Le contrôle fin de la structure et de la chimie de surface en milieu confiné a été développé dans des silices poreuses mésostucturées de type MCM-41 pour synthétiser des catalyseurs hétérogènes combinant confinement moléculaire, hydrophobicité et spécificité de sites à l'instar des métalloprotéines. La surface considérée comme lisse a en fait une rugosité de type alvéolaire due à l'empreinte de la tête ammonium du tensioactif de synthèse. Pour des températures croissantes du traitement hydrothermal, la taille des mésopores augmente par érosion de cette rugosité puis diminue par épaississement des parois. On a aussi trouvé des conditions de synthèse de zéolihes mésoporeuses avec une micro- et mésoporosité hiérarchisée. Ces surfaces sont polyfonctionnalisées grâce à la technique de pochoir moléculaire pour isoler des fonctions bidentatés aminoéthylaminopropyles par des groupements hydrophobes triméthylsimyles. Les ions cuivriques sont alors retenus dans le matériau par complexation à ces fonctions diamino.

Confining walls induce qualitative changes in adsorbed fluids. Among the most intriguing phenomena is hysteresis, where a pore fills with fluid at a greater pressure than it empties. The causes and mechanisms by which this occurs are intensely investigated yet still poorly understood. Ordered mesoporous silicas, recently discovered materials with well-defined pore size distributions, provide an opportunity to deepen our understanding of the fundamental physics of the interaction of fluids with complex solids.In part of this computational investigation we examine idealized pores. In agreement with other recent studies, we find that in 'inkbottle'-shaped pores, where a large cavity is accessible to the bulk fluid only by constrictions, there is no evidence of the long-hypothesized phenomenon of `pore blocking', where the constrictions inhibit fluid desorption from the cavity. We find that even in these simple systems the mechanism of hysteresis depends on pore characteristics, fluid properties and external conditions.For silicas containing cylindrical holes of nearly uniform diameter, such as MCM-41, the state-of-the-art is to consider only a single pore, but the poor qualitative agreement of theoretical with experimental results has improved little as wall representations of increasing sophistication have been developed. Using only a one-dimensional potential, we reproduce features of isotherms, including in the hysteresis region, by averaging over a narrow distribution of pore sizes. The qualitative behavior is shown to be a collective phenomenon not representative of any individual pore. Adding surface roughness and a constriction to the pores yields results quantitatively nearly indistinguishable from experiments.For materials larger than MCM-41, a continuum simulation proves too computationally taxing. Thus, a lattice model with adjustable fineness of site spacing is developed. It is found that a surprisingly low level of fineness is needed for confined systems to closely approximate continuum results. This model is applied to cubically symmetric materials, such as MCM-48 and SBA-16, finding that simulations are able to reproduce much of the qualitative behavior seen experimentally, but the lack of existing knowledge of the nature of silica walls proves to be a limiting factor.

