Global climate change is one of the most challenging problems that human beings are facing. The large anthropogenic emission of CO2 in the atmosphere is one of the major causes for the climate change. Coal-fired power plants are the single-largest anthropogenic emission sources globally, accounting for approximately one third of the total CO2 emissions. It is therefore necessary to reduce CO2 emission from coal-fired power plants. Current technologies for the post-combustion CO2 capture from flue gas streams can be broadly classified into the three categories: absorption, adsorption, and membrane processes. Despite challenges, CO2 capture by adsorption using solid sorbents and membranes offers opportunities for energy-efficient capture and storage of CO2. Nanoporous materials have attracted tremendous interest in research and development due to their potential in conventional applications such as catalysis, ion-exchange, and gas separation as well as in advanced applications such as sensors, delivery, and micro-devices. In the first part of this dissertation, we will study the synthesis of membranes using an emerging class of nanoporous materials, metal-organic frameworks (MOFs) for carbon dioxide (CO2) separations. Due to the unique chemistry of MOFs which is very different from that of zeolites, the techniques developed for the synthesis of zeolite membranes cannot be used directly. In order to overcome this challenge, a couple of novel techniques were developed: 1) "thermal seeding" for the secondary growth and 2) "surface modification" for the in situ growth. Membranes of HKUST-1 and ZIF-8, two of the most important MOFs, were prepared on porous α-alumina supports using thermal seeding and the surface modification techniques, respectively. The second part of this dissertation demonstrates a simple and commercially viable application of nanoporous materials (zeolite 5A and amine-functionalized mesoporus silica), storing CO2 as a micro-fire extinguishers in polymers. Materialist is observed that by dispersing these highly CO2-philic nanoporous materials in polymer matrices, the propagation of flame was greatly retarded and extinguished. This flame retarding behavior is attributed to the fact that CO2 released from the sorbents (zeolite 5A and mesoporous silica), blocks the flow of oxygen, therefore causing the fire to be effectively extinguished. Our results suggest that the binding strength of CO2 on sorbents play an important role. If the binding strength of CO2 is too low, CO2 releases too early, thereby ineffective in retarding the flame.

La tesis Doctoral está dividida en dos grandes bloques: el primero relacionado con el estudio estructural y de flexibilidad de distintos "Zeolític imidazolate fremewroks (ZIFs) utilizando distintas técnicas de caracterización de alta resolución y, además, simulación molecular; así como el efecto en la adsorción de distintas moléculas en fase gas. El segundo bloque hace referencia al estudio de MOFs en aplicaciones biomédicas, en específico en el estudio de adsorción y liberación en fase líquida de fármacos para el tratamiento del glaucoma.

Porous materials are essential to our everyday lives, for example as an effective catalyst in the cracking of crude oil, or as water softeners in washing powder. When developing novel functional porous materials, it is necessary to fully understand their structure-property relationships to maximise their ability to be used in industrially relevant settings. This thesis aims to understand the mechanical and adsorption properties of a class of porous solids metal-organic frameworks (or MOFs), which have many potential applications owing to their tuneable structures. Due to the inherent 3-D crystalline structure of MOFs, a wide range crystallographic techniques were used to determine structure-property relationships. To achieve maximum in-depth structural knowledge, both classical and quantum theoretical approaches were also applied to complement the understanding of both the energetics and structural details. Chapters One and Two begin with an overview of the state of the art studies carried out on MOFs, focusing on the use of high-pressure crystallography to understand their properties. In addition, there is emphasise on the importance of complementary computational methods that are used in the characterisation of MOFs. In Chapter Three, an isostructural series of MOFs (zeolitic imidazolate frameworks, or ZIFs) were studied for methanol adsorption by employing both experimental and molecular simulation techniques. These frameworks are gating materials, where the imidazole linker rotates upon adsorption of guest, and it was found that through ligand substitution the gate opening angle and onset pressure to gating could be tuned. By using high-pressure Xray crystallography the structure of the ZIFs were studied upon the uptake of guest and the degree of ring rotation quantified. In combination with periodic DFT and grand canonical Monte Carlo simulations the energy barrier to rotation and energies of adsorption could be calculated, respectively. Chapter Four focuses on one ZIF in particular, ZIF-8 ((Zn6(MeIm)12, MeIm = 2- methylimidazole) and details the adsorption of a selection of gases into the pores. The experimental method of cryogenic gas loading into a diamond anvil cell in this chapter is novel to MOFs. This method, in combination with molecular crystallography, is used to determine the structural response of the framework to guest-uptake as well as the crystallographic positions of the adsorption sites. In combination with in silico methods, the adsorption energies of guest-sites could be calculated, detailing which interactions drive the gating behaviour. The method of cryogenic loading highlighted how extreme conditions can be used to extract useful information about structural behaviour of MOFs on uptake of gas molecules into the pores, and when used in combination with computational methods, we have a powerful tool to analyse both positions and energies of adsorption sites. With this information, progress can be made in developing MOFs to maximize favourable interactions and lead to the development of MOFs with better selective gas storage properties. Chapter Five focuses on the synthesis and characterisation of the physical properties of a series of Zr-containing MOFs, called UiO-MOFs. The high valency of Zr(IV) and 12-fold coordination of the metal cluster in these materials, are associated with high shear and bulk moduli, which surpass those of other MOFs. A combination of single-crystal nano-indentation, high-pressure X-ray diffraction studies, density functional theory (DFT) calculations, and first-principles molecular dynamics (MD) simulations were used to determine the compressibility, elasticity and hardness of these materials, whose mechanical robustness was correlated to their different structural features, in-particular, how using non-linear linkers between the metal clusters stabilises the framework to compression. Chapter Six expands upon the series of Zr-MOFs in Chapter Five, and looks at how the mechanical properties of these MOFs are affected upon increasing the linker length. The experimentally determined elastics modulus of one of the frameworks, UiO-sdc (Zr6O4(OH)4(sdc)6 where sdc =4,4’-stillbene dicarboxylate), was found to lie above those of other highly porous MOFs. In addition, the elastic modulus was found to decrease linearly as a function of increasing the linker length, extending the structure-property relationships determined in Chapter Five.

Propylene is one of the most important feedstocks of the petrochemical industry with an estimated 2015 worldwide demand of 100 million tons. Retrofitting conventional C3 splitters is highly desirable due to the huge amount of thermal energy required to separate propylene from propane. Membrane separation is among the alternatives that both academia and industry have actively studied during the past decades, however; many challenges remain to advance membrane separation as a scalable technology for energy-efficient propylene/propane separations. The overarching goal of this research is to provide a framework for development of scalable ZIF-based mixed-matrix membrane that is able to deliver attractive transport properties for advanced gas separations. Zeolitic imidazolate frameworks (ZIFs) were pursