The research presented in this thesis aims to assess the capacity of metal organic frameworks with open metal sites for the separation of olefin mixtures. Chapter 1 provides a background to the field, including industrial separation techniques, metal organic frameworks and their applications and the current state-of-the- art for olefin separation. Chapter 3 describes the experimental techniques used in this research. Ethylene and propylene adsorption and desorption isotherms on Ni-CPO-27 and HKUST-1 at a range of temperatures are presented and compared in Chapter 4, and used to calculate isosteric heats of adsorption at varying coverages using the virial method. These pure component isotherms are used in Chapter 5 to predict selectivities for the separation of binary mixtures using ideal adsorbed solution theory. Temperature programmed desorption is used in Chapter 5 to calculate the enthalpy of desorption using Redhead's method and the heating rate variation method, and the two results are compared. The results presented in Chapters 4 and 5 conclude that propylene/ethylene separation is possible using adsorption onto metal organic frameworks with open metal sites. A new in situ environmental gas cell for single crystal X-ray diffraction is developed in Chapter 6, and the challenges encountered during this development process are discussed. The dehydration of one framework, Co-CPO-27, is studied in detail using the environmental gas cell. A dehydrated structure of HKUST-1, obtained using the gas cell, is presented for the first time. Crystal structures for the complete dehydration-adsorption-delivery cycle for biologically active NO on Co-CPO-27 are presented in Chapter 7, showing the utility of the in situ gas cell for prolonged experiments in multiple different gaseous environments. The crystal structure of NO-loaded Co-CPO-27 improves upon the models suggested in the literature, and the treatment of the dual occupancy of the open metal sites by water and NO is discussed in depth. A crystal structure of CO-loaded Co-CPO-27 is obtained for the first time, and crystal structures of Co-CPO-27 in ethylene and propylene environments are presented.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Solid catalyst supports of SiOx-RGO (Reduced Graphene Oxide) and UiO-67 (Universitet i Oslo) have been successfully synthesized and were loaded with palladium nanoparticles to test for a series of heterogeneous reactions. The SiOx/RGO catalysts were synthesized through laser ablation of silicon and graphite oxide micron powder and UiO-67 metal-organic framework (MOF) was synthesized through mixing of precursors with DMF/HCl solution and washing the resultant powder from impurities. The SiOx/RGO supports were later impregnated with palladium precursors which were then subject to Microwave Irradiation (MWI). The UiO-67 framework was impregnated with palladium precursors and was irradiated with pulsed Nd:YAG 532 nm laser and was purified through washing and centrifugation. The resulting catalyst supports were characterized with UV-Vis, FTIR, Raman, XRD and XPS techniques and the UiO-67 framework was subject to Brunauer-Emmet-Teller (BET) surface area measurements before and after the catalytic reactions. The catalytic activity of palladium nanoparticles supported on SiOx/RGO and UiO-67 framework was tested in carbon cross-coupling reactions of Suzuki-Miyaura, Sonogashira reactions and oxidation of benzyl alcohol respectively. The catalysts have demonstrated excellent performance and have yielded a promising future for the catalytic supports in the previously stated reactions.

Nanoparticles are involved in a broad range of applications, including heterogeneous catalysis. Nanoparticles tend to quickly lose their well-defined shapes and facets due to aggregation under duress such as heat. A series of highly studied materials are explored as support materials for nanoparticle supports. These supports include metal-organic frameworks (MOF), graphene oxide (GO), and a MOF-PRGO (partially reduced graphene oxide) hybrid. The inclusion of a support with the palladium increased lifespan of the catalyst by separation of nanoparticles. The choice of support material not only allowed for supporting of palladium nanoparticles, but allowed for rational catalyst synthesis in order to design catalysts with improved catalytic activity. CO oxidation, vanillin hydrogenation, and Suzuki cross coupling were studied. For the CO oxidation reaction, a cerium-based MOF, Ce-MOF, is shown to increase activity of palladium nanoparticles by capturing reactant gases and acting as an oxygen reservoir that cycles between (III) and (IV) states while transferring oxygen to palladium nanoparticles at the Pd/Ce-MOF interface. A hybrid Ce-MOF-PRGO was synthesized to increase the surface area and acidity of Ce-MOF materials and was shown to be active for vanillin hydrogenation. Smaller rod-like Ce-MOF crystals were observed, indicating intercalation of crystals on GO. Zirconium-based MOF UiO-66-NH2 was acidified via incorporation of tungstophosphoric acid (HPW), which increased the selectivity of products by adjusting the mechanistic pathway. GO was partially functionalized with aromatic amines to improve the coupling of bromobenzene and phenylboronic acid. Small amounts of aromatic amines increased the Pd(0) content and decreased nanoparticle size.

Cette thèse s'inscrit dans un projet Européen TOPCOMBI de 22 partenaires. Plus spécifiquement, ce travail estle résultat d'une collaboration entre ENI (Italie), ITQ (Espagne), Repsol (Espagne) et IRCELYON (France).Ce travail est composé de 2 thématiques différentes dont les améliorations peuvent s'obtenir en trouvant denouveaux matériaux adaptés aux besoins.Les demandes énergétiques mondiales sont et seront en constante hausse ces prochaines années. Dans l'optiquede pallier à ce besoin, de nouvelles ressources doivent être trouvées et d'autres optimisées. Les énergies fossiles fontparties des ressources les plus utilisées dans le monde. Parmi c'est 3, le gaz naturel semble être le plus prometteur dupoint de vu du rendement énergétiques ou de l'impact écologique. Cependant, de nombreux champs de gaz ne peuventpas être traités car trop petit ou trop contaminés pour être économiquement viable. L'un des moyens pour les rendreattractifs est d'abaisser le coût de purification en utilisant de nouvelles techniques de séparation comme le système PSA.Cependant, il n'existe pas à l'heure actuelle d'adsorbant efficace pour permettre une purification économique viable.De nos jours, les réactions d'alkylation représentent un intérêt économique très important. Les procédésindustriels sont généralement effectués par des réactions acides homogènes ou non. A la vue des nouvelles restrictionsécologiques, certains procédés de catalyse homogène doivent être remplacés par des réactions catalytiques hétérogènespossédant les mêmes rendements. Pour ce faire, de nouveaux matériaux à caractères acide ont été utilisés : les zéolithes.En revanche la faible taille de pores de ces composés empêche les réactions d'alkylation sélective de molécules tropgrosse comme les composés poly-aromatiques.Depuis une vingtaine d'année, de nouveaux composés cristallins microporeux ont vu le jour. Les MOFs, MetalOrganic Frameworks. Ces composés ont la particularité d'être obtenus avec différents cations métalliques et ligandsorganiques. Ces combinaisons donnent une très grande diversité de ces composés au niveau des réactivités, du volumeporeux et de la taille des pores. Dans ce travail, nous avons essayé d'obtenir différents matériaux avec descaractéristiques précises afin de pouvoir les utiliser dans des procédés de purification du méthane ou dans la catalyseacide. Pour ce faire, nous avons mis en place un protocole de synthèses de MOFs à haut débit ainsi que d'un protocolede caractérisation adapté à nos besoins. Les différents composés remplissant les différents critères étant testés dans lesréactions adéquates.

The primary goal of this research concerns the synthesis of organic ligands in an effort to create metal-organic porous materials for the storage of gas molecules for alternative energy applications as well as other applications such as catalysis, molecular sensing, selective gas adsorption and separation. Initially, the focus of this work was on the synthesis of metal-organic polyhedra, yet the research has to date not progressed past the synthesis of ligands and the theoretical polyhedron that may form. Further efforts to obtain polyhedra from these ligands need to be explored. Concurrently, the search for a metal-organic framework that hopefully breaks the record for methane adsorption at low pressure and standard temperature was undertaken. A framework, PCN-80, was synthesized based off a newly synthesized extended bianthracene derivative, yet was unstable to the atmosphere. Hydrogen and methane adsorption capacities have been evaluated by molecular simulations; these adsorption isotherms indicated a gravimetric hydrogen uptake of 9.59 weight percent and a volumetric uptake of methane of 78.47 g/L. Following the synthesis of PCN-80, a comparison study involving the effect of the stepwise growth of the number of aromatic rings in the ligand of a MOF was pursued; the number of aromatic rings in the ligand was varied from one to eight while still maintaining a linear, ditopic moiety. The synthesis of another bianthracene-based ligand was used to complete the series of ligands and PCN-81, a two-dimensional framework with no noticeable porosity as evident by the simulated hydrogen uptake of 0.68 weight percent, was synthesized. All of these MOFs were synthesized from zinc salts to reduce the number of variables. No clear relationship was established in terms of the number of aromatic rings present in the ligand and the hydrogen adsorption capacity. However, it was confirmed that the density and hydrogen uptake in weight percent are inversely proportional. Further work needs to be done to determine what advantages are offered by these novel frameworks containing extended bianthracene derivatives. For example, with the highly fluorescent nature of the ligands from which they are composed, both PCN-80 and PCN-81 should be studied for the potential use in the application of fluorescent materials.