Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-Graduação em Química, Florianópolis, 2013 / Made available in DSpace on 2013-12-06T00:03:56Z (GMT). No. of bitstreams: 0
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317587.pdf: 6978464 bytes, checksum: cb7abe871f7b81e054b2bf18b06d416c (MD5) / A proposta deste trabalho está enfocada no preparo e caracterização de catalisadores na forma de misturas de Al2O3-MgO com quantidades crescentes de MgO. Inicialmente, estes catalisadores foram empregados na degradação do paraoxon metílico (DMPNPP). Os resultados serviram para identificar a eficiência mais pronunciada do catalisador com a fase espinélio (MgAl2O4) incipiente, o qual permitiu um aumento na velocidade da reação de aproximadamente 7×105 vezes em relação à reação em propan-1-ol sem a presença do catalisador. A etapa seguinte envolveu estudos de reações de propanólise com uma série de triésteres e diésteres de fosfato e o catalisador MgAl2O4. O foco foi avaliar os efeitos da natureza química dos substratos aliados às propriedades da superfície. Os experimentos indicaram que existe uma relação direta entre as propriedades texturais e estruturais dos catalisadores com as especificidades das interações catalisador-substrato. Triésteres e diésteres de fosfato com grupos de saída piridin-2-ol apresentaram um efeito catalítico diferenciado. Isso sugere que os centros bimetálicos do catalisador espinélio devem favorecer a interação com os grupos piridin-2-ol. Por fim, os estudos mostraram que o catalisador espinélio atua eficientemente na degradação de triésteres de fosfato, gerando metabólitos menos tóxicos, sendo esse um dos objetivos fundamentais do presente trabalho. <br> / Abstract: The development of catalysts that are active in the cleavage between phosphorous and oxygen bond has always been strongly appealing due to the properties related with the chemical stability of such bonds. The proposal of this Thesis is focused on the preparation and characterization of solid catalysts in the form of Al2O3-MgO mixtures with increasing amounts of MgO. The reactions were performed under heterogeneous catalysis conditions with the use of 1- propanol as solvent and the mixed oxides. Firstly, these catalysts were employed in the degradation of methyl paraoxon (DMPNPhP). The results enabled identification of the spinel incipient phase (MgAl2O4) as the best catalyst, allowing a constant rate increase of about 7×105 times when compared to the reaction with 1-propanol without catalyst. DMPNPhP was used as standard substrate in further studies of the effect of the thermal treatment conditions of the catalyst; the effect of water in the reaction system and substrate concentration optimization studies for maximum catalytic efficiency. The next step involved studies of the propanolysis reaction with a series of phosphate triesters and diesters using MgAl2O4 as the catalyst. At this point, the focus was to evaluate the effects of the chemical nature of the substrates allied with the surface effects, such as the limitations in the catalytic effect, for exemple steric hindrance factors important for the bulky molecules, such as the triaryl triesters. The experimental results have indicated that there is a direct relationship between the structural and textural properties and the specificities of the catalyst-substrate interactions. Triester and diester phosphates with 2-hydroxypyridine derivatives leaving group have shown different catalytic effects compared to substrates which have leaving groups with very close pKa values. This suggests that the spinel catalyst bimetallic centers should favor the interaction with such groups and this may additionally contribute in the transition state stabilization of these reactions. Finally, studies have shown that the spinel catalyst acts efficiently in the degradation of phosphate triesters, generating less toxic products, which is one of the most important goals of this Thesis.
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.ufsc.br:123456789/107415 |
| Date | January 2013 |
| Creators | Zimmermann, Lizandra Maria |
| Contributors | Universidade Federal de Santa Catarina, Nome Aguilera, Faruk José |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis |
| Format | 181 p.| il., grafs., tabs. |
| Source | reponame:Repositório Institucional da UFSC, instname:Universidade Federal de Santa Catarina, instacron:UFSC |
| Rights | info:eu-repo/semantics/openAccess |
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