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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.
1

Estudo da parti??o de Carbon Dots em sistemas aquosos bif?sicos: potencialidades para cat?lise de transfer?ncia de fase

Huaman?, Edgard Ronny Delgado 19 May 2017 (has links)
Data de aprova??o retirada da vers?o impressa do trabalho. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-01-04T19:50:32Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) edgard_ronny_delgado_huamani.pdf: 5898825 bytes, checksum: 78eee370de5fed297b3181e82d98f63d (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-01-17T18:40:25Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) edgard_ronny_delgado_huamani.pdf: 5898825 bytes, checksum: 78eee370de5fed297b3181e82d98f63d (MD5) / Made available in DSpace on 2018-01-17T18:40:25Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) edgard_ronny_delgado_huamani.pdf: 5898825 bytes, checksum: 78eee370de5fed297b3181e82d98f63d (MD5) Previous issue date: 2017 / Neste trabalho, Carbon Dots (CD) oxidados foram preparados a partir de rea??es de desidrata??o/oxida??o ?cida da celulose, e posteriormente desoxigenados em meio alcalino e rea??o com sulfato de hidrazina. As caracteriza??es dos CD foram feitas com Microscopia eletr?nica de Transmiss?o, FTIR, titula??o potenciom?trica, Resson?ncia Magn?tica Nuclear de 13C e espectroscopia UV-Vis e fluoresc?ncia. Os resultados obtidos com estas caracteriza??es mostraram que a amostra oxidada apresenta um tamanho m?dio aproximadamente de 2,7 nm com uma significativa quantidade de grupos funcionais oxigenados ?cidos, dos quais 63% s?o ?cidos carbox?licos. Ap?s as rea??es de modifica??o superficial foi verificado que em meio alcalino ocorre somente uma elimina??o de nanoestruturas mais oxidadas, enquanto que na rea??o com hidrazina ocorre a redu??o de alguns grupos carbox?licos e ep?xidos com forma??o de grupos funcionais hidrazonas. Como consequ?ncia da modifica??o superficial, as propriedades ?pticas dos CD s?o alteradas significativamente. Com a redu??o, o band gap diminui e a energia da emiss?o aumenta, deslocando-se para a regi?o azul do espectro eletromagn?tico. Uma vez caracterizados, a parti??o de todos os CD preparados foi investigada em diferentes Sistemas Aquosos Bif?sicos (SAB), nos quais foram avaliados os efeitos dos c?tions e ?nions dos sais, dos pol?meros e do pH inicial do sistema no coeficiente de parti??o (K). Em adi??o foi avaliado o efeito da modifica??o superficial das nanopart?culas. A rela??o do K com comprimento da linha de amarra??o (CLA), o par?metro termodin?mico dos SAB foi estudado para todos os sistemas. Os resultados obtidos mostraram que a melhor separa??o ocorreu com o sistema PEO1500+sulfato de l?tio+?gua em pH=3 e usando os Carbon Dots reduzidos com hidrazina. O valor do K para este sistema foi de 64,4. Por outro lado, o menor valor de K foi 0,79, foi obtido para o sistema PEG1500+tartarato de s?dio+?gua em pH=6 e usando Carbon Dots oxidados. As an?lises detalhadas das fases superior e inferior de alguns destes sistemas com espectroscopia de fluoresc?ncia mostraram que os SAB s?o capazes, al?m de particionar, separar as nanopart?culas com diferentes propriedades ?pticas, as quais est?o diretamente associadas ?s propriedades superficiais e tamanho de part?culas. Por fim, n?s avaliamos a atividade catal?tica foto-Fentom dos CD na degrada??o do corante ani?nico ?ndigo de carmim e os resultados mostraram que os CD apresentam atividade fotocatal?tica neste sistema. Devido ? alta parti??o verificada para o sistema PEG1500+ sulfato de l?tio+?gua, este foi usado para avaliar a potencialidade de seu uso em cat?lise de transfer?ncia de fase usando CD como fotocatalisador e o corante ?ndigo de carmim como mol?cula modelo. Apesar da complexidade e da dificuldade de caracteriza??o dos produtos da foto-oxida??o no SAB, os resultados obtidos indicam que o sistema testado pode ser usado em rea??es de transfer?ncia de fase fotocatalisadas. Como conclus?o final, acredita-se que os resultados apresentados, em especial, a parti??o/sele??o das nanopart?culas com distintas propriedades ?pticas s?o de extrema import?ncia para o desenvolvimento de novas e eficazes aplica??es dos CD. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / In this work, oxidized Carbon Dots (CD) were prepared by a dehydration/oxidation reaction of cellulose and subsequently deoxygenated in alkaline medium and reaction with hydrazine sulfate. The CD characterizations were made with Transmission Electron Microscopy, FTIR, potentiometric titration. 13C Nuclear Magnetic Resonance, UV-Vis and fluorescence spectroscopy. The results obtained with these characterizations showed that the oxidized sample has an average size of 2.7 nm with a significant amount of acid oxygenated functional groups, of which 63% are carboxylic acids. After the superficial modification reactions, it was verified that in alkaline conditions only one elimination of more oxidized nanostructures occurs, whereas in the reaction with hydrazine the reduction of some carboxylic groups and epoxides with formation of hydrazones functional groups. As a consequence of the surface modification, the optical properties of the CD are significantly changed. The band gap decreases and the emission energy increases, shifting to the blue region of the electromagnetic spectrum. Once characterized, the partitioning of all CD prepared was investigated in differente Aqueous two-phase systems (ATPS), in which the effects of the cations and anions of salts, of the polymers and the initial pH of the system in the partition coefficient (K) were evaluated. In addition, the surface modification effect of the nanoparticles was evaluated. The relationship of K with Tie Line Length (TLL), the thermodynamic parameter of the ATPS was studied for all systems. The results showed that the best separation occurred with the system PEO1500 + lithium sulfate + water at pH = 3 and using the reduced carbon dots with hydrazine. The K value for this system was 64,4. On the other hand, the lowest K value was 0,79, it was obtained for the system PEG1500 + sodium tartrate + water at pH = 6 and using oxidized carbon dots. The detailed analysis of the upper and lower phases of some of these systems with fluorescence spectroscopy showed that the ATPS are capable, in addition to partition, to separate the nanoparticles with different optical properties, which are associated directly to the surface properties and particle size. Finally, we evaluated the photo-Fentom catalytic activity of the CD in the degradation of the anionic anion dye indigo carmine and the results showed that the CD present photocatalytic activity in this system. Due to the high partition found for the PEG1500 + lithium + water sulfate system, it was used to evaluate the potentiality of its use in phase transfer catalysis using CD as a photocatalyst and the indigo carmine dye as a model molecule. Despite the complexity and difficulty of characterizing the photo-oxidation products in ATPS the results indicate that the system tested can be used in photocatalysed phase transfer reactions. As a final conclusion, we believe that the results presented, in particular, the partitioning / selection of nanoparticles with different optical properties are of extreme importance for the new and effective applications of CD.

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