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Submitted by Pedro Barros (pedro.silvabarros@ufpe.br) on 2018-07-19T22:53:08Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) TESE Guilherme de Coimbra Santos.pdf: 6601677 bytes, checksum: 98f83ae5c0517751b976e593f82b4003 (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-07-20T21:39:55Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) TESE Guilherme de Coimbra Santos.pdf: 6601677 bytes, checksum: 98f83ae5c0517751b976e593f82b4003 (MD5) / Made available in DSpace on 2018-07-20T21:39:55Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) TESE Guilherme de Coimbra Santos.pdf: 6601677 bytes, checksum: 98f83ae5c0517751b976e593f82b4003 (MD5) Previous issue date: 2017-02-15 / CNPQ / Este trabalho apresenta a síntese da já conhecida MOF [Zn2(BDC)2(dpNDI)]n (BDC = 1,4-benzenodicarboxilato, dpNDI = N’N’-di(4-piridil)-1,4,5,8-naftalenodiimida), mas, agora dopada em diferentes percentagens (0,1%, 0,5%, 1%, 2% e 5%) com o íon európio (íon sonda), por via solvotermica. Após suas caracterizações, observam-se respostas espectroscópicas, frente à monoaromático, favoráveis na identificação de moléculas hóspedes. A síntese e caracterização de redes de coordenação cristalinas, bem como de compósitos a base de carvão ativado, a partir de íons lantanídeos (Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺, Er³⁺, Tm³⁺ e o Yb³⁺) com emprego do ligante flexível, succinato, utilizando-se a técnica hidrotermal para obtenção desses sistemas, foram realizadas, além de investigações de sistemas mixmetal nessa mesma matriz carbonácea. Novos compósitos porosos LnBDC@CA (CA = Carvão ativado, Ln = Pr³⁺; Nd³⁺; Sm³⁺; Eu³⁺; Gd³⁺; Er³⁺; Tm³⁺ e Yb³⁺ e BDC = 1,4benzenodicaboxilato) e CB[6]@CA (CB[6] = Cucurbit[6]uril) foram obtidos utilizando via hidrotermal. O LnBDC e o CB[6] estão localizados dentro dos poros do carvão, como foi observado em análise MEV-EDS, Raio X de pó e IV. A análise de porosimetria mostrou valores tipicamente entre o material CA e LnBDC, com tamanho de poro e área de superfície, respectivamente, 29,56 Å e 353,98 m²g⁻¹ para LnBDC@CA e 35,53 Å e 353,98 m²g⁻¹ para CB[6]@CA. Ambos os materiais mostraram boa capacidade de adsorção para o alaranjado de metila (MO) e o azul de metileno (MB) com seletividade em função do pH. Em meio ácido, ambos os materiais apresentam seletividade por MB e em pH alcalino para o MO, com desempenho perceptível para o CB[6]@CA. Adicionalmente, a luminescência do európio foi utilizada como sonda estrutural para investigar o ambiente de coordenação do íon Eu³⁺ no compósito EuBDC@CA após experimentos de adsorção. / This work presents the synthesis Already known of MOF [Zn2(BDC)2(dpNDI)] (BDC = 1,4-benzenedicarboxylate, dpNDI = N'N'-di (4-pyridyl) -1,4,5,8 - naphthalenediimide), but now doped in different percentages (0.1%, 0.5%, 1%, 2% and 5%) with the europium ion (probe ion) by Solvothermal synthesis. After their characterizations, spectroscopic responses are observed, in touch to monoaromatic, favorable in the identification of guest molecules. The synthesis and characterization of crystalline coordination networks, as well as activated carbon based composites, from lanthanide ions (Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺, Er³⁺, Tm³⁺ e o Yb³⁺) with the use of flexible ligands, succinate, using the hydrothermal technique to obtain these systems, were performed, in addition to investigations of mixmetal systems in this same carbonaceous matrix. New porous composites LnBDC@AC (AC= Activated carbon, Ln= Pr3+; Nd³⁺; Sm³⁺; Eu³⁺; Gd³⁺; Er³⁺; Tm³⁺ e Yb³⁺ and BDC= 1,4benzenedicaboxylate) and CB[6]@AC (CB[6]= Cucurbit[6]uril) were obtained using hydrothermal route. The LnBDC and CB[B] are located inside the pore of the carbon materials as was observed in SEM-EDS, XRPD and FT-IR analysis. Porosimetry analysis showed values typically between AC and LnBDC material, with pore size and surface area, respectively, 29,56 Å and 353.98 m2g-1 for LnBDC@AC and 35,53 Å and 353.98 m²g⁻¹ for CB[6]@AC. Both materials showed good absorptive capacity of metil orange (MO) and methylene blue (MB) with selectivity as a function of pH. In acid medium, both materials present selectivity by MB and alkaline pH for MO, with notable performance for CB[6]@AC. Additionally, europium luminescence was used as structural probe to investigate the coordination environment of Eu³⁺ ions in the EuBDC@AC composite after adsorption experiment.

