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Previous issue date: 2016-04-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / As Redes Metalorg?nicas (Metal Organic Frameworks ? MOF?s) s?o materiais h?bridos, geralmente cristalinos, constitu?dos por ?tomos ou clusters met?licos, coordenados ? ligantes org?nicos polifuncionais, geralmente, observando-se a presen?a de poros/canais de dimens?es nanom?tricas. Suas estruturas s?o de baixa densidade em fun??o da porosidade, e apresentam alta ?rea superficial, bem como um grande volume de poro, o que ?s levam a lugar de destaque do ponto vista cient?fico-tecnol?gico, sendo aplic?veis na cat?lise, adsor??o, separa??o, estocagem de gases, entrega de f?rmacos, etc. Cu-MOF?s foram sintetizadas via m?todo eletroqu?mico a partir de dois ligantes distintos, 1,3-H2BDC e 1,4-H2BDC. Os par?metros sint?ticos empregados, tais como, meio reacional (raz?o H2O/DMF), diferen?a de potencial e corrente el?trica, foram avaliados e sua influ?ncia sobre a estrutura cristalina determinada. Os materiais foram obtidos em uma hora, sugerindo que esta ? uma rota cineticamente vantajosa para a obten??o de redes metalorg?nicas de cobre. O produto da s?ntese da rede Cu(1,4-BDC) ? composto de duas estruturas cristalinas lamelares (em camadas) e microporosas. A cristaliza??o destas diferentes estruturas est? diretamente relacionada ao valor de corrente el?trica empregada. As duas estruturas se diferenciam basicamente pelo deslocamento entre camadas consecutivas, 60? e 120?, respectivamente. O deslocamento das camadas resultou em estruturas com diferentes volumes de canais, sendo a estrutura com deslocamento de 60? a que apresenta canais com maior volume, mais indicado para a adsor??o. Essa estrutura, denominada Cu(1,4-BDC) 2, foi aplicada na adsor??o de azul de metileno, sendo avaliadas as influ?ncias de pH, temperatura e concentra??o. Observou-se que valores de pH entre 5,0 e 6,0 promovem uma melhor adsor??o. Diferentes condi??es foram testadas, tais como concentra??es entre 25 e 250 mg/L e temperaturas entre 293,15 e 313,15 K. Adicionalmente, tamb?m foram avaliados fatores cin?ticos, termodin?micos e de equil?brio para a adsor??o. Constatou-se que o modelo cin?tico de pseudo-segunda ordem ? o mais compat?vel com o processo. Para os fatores termodin?micos, verificou-se que o processo ? exot?rmico, espont?neo e com maior efici?ncia ? uma temperatura de 293,15 K. Foram testados dois modelos de isotermas, o de Langmuir e o de Freundlich, sendo o modelo de Langmuir o que apresentou maior compatibilidade, prognosticando uma capacidade adsortiva m?xima te?rica de 76,63 ?mol/g, sendo que para as condi??es otimizadas (14 horas), a capacidade experimentalmente obtida foi de 75,91 ?mol/g, (99,06% do valor te?rico). Foram realizados ensaios de reuso do material, onde foi constatada uma efici?ncia superior ? 60% para at? quatro ciclos de adsor??o/dessor??o. / The metal organic frameworks (MOF's) are hybrid materials, generally crystalline, consisting of metallic atoms or metallic clusters, coordinated to polyfunctional organic ligands, generally observing the presence of pores/channels in nanometer dimensions. Their structures shows low density due to the porosity, have high surface area and a high pore volume, which lead to the prominent place of scientific-technological area, applicable in various fields as catalysis, adsorption, separation, gases storage, drug delivery, etc. Cu-MOFs were synthesized by the electrochemical method, using the 1,3-H2BDC and 1,4-H2BDC linkers in different H2O/DMF solvent proportions. The influence of electrochemical variables of process, such as voltage and electric current, and their influence on the final structure of the material was examined. The materials were obtained within one hour, showing that this method is kinetically advantageous for the preparation of the copper network. The product of the synthesis of Cu (1,4-BDC) network is composed of two lamellar (layered) and microporous crystalline structures. The formation of different structures are directly relate to the electrical current condition imposed on the synthesis. The two structures differ mainly by the displacement between subsequent layers, 60? and 120?, respectively. The displacement of the layers resulted in structures with different channels volumes, where the structure with 60? of displacement presents channels with greater volume, what may be applicable in adsorption. This structure, called Cu(1,4-BDC)2, was applied for the blue methylene adsorption, where the study of the influence of pH, temperature and concentration was performed. It revealed that for pH values between 5.0 and 6.0 there is an increased amount of the adsorbed dye. Different conditions were tested, such as concentrations between 25 and 250 mg/L and temperatures between 293.15 and 313.15 K. Varying concentrations of the dye solution, the kinetic factors, thermodynamic and equilibrium for adsorption, were evaluated. It was find that the kinetic model of pseudo-second order is the most compatible with the process. For the thermodynamic factors, it was find that the process is exothermic, spontaneous and has the highest efficiency at 293.15 K. Two models were tested for adsorption isotherm, the Langmuir and Freundlich, and the most compatible with the data was the Langmuir model, theoretically predicting a maximum adsorption capacity of 76.63 ?mol/g, and for the optimized conditions (14 hours), the capacity obtained experimentally was 75.91 ?mol/g, (99.06% theoretical). Reuse tests of the material were carried out and it was found that the material can reach the reuse efficiencies higher than 60% for up to four adsorption/desorption recycles.
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.ufrn.br:123456789/22559 |
| Date | 15 April 2016 |
| Creators | Monteiro, Arthur Felipe de Farias |
| Contributors | 00735018405, http://lattes.cnpq.br/8938691250105531, Oliveira, Jo?o Bosco Lucena de, 19127537404, http://lattes.cnpq.br/1360004695124740, Kulesza, Joanna Elzbieta, 70134641477, http://lattes.cnpq.br/1568423340359601, Barros, Braulio Silva |
| Publisher | PROGRAMA DE P?S-GRADUA??O EM QU?MICA, UFRN, Brasil |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Source | reponame:Repositório Institucional da UFRN, instname:Universidade Federal do Rio Grande do Norte, instacron:UFRN |
| Rights | info:eu-repo/semantics/openAccess |
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