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.

Disponibiliza??o do conte?do parcial, conforme Termo de Autoriza??o no trabalho. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2016-12-21T19:05:57Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-01-31T14:19:01Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) / Made available in DSpace on 2017-01-31T14:19:01Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wbiratan_cesar_macedo_oliveira_parcial.pdf: 128173 bytes, checksum: 9c9067430cf3b7ef9b7952182484b258 (MD5) Previous issue date: 2016 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Funda??o de Amparo ? Pesquisa do Estado de Minas Gerais (FAPEMIG) / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Neste trabalho foi estudado o comportamento de extra??o do lant?nio em sistemas aquosos bif?sicos (SAB) e foi desenvolvido um novo m?todo hidrometal?rgico ambientalmente seguro para a extra??o seletiva de La a partir de lixiviado de baterias NiMH. O comportamento de extra??o do La foi avaliado verificando a influ?ncia dos seguintes par?metros: presen?a e concentra??o de diversos agentes extratantes (Alaranjado de xilenol, 1-(2-piridilazo)-2-naftol, Ditizona, 8-hidroxiquinolina, e 1,10-fenantrolina); pH (3,00, 6,00 e 9,00); eletr?lito (Li2SO4, Na2SO4, MgSO4, Na2C4H4O6 e Na3C6H5O7 ) e pol?mero (L64 e PEO1500) formadores do sistema. A efici?ncia de recupera??o foi avaliada atrav?s da an?lise da porcentagem de extra??o (% E) e as melhores condi??es de extra??o do analito foram obtidas no SAB formado por PEO1500 + Li2SO4 + H2O, pH = 6,00; empregando o extratante 1,10-fenantrolina, atingindo um valor m?ximo de %E = 74,1 %. Na sequencia o m?todo foi aplicado a um lixiviado de bateria NiMH. Os terras raras foram precipitados mediante ajuste de pH (2,50) e posteriormente solubilizado em solu??o de H2SO4 0,1 M. Ap?s 3 etapas sucessivas de extra??o foram obtidos altos valores de fator de separa??o (S) entre o analito e os concomitantes met?licos (SLa,Co = 6.3 x 103, SLa,Ni= 2,55 x 104, SLa,Fe= 1,15 x 103 and SLa,Ce= 30,9). Al?m disso, foi realizado um ensaio de stripping no qual 88,5% de La, em uma ?nica etapa, foi redisponibilizado sob a forma i?nica na FI para uma poss?vel etapa posterior de eletrodeposi??o. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / In this work was investigated the extraction behavior of lanthanum in the aqueous two-phase system (ATPS) and new environmentally safe hydrometallurgical method was developed for the selective extraction of La from NiMH battery leachate. The extraction behavior of La was evaluated verifying the influence of the following parameters on the metals extraction: presence and concentration of the several extractants 1-(2-piridil-azo)-2-naphtol, dithizone, 8-hydroxyquinoline, 1-10 phenanthroline and xylenol oragne; pH (3.00, 6.00 and 9.0); ATPS-forming electrolyte ((Li2SO4, Na2SO4, MgSO4, Na2C4H4O6 e Na3C6H5O7); ATPS-forming polymer (L64 or PEO1500). The recovery efficiency was evaluated through analyzing the extraction percentage (%E) and the best conditions for analyte extraction were achieved for the PEO1500 + Li2SO4 ATPS, pH = 6.00, using 1-10 phenanthroline as extractant agente (%E = 74,1 %). In the following section, the method was applied to a real NiMH battery leachate. The rare earths were precipitated by pH adjustment (2.50), which was solubilized in 0,1 M H2SO4 solution. After 3 steps of successive extractions it was possible to obtain high separation factor (S) values between the analyte and mettalic concomitant (SLa,Co = 6.3 x 103, SLa,Ni = 2,55 x 104, SLa,Fe = 1,15 x 103 and SLa,Ce = 30,9). Moreover, a stripping assay was carried out and after one single step, 88.5% of lanthanum was available to a possible electro winning step.

