N2 adsorption and desorption isotherms type IV and loss mass similar to mesoporous materials. The formed material from calcined and leached chrysotile, without calcination, applied to phenol remotion carried high performance liquid chromatography and evaluated with organophilic clays with different treatments. By the characterization techniques were proved that mesoporous materials with lesser order that reference samples. The material formed from rice hulls ash without the calcination step achieved better adsorption results than organophilic clays
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The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc
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Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it
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Oxygen carriers are metal oxides which have the ability to oxidize and reduce easily by various cycles. Due to this property these materials are widely usedin Chemical-Looping Reforming processes to produce H2 and syngas. In this work supports based on MCM-41 and La-SiO2 were synthesized by hydrothermal method. After the synthesis step they were calcined at 550°C for 2 hours and characterized by TG, XRD, surface area using the BET method and FTIR spectroscopy. The deposition of active phase, in this case Nickel, took place in the proportions of 5, 10 and 20% by weight of metallic nickel, for use as oxygen carriers.The XRD showed that increasing in the content of Ni supported on MCM-41 resulted in a decrease in spatial structure and lattice parameter of the material. The adsorption and desorption curves of the MCM-41 samples exhibited variations with the increase of Ni deposited. Surface area, average pore diameter and wall density of silica showed significant changes , due to the increase of the active phase on the mesoporous material. By other hand, in the samples with La-SiO2 composition was not observed peaks characteristic of hexagonal structure, in the XRD diffractogram. The adsorption/desorption isotherms of nitrogen observed are type IV, characteristic of mesoporous materials. The catalytic test indicates that the supports have no influence in the process, but the nickel concentration is very important, because the results for minor concentration of nickel are not good. The ratio H2/O2 was close to 2, for all 15 cycles involving the test storage capacity of O2, indicating that the materials are effective for oxygen transport