Fast depletion of oil reserves necessitates the development of novel alternative motor vehicle fuels. Global warming problems also initiated new research to develop new fuels creating less CO2 emission. Nowadays, dimethyl ether (DME) and diethyl ether (DEE) are considered as important alternative clean energy sources. These valuable ethers are produced by the dehydration reaction of methanol and ethanol, respectively, in the presence of acidic catalysts. Besides DEE, ethylene which is very important in petrochemical industry, can also be produced by ethanol dehydration reaction. In the first part of this study, the catalytic activity of tungstophosphoric acid (TPA), silicotungstic acid (STA) and molybdophosphoric acid (MPA), which are well-known heteropolyacids were tested in ethanol dehydration reaction. The activities of other solid acid catalysts, such as Nafion and mesoporous aluminosilicate, were also tested in the dehydration reaction of ethanol. In the case of DME production by dehydration of methanol, activities of STA, TPA and aluminosilicate catalysts were tested. Among the heteropolyacid catalysts, STA showed the highest activity in both ethanol and methanol dehydration reactions. With an increase of temperature from 180oC to 250oC, Ethylene selectivities increased while DEE selectivities decreased. Ethylene yield values over 0.70 were obtained at 250oC. The presence of water in the feed stream caused some reduction in the activity of TPA catalyst. Very high DME yields were obtained using mesoporous aluminosilicate catalyst at about 450oC. The surface area of heteropolyacids are very low and they are soluble in polar solvents such as water and alcohols. Considering these drawbacks of heteropolyacid catalysts, novel mesoporous STA based high surface area catalysts were synthesized following a hydrothermal synthesis route. These novel catalysts were highly stable and they did not dissolve in polar solvents. The catalysts containing W/Si ratios of 0.19 (STA62(550)) and 0.34 (STA82(550)) have BJH surface area values of 481 m2/g and 210 m2/g, respectively, with pore size distributions ranging in between 2-15 nm. These catalysts were characterized by XRD, EDS, SEM, TGA, DTA, DSC, FTIR and Nitrogen Adsorption techniques and their activities were tested in ethanol dehydration reaction. Calcination temperature of the catalysts was shown to be a very important parameter for the activities of these catalysts. Considering the partial decomposition and proton lost of the catalysts over 375oC, they are calcined at 350oC and 550oC before testing them in ethanol dehydration reaction. The catalysts calcined at 350oC showed much higher activity at temperature as low as 180oC. However, the catalysts calcined at 550oC showed activity over 280oC. Ethylene yield values approaching to 0.90 were obtained at about 350oC with catalysts calcined at 350oC. DEE yield past through a maximum with an increase in temperature indicating its decomposition to Ethylene at higher temperatures. However, at lower temperatures (&lt / 300oC) Ethylene and DEE were concluded to be formed through parallel routes. Formation of some acetaldehyde at lower temperatures indicated a possible reaction path through acetaldehyde in the formation of DEE. DRIFTS results also proved the presence of ethoxy, acetate and ethyl like species in addition to adsorbed ethanol molecules on the catalyst surface and gave additional information related to the mechanism.

Plastic materials are widely used throughout the world due to their low prices and easy processing methods. A serious problem of environmental pollution is brought with the widespread use of these materials due to their non-biodegradabilty. For this reason, plastic materials are degraded into lower molecular weight liquid and gaseous products which are potential raw materials and fuels for petrochemical industry. The use of catalysts enhances the formation of more valuable hydrocarbons at lower reaction temperatures and residence times. In this study, aluminum containing MCM-41 and tungstophosphoric acid (TPA) loaded SBA-15 materials were synthesized by impregnation of Al and TPA into hydrothermally synthesized MCM-41 and SBA-15, respectively to be used in catalytic degradation of polyethylene. Al was incorporated into MCM-41 framework with different Al/Si ratios using aluminum triisopropylate as the aluminum source and TPA was incorporated to the porous framework of SBA-15 with different W/Si ratios, using tungstophosphoric acid hydrate as the acid source. From XRD analysis, it was observed that introducing acidic compounds did not cause deformations in the regularity and by EDS analysis, it was found out that at lower loadings, acidic compounds were introduced more effectively for MCM-41 materials. Nitrogen adsorption-desorption isotherms showed that the synthesized materials exhibited type IV isotherms. SEM and TEM pictures showed the hexagonal regularly ordered structure of SBA-15 and MCM-41 materials. FTIR analysis of the pyridine adsorbed synthesized materials revealed the existence of Lewis and Br&oslash / nsted acid sites in the synthesized materials. From TGA analysis it was observed that aluminum impregnated MCM-41 samples reduced the temperature of the degradation reaction significantly and TPA loaded SBA-15 samples reduced activation energy of the reaction effectively. In the degradation reaction system, non-catalytic and catalytic degradation experiments of polyethylene were performed. In non-catalytic degradation and catalytic degradation reactions carried out using aluminum containing MCM-41 materials, selectivity of C3 and C4 hydrocarbon gases was high and in catalytic degradation reactions carried out using TPA impregnated SBA-15 materials, selectivity of ethylene was high. In the liquid analysis of non-catalytic degradation reactions, it was observed that the product distribution was mainly composed of hydrocarbons greater than C18. The use of aluminum loaded MCM-41 and TPA loaded SBA-15 materials resulted in a liquid product distribution in the range of C5-C14, which is the hydrocarbon range of gasoline fuel.