Data de aprova??o ausente. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-03-29T18:49:58Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wagner_barbosa_souza.pdf: 2617971 bytes, checksum: 3d7e6b01cafdb0a61d93af504071663c (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-04-24T16:36:52Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wagner_barbosa_souza.pdf: 2617971 bytes, checksum: 3d7e6b01cafdb0a61d93af504071663c (MD5) / Made available in DSpace on 2017-04-24T16:36:52Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wagner_barbosa_souza.pdf: 2617971 bytes, checksum: 3d7e6b01cafdb0a61d93af504071663c (MD5) Previous issue date: 2016 / Com o avan?o exponencial da ind?stria de eletr?nicos, o consumo destes produtos tamb?m est? crescendo largamente. Com isso, os descartes destes equipamentos tamb?m crescem na mesma propor??o. Por ano, no mundo, estima-se que mais de 25 milh?es de toneladas de lixo eletr?nico sejam descartadas. Neste trabalho foi desenvolvido um novo m?todo hidrometal?rgico ambientalmente seguro para a extra??o seletiva de cobre, n?quel e prata provenientes de res?duos de placas de circuito impresso (PCI), empregando Sistemas Aquosos Bif?sicos (SAB) como t?cnica de extra??o. O comportamento de extra??o dos ?ons met?licos Cu (II), Ni(II), Fe(III) e Ag(I)em SAB formado por copol?mero tribloco L64 + MgSO4 + H2O foi avaliado para a otimiza??o do m?todo, verificando a influ?ncia dos seguintes par?metros experimentais sobre a extra??o dos analitos: valores de pH do SAB (3,0; 6,0; 9,0 e 11,0); natureza e concentra??o dos agentes extratores 1-(2-piridil-azo)-2-naftol (PAN) para os estudo de extra??o do Cu(II), 1-nitroso-2-naftol (1N2N) e dimetilglioxima (DMG) para a extra??o do ?on Ni(II), tiocianato (SCN) e ditizona (Dz) para a extra??o da Ag(I). A efici?ncia de recupera??o seletiva dos metais foi avaliada por meio da an?lise da porcentagem de extra??o (%E) e do fator de separa??o (S) entre os ?ons de interesse. As melhores condi??es para extra??o seletiva foram: PAN [3,5 mmol.Kg-1] em pH = 6,0 em 6 etapas consecutivas para separa??o do Cu(II), DMG [5,00 mmol.Kg-1] em pH = 9,0 para o Ni(II) e SCN[5,20 mmol.Kg-1] em pH = 9,0 para a Ag(I) . Em todas as situa??es foram obtidos valores de fator de separa??o(S) entre o analito e os concomitantes met?licos maiores que 103. As condi??es ?timas obtidas foram aplicadas ao lixiviado de PCI para a extra??o de cobre, n?quel e prata de forma sequencial, obtendo-se altos valores de S entre o analito e os concomitantes met?licos (SCu,Ni= 1,46 x 103, SCu,Fe= 1,55 x 104, SCu,Ag= 1,59 x 104, SNi,Fe= 3,27 x 104, SNi,Ag= 3,47 x 104 eSAg,Fe= 4,80 x 103).Ap?s a extra??o de cada metal foi realizado um estudo de stripping em uma ?nica etapa, onde 89,5%, 92,5% e 82,5% de Cu(II), Ni(II) e Ag(I), respectivamente foram disponibilizados para a etapa de eletrodeposi??o. Portanto o m?todo utilizando SAB se mostrou eficiente e dentro dos princ?pios da qu?mica verde, pois utiliza componentes at?xicos, biodegrad?veis e recicl?veis e de r?pida separa??o de fases sem a forma??o de emuls?es est?veis. Sendo um m?todo alternativo para a extra??o liquido ? liquido tradicional. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, [2016]. / With the exponential advancement of electronic industry, the consumption of these products is also growing wide. With this, the drops of this equipment also grow at the same rate. A year in the world, it is estimated that more than 25 million tons of electronic waste are disposed.This work developed a new environmentally safe hydrometallurgical method for the selective extraction of copper, nickel and silver from waste printed circuit board (PCB) using Aqueous Two-Phase Systems (SAB) as extraction technique. The extraction behavior of metal ions Cu (II), Ni (II), Fe (III) and Ag (I) SAB formed by tri-block copolymer L64 + MgSO4 + H2O was evaluated for the optimization of the method by checking the influence of the following experimental parameters on the extraction of analytes: the SAB pH (3.0, 6.0, 9.0 and 11.0); nature and concentration of agents extractors 1- (2-pyridyl-azo) -2-naphthol (PAN) Cu for the extraction method (II), the 1-nitroso-2-naphthol (1N2N) and dimethylglyoxime (DMG) for ion extraction Ni (II), thiocyanate (SCN) and dithizone (Dz) for the extraction of Ag (I).The selective metal recovery efficiency was evaluated by the percentage extraction analysis (% E) and separation factor (S) between the ions of interest. The best conditions for selective extractions were NAP [3,5 mmol.Kg-1] at pH 6.0 in 6 consecutive stages for separation of Cu (II) DMG [5.00 mmol.Kg-1] pH = 9.0 for Ni (II) and SCN [5,20 mmol.Kg-1] at pH = 9.0 for Ag (I). In all cases they were obtained separation factor values (S) between the analyte and the larger metal Concomitant 103. The obtained optimum conditions were applied to the PCI leached copper extraction, nickel and silver sequentially, yielding if high S values between the analyte and the metal concomitant (SCU, Ni = 1.46 x 103, SCU, Fe = 1.55 x 104, SCU, Ag = 1.59 x 104, SNI, Fe = 3.27 x 104, SNI, Ag = 3.47 x 104 and SAg, Fe = 4.80 x 103).After extraction of each metal it was made a study stripping in one step, where 89.5%, 92.5% and 82.5% Cu (II), Ni (II) and Ag (I), respectively, were available for the electroplating step. Therefore, the method using BSA was efficient and within the principles of green chemistry, because it uses non-toxic, biodegradable and recyclable and fast phase separation without the formation of stable emulsions components. As an alternative method for liquid - liquid extraction traditional.