Submitted by Fernanda Rodrigues de Lima (fernanda.rlima@ufpe.br) on 2018-08-20T20:30:39Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Débora Dolores Nascimento.pdf: 3594688 bytes, checksum: cdf7df39006953035bd1e74095fb8d37 (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-08-28T18:14:14Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Débora Dolores Nascimento.pdf: 3594688 bytes, checksum: cdf7df39006953035bd1e74095fb8d37 (MD5) / Made available in DSpace on 2018-08-28T18:14:15Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Débora Dolores Nascimento.pdf: 3594688 bytes, checksum: cdf7df39006953035bd1e74095fb8d37 (MD5) Previous issue date: 2017-05-26 / FACEPE / A carbamazepina (CBZ) é um derivado tricíclico do iminoestilbeno com atividade farmacológica antiepiléptica. Entre os problemas deste fármaco está a sua autoindução com a necessidade de administração de até 4 vezes por dia, além da alta incidência de reações adversas, o que provavelmente está relacionado com a sua baixa solubilidade, visto que pertence à classificação biofarmacêutica de classe II. Dessa maneira, a tecnologia farmacêutica auxilia na redução de alguns desses problemas como, por exemplo, através da adsorção da CBZ a um excipiente inovador para que auxilia com a sua solubilidade e altere sua liberação, modulando e prolongando a dissolução do fármaco. Assim, esse trabalho objetivou desenvolver e caracterizar sistemas formados entre a CBZ e uma estrutura organometálica chamada ZIF-8, com a finalidade de ser empregada nos estudos de pré-formulação de forma farmacêutica de liberação prolongada para o tratamento da epilepsia. Os sistemas foram obtidos após agitação do fármaco e da ZIF-8 em diferentes solventes (metanol, etanol, e etanol:H₂O 61%) e proporções molares para que fosse escolhido o melhor meio reacional, através da melhor eficiência de incorporação. As caracterizações dos sistemas desenvolvidos foram realizadas, em seguida, através várias técnicas analíticas para assegurar a obtenção do sistema, procedendo com os ensaios de dissolução in vitro sob condições sink para verificar o comportamento da liberação da CBZ quando adsorvido à ZIF-8 em diferentes pH’s e em meios com presença e ausência de tensoativo. Os perfis de dissolução foram analisados através da área sob a curva (AUC), eficiência de dissolução (ED%), modelo-independente através do fator de similaridade (ƒ2). Por meio do método desenvolvido o escolhido para obtenção foi o realizado com etanol:H₂O 61% como solvente, na proporção molar 1:1 após 3 horas de agitação sem intervalos. Através das análises térmicas pode-se comprovar a obtenção do sistema, indicando que o mesmo também pode influenciar positivamente na estabilidade térmica do fármaco. Os espectros de FT-IR, difratogramas de DR-X e demais análises realizadas, corroboraram com os resultados, confirmando a formação do sistema CBZ-ZIF-8. O estudo de dissolução possibilitou verificar modulação da liberação do fármaco independente do pH utilizado, obtendo resultados de uma liberação máxima de 36,2% em pH 1,2 com 1% de lauril sulfato de sódio (LSS), contra 17,7%, 12,5% e 11,2% quando submetido aos meios sem LSS, com pH 1,2, pH 4,5 e pH 7,6, respectivamente, durante o período de 24 horas. O presente trabalho através dos resultados de liberação prolongada independente de pH, trouxe informações relevantes para o desenvolvimento de formas farmacêuticas de liberação modificada que utilize CBZ como insumo farmacêutico ativo. / Carbamazepine (CBZ) is a tricyclic derivative of iminostilbene with pharmacological antiepileptic activity. Among the problems of this drug is its self-induction with the need to administer up to 4 times a day, in addition to the high incidence of adverse reactions, which is probably related to its low solubility, since it belongs to the class II biopharmaceutical classification. Thus, pharmaceutical technology assists in the reduction of some of these problems, for example by adsorbing CBZ to an innovative excipient, which assists with its solubility and alters its release, modulating and prolonging the dissolution of the drug. Thus, this work aimed to develop and characterize systems formed between CBZ and an organometallic structure called ZIF-8, with the purpose of being used in the preformulation studies of pharmaceutical form of extended release for the treatment