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The active sites for epoxydation of alkenes in silica supported titanium catalysts are isolated Ti(IV) ions. The strategy for site isolation consists here to graft titanium isopropoxyde by reaction with surface silanol groups, the density of which is decreased by chemical capping instead of the energy consuming thermal treatment. The molecular stencil patterning technique (MSP) is applied to enforce site isolation. In mesostructured porous silicas, the partly extracted templating surfactant plays the role of a MSP mask during capping. Then, the elimination of the remaining surfactant liberates silanol islands for the grafting of Ti(IV) ions. Quantitative FT-IR and 29Si MAS-NMR studies reveal that the inverse organic stencil made of grafted organosilyls groups is maintained at each synthesis steps. Diffuse reflectance UV spectroscopy in correlation with the catalytic activity in epoxidation of cyclohexene show that these original surfaces favor the formation of a much larger number of isolated mononuclear sites than the unmodified silica surfaces. The demonstration is obtained using a dipodal organosilyl function, 1-2-ethanebis (dimethylsilyl) (EBDMS) that is much more stable than the classic and monopodal, trimethylsilyl (TMS). Besides, it is shown that the inverse organic stencil (from EBDMS or TMS) is stabilized further by thermal treatment while its dispersive effect on titanium can be preserved. The proof relies on a quantitative 29Si solid State NMR study. Finally, a refined description of the grafting mode of titanium was realized by simulation of the UV spectra of a large series of catalysts assuming only 5 different types of species including isolated species and clusters differentiated by the range of sizes.

Discovery of mesoporous materials by Mobil researchers in 1992 opened a new field in catalytic applications. The materials designated as M41S family are MCM-41 with one-dimensional hexagonal structure, MCM-48 with three-dimensional cubic structure and MCM-51 with unstable lamellar structure. This family of materials have high surface areas up to 1500 m2/g, narrow pore size distributions with pore sizes varying from 20 to 100 &Aring / . These materials can be activated by incorporation of metals or active compounds into their structures. In this study, copper and nickel incorporated MCM-41 type catalytic materials were synthesized via different methods namely, impregnation, high temperature and low temperature direct synthesis methods. The Cu-MCM-41, and Ni-MCM-41, as well as synthesized MCM-41 were characterized by using XRD, TEM, N2 sorption, SEM, XRF, EDS, AAS and TPR. MCM-41 was synthesized with high temperature direct synthesis method. High surface area values up to 1400 m2/g of MCM-41 mesoporous materials were obtained with high pore volumes up to 1.17 cc/g. Cu-MCM-41 type catalytic materials were synthesized with three different methods. Impregnation and high temperature direct synthesis methods gave better results than those of low temperature direct synthesis method. In impregnation, relatively high surface area values (730 m2/g) were obtained with Cu/Si mole ratio as high as 0.3 in the product. For the case of high temperature direct synthesis products, Cu/Si mole ratios as high as 0.26 were obtained with somewhat smaller surface areas (400 m2/g). Low temperature direct synthesis method is the least favorable method in metal loading. Ni-MCM-41 type of catalytic materials were synthesized by impregnation and high temperature direct syntheses methods. Ni incorporation by high temperature direct synthesis method gave high surface area values (560-930 m2/g) having Ni/Si mole ratios of 0.12-0.28.