of epilepsy. The systems were obtained after agitation of the drug and ZIF-8 in different solvents (methanol, ethanol, and ethanol: H₂O 61%) and molar ratios to the best reaction medium chosen, through the best incorporation efficiency. The characterization of the developed systems was then performed through several analytical techniques to ensure the system was obtained, proceeding with the in vitro dissolution tests under sink conditions to verify the CBZ release behavior when adsorbed to ZIF-8 at different pH's And in media with presence and absence of surfactant. The dissolution profiles were analyzed through the area under the curve (AUC), dissolution efficiency (ED%), model-independent through the similarity factor (ƒ2). Using the developed method the chosen one was obtained with ethanol: H₂O 61% as solvent, in the 1: 1 molar ratio after 3 hours of agitation without intervals. Through the thermal analysis, it is possible to prove the system, indicating that it can also positively influence the thermal stability of the drug. The FT-IR spectra, DR-X diffractograms and other analyzes, corroborated the results, confirming the formation of the CBZ-ZIF-8 system. The dissolution study allowed to verify the modulation of the drug release independent of the pH used, obtaining results of a maximum release of 36.2% in pH 1.2 with 1% of sodium lauryl sulfate (LSS), against 17.7% 12.5% and 11.2% when submitted to the media without LSS, with pH 1.2, pH 4.5 and pH 7.6, respectively, during the 24 hour period. The present work through the results of independent release of pH, has brought important information for the development of pharmaceutical forms of modified release that uses CBZ as active pharmaceutical ingredient.

Microporous metal organic frameworks (MOFs) are a novel class of materials formed through self-assembly of inorganic and organic structural building units (SBUs). They show great promise for many applications thanks to record-breaking internal surface areas, high porosity as well as a wide variety of possible chemical compositions. Molecular simulation has been instrumental in the study of MOFs to date, and this thesis work aims to validate and expand upon these efforts through two distinct computational MOF investigations. Current separation technologies used for CO2/N2 mixtures, found in the greenhouse gas-emitting flue gas generated by coal-burning power plants, could greatly benefit from the improved cost-effective separation MOF technology offers. MOFs have shown great potential for CO2 capture due to their low heat capacities and high, selective uptake of CO2. To ensure that simulation techniques effectively predict quantitative MOF gas uptakes and selectivities, it is important that the simulation parameters used, such as force fields, are adequate. We show that in all cases explored, the force field in current widespread use for N2 adsorption over-predicts uptake by at least 50% of the experimental uptake in MOFs. We propose a new N2 model, NIMF (Nitrogen in MoFs), that has been parameterized using experimental N2 uptake data in a diverse range of MOFs found in literature. The NIMF force field yields high accuracy N2 uptakes and will allow for accurate simulated uptakes and selectivities in existing and hypothetical MOF materials and will facilitate accurate identification of promising materials for CO2 capture and storage as well as air separation for oxy-fuel combustion. We also present the results of grand canonical and canonical Monte Carlo (GCMC and canonical MC), DFT and molecular dynamics (MD) simulations as well as charge density analyses, on both CO2 and N,N-dimethylformamide adsorbed in Ba2TMA(NO3) and MIL-68(In), two MOFs with non-equivalent inorganic structural building units. We demonstrate the excellent agreement found between our simulation results and the solid-state NMR (SSNMR) experiments carried out by Professor Yining Huang (Western University) on these two MOFs. Molecular simulation enables discoveries which complement SSNMR such as the number, distribution and dynamics of guest binding sites within a MOF. We show that the combination of SSNMR and molecular simulation forms a powerful analytical procedure for characterizing MOFs, and this novel set of microscopic characterization techniques allows for the optimization of new and existing MOFs.