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-03-23T19:40:24Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alenice_ferreira_cruz.pdf: 3398178 bytes, checksum: 4f7c2c8ff0a3c9856be63b637e43306b (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-04-20T16:59:10Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alenice_ferreira_cruz.pdf: 3398178 bytes, checksum: 4f7c2c8ff0a3c9856be63b637e43306b (MD5) / Made available in DSpace on 2017-04-20T16:59:11Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alenice_ferreira_cruz.pdf: 3398178 bytes, checksum: 4f7c2c8ff0a3c9856be63b637e43306b (MD5) Previous issue date: 2016 / O bisfenol-A ? um importante produto qu?mico, amplamente utilizado em ind?strias para a produ??o de policarbonatos, resinas epoxi e outros pl?sticos. Existe uma car?ncia em desenvolver m?todos eficazes para remov?-lo de efluentes. Uma vez que, o mesmo faz parte dos chamados poluentes emergentes, pois ? um contaminante prejudicial para os organismos, mesmo em baixas concentra??es, devido ao seu efeito nocivo sobre sa?de. Neste trabalho, buscou-se avaliar o desempenho de dois silicatos mesoporosos (MCM-41 e Co-silicato) frente ? adsor??o do bisfenol-A. Os perfis de difra??o de raio-X dos materiais confirmaram a forma??o da MCM-41 e o material modificado (Co-silicato) demonstrou alterar ao ?nico elemento de ordem estrutural, que ? a disposi??o dos canais paralelos (2?=2). As imagens de MEV mostraram que os materiais n?o apresentaram morfologia definida. Dados indicaram que ambos os materiais apresentam elevada ?rea espec?fica, sendo 988 m2g-1 para MCM-41 e 729 m2g-1 para Co-silicato. O material Co-silicato mostrou elevado potencial como adsorvente, frente ? MCM-41. A elevada ?rea superficial, aliada ao tamanho dos poros, juntamente com a presen?a de ?ons met?licos (cobalto) favoreceram o processo de adsor??o. A forma??o de s?tios ativos no silicato, ap?s a inser??o de cobalto, favoreceu a adsor??o do contaminante. A partir dos testes de adsor??o realizados em pH 3, 6 e 9 foi poss?vel notar que o material que teve uma melhor capacidade de adsor??o foi o material Co-silicato. Diante dos testes de cin?tica, o material Co-silicato nas faixas de pH analisadas demonstrou maior potencial de adsor??o do bisfenol-A, em rela??o ao resultados de remo??o obtidos com o material MCM-41. Os modelos utilizados para os ajustes matem?ticos da adsor??o foram as isotermas de Langmuir, Freundlich, e Redlich-Peterson. O valor do coeficiente de correla??o (R2) 0,9641 pH 3; (R2) 0,9834 pH 6 e (R2) 0,9959 pH 9 dos par?metros de Redlich-Peterson sugeriram que o modelo de Redlich-Peterson descreve melhor o comportamento de adsor??o de bisfenol-A no material Co-silicato, j? que apresenta maior valor do coeficiente de correla??o em pH testados, comparando com os valores de correla??o (R2) de Langmuir e Freundlich. Os dados revelaram que a modifica??o da MCM-41 com ?tomos de cobalto alteraram as propriedades f?sico-qu?mica do material, e potencializou o adsorvente para adsor??o da mol?cula de bisfenol-A. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / Bisphenol-A is an important chemical, widely used in industries for the production of polycarbonates, epoxy resins and other plastics. There is a lack of effective methods to remove it from effluents. Since it is part of so-called emerging pollutants, it is a harmful contaminant for organisms, even in low concentrations, because of its harmful effect on health. This work aimed to evaluate the performance of two mesoporous silicates (MCM-41 and Co-silicate) against the adsorption of bisphenol-A. The X-ray diffraction profiles of the materials confirmed the formation of MCM-41 and the modified material (Co-silicate) was shown to change to the only structural element, which is the arrangement of the parallel channels (2? = 2). The SEM images showed that the materials did not present definite morphology. Data indicated that both materials presented a high specific area, being 988 m2g- 1 for MCM-41 and 729 m2g-1 for Co-silicate. Co-silicate material showed high adsorbent potential compared to MCM-41. The high surface area, together with the pore size, together with the presence of metallic ions (cobalt) favored the adsorption process. The formation of active sites in the silicate, after the insertion of cobalt, favored the adsorption of the contaminant. From the adsorption tests carried out at pH 3, 6 and 9 it was possible to observe that the material with the best adsorption capacity was the Co-silicate material. Due to the kinetic tests, the Co-silicate material in the analyzed pH ranges showed a higher adsorption potential of bisphenol-A in relation to the removal results obtained with the MCM-41 material. The models used for the mathematical adjustments of the adsorption were the isotherms of Langmuir, Freundlich, and Redlich-Peterson. The value of the correlation coefficient (R2) 0.9641 pH 3; (R2) 0.9834 pH 6 and (R2) 0.9959 pH 9 of the Redlich-Peterson parameters suggested that the Redlich-Peterson model better describes the adsorption behavior of bisphenol-A in the Co-silicate material, since it presents Higher value of the pH correlation coefficient tested, compared with the Langmuir and Freundlich correlation values (R2). The data revealed that the modification of MCM-41 with cobalt atoms altered the physicochemical properties of the material and potentiated the adsorbent for adsorption of the bisphenol-A molecule.

Made available in DSpace on 2016-06-02T19:56:53Z (GMT). No. of bitstreams: 1 5790.pdf: 8879884 bytes, checksum: 256bcf8b3832d498d50cb0b4fea7cecc (MD5) Previous issue date: 2014-02-25 / Universidade Federal de Sao Carlos / The increasing demand for it in today s world and the problems caused by fossil fuel usage lead to a search for alternative sources that may integrate the world s energy matrix. In this context, because this product is essential to technological, social and environmental development of a country, biofuels like ethanol and biodiesel are strong candidates to minimize the worries about energy availability. Biodiesel is often produced by transesterification reaction using homogeneous catalyst as sodium hydroxide (NaOH) or potassium hydroxide (KOH). However, these materials present issues like the soap formation and need for additional steps in the process to neutralize and purify the product in order to be under specification of Brazilian National Agency of Petroleum, Natural Gas and Biofuels. This fact has stimulated research to find new materials to replace the current route of biofuels production and one promising material is the heterogeneous catalyst. With this motivation, this work presents a new alternative to the synthesis of a solid recently classified as heterogeneous catalyst, the MCM-41, aiming the minimization of costs for its production. The material was synthesized using sodium trisilicate as silica source and it was later tested, without modification, in transesterification reaction between an ester and an alcohol. The results showed catalyst activity and the conversion was around 40%, but its reuse reveals intense loss of activity because of CTA+ cations removal. However, new techniques are under development to guarantee more stability to the catalyst. / A demanda por energia no mundo atual e os problemas que os combustíveis fosseis oca-sionam, tem impulsionado a procura por fontes alternativas de energia que associadas as fontes já utilizadas possam suprir toda a necessidade energetica. Neste contexto, sabendo que esse produto e essencial para o desenvolvimento tecnológico, social e ambiental de um país, os combustíveis líquidos baseados em biomassa sao fortes candidatos a garantir a se¬gurança energetica mundial, o etanol e o biodiesel são exemplos de produtos com potencial para esse fim. O biodiesel e comumente obtido atraves da reação de transesterificação na presença de catalisadores homogêneos como o hidróxido de sodio (NaOH) ou de potassio (KOH). Entretanto o uso desses materiais apresenta problemas como a possibilidade de formação de sabões e a necessidade de etapas adicionais ao processo para neutralizar e purificar o biodiesel deixando-o dentro das especificações estabelecidas pela Agencia Naci¬onal do Petroleo, Gás Natural e Biocombustóveis. Este fato tem estimulado pesquisas no sentido de sugerir materiais que possam substituir o caminho utilizado atualmente, um desses materiais seria o catalisador heterogeneo. Diante deste cenario, o presente trabalho propoe uma rota alternativa para a síntese de um solido recentemente classificado com catalisador heterogeneo, a CTA-MCM-41, visando minimizar os custos de obtenção deste catalisador. O sílido foi sintetizado utilizando como fonte de sílica o trissilicato de sodio e posteriormente testado sem nenhuma modificacao numa reação modelo entre um ester e um alcool e na reação de transesterificação de oleos vegetais. Os resultados mostram que o catalisador apresentou atividade nas duas reacães, atingindo conversões em torno 40% porém o reuso do catalisador revela uma intensa perda de atividade devido a remoçcaão dos cations CTA+. Entretanto novas tecnicas estao sendo desenvolvidas para garantir uma maior estabilidade ao catalisador.

Submitted by Rosana Amâncio (rosana.amancio@ufcg.edu.br) on 2018-07-11T16:43:30Z No. of bitstreams: 1 Tacia Thaisa de Lima Silva UFCG PPGCNBio.pdf: 3218128 bytes, checksum: 07c42fd45987f76fb62c91ebfa9dad6e (MD5) / Made available in DSpace on 2018-07-11T16:43:30Z (GMT). No. of bitstreams: 1 Tacia Thaisa de Lima Silva UFCG PPGCNBio.pdf: 3218128 bytes, checksum: 07c42fd45987f76fb62c91ebfa9dad6e (MD5) Previous issue date: 2016-07-22 / Capes / A pirólise de biomassa utiliza rejeitos orgânicos por conversão termoquímica produzindo compostos oxigenados de menor peso molecular, visando principalmente à produção de energia. O teor dos componentes lignocelulósicos (celulose, hemicelulose, lignina) além da umidade e cinzas é o que confere os produtos finais do processo, sendo eles o bio-óleo, carvão e gás. O presente trabalho teve como objetivo avaliar a influência do catalisador Ni/MCM-41 no processo de pirólise rápida do bagaço de sisal (Agave sisalana). A biomassa foi caracterizada segundo sua composição lignocelulósica, análise termogravimétrica, miscroscopia eletrônica de varredura, espectroscopia de infravermelho e por fim foi realizado o estudo cinético para avaliar a energia de ativação aparente da decomposição térmica dos componentes lignocelulósicos do bagaço do sisal. O catalisador foi sintetizado e caracterizado por difração de raios X, espectroscopia na região do infravermelho e análise termogravimétrica e por fim foram realizadas as pirólises num micro pirolisador da CDS 5200 HP-R da CDS Analytical, em uma faixa de temperatura 500°C. Foram analisados 31 picos no cromatograma produzido pelo processo pirolítico do bagaço de sisal. Pela análise das influências dos resultados da pirólise rápida, com a catalítica contendo apenas o MCM-41 e outra com Ni/MCM-41. Os resultados da caracterização do bagaço de sisal mostraram que esta biomassa tem um alto teor de celulose, O uso do catalisador de Ni/MCM-41 não favoreceu significativamente a redução dos compostos oxigenados. Além disso, o bagaço de sisal como rejeito orgânico pode ser aproveitado por meio de processos termoquímicos gerando novos produtos e reduzindo os impactos ambientais causados pelo seu acúmulo. / The pyrolysis of biomass use organic waste thermochemical conversion of oxygenates to produce lower molecular weight, aiming at the production of energy. The content of the lignocellulosic components (cellulose, hemicellulose, lignin) in addition to the moisture and ash is what gives the end products of the process, namely bio-oil, coal and gas. This study aimed to evaluate the influence of Ni / MCM-41 catalyst in the fast pyrolysis process sisal bagasse (Agave sisalana). Biomass was characterized according to their lignocellulosic composition, thermal analysis, scanning electron miscroscopia, infrared spectroscopy and finally was performed kinetic study to evaluate the apparent activation energy of thermal decomposition of lignocellulosic components sisal bagasse. The catalyst was synthesized and characterized by X-ray diffraction, spectroscopy in the infrared region and thermogravimetric analysis were performed and finally the pyrolysis in a micro pyrolyser CDS HP 5200-R CDS Analytical, in a temperature range of 500 ° C. They analyzed 31 peaks in the chromatogram produced by the pyrolytic process sisal bagasse. The analysis of the influences of the results of fast pyrolysis with the catalyst only containing MCM-41 and another Ni / MCM-41. The results of the characterization of sisal pulp showed that biomass has a high cellulose content, the use of the catalyst Ni / MCM-41 did not significantly favors the reduction of oxygenated compounds. Furthermore, sisal pulp as organic waste can be passed through thermochemical processes generate new products, and reducing the environmental impact caused by its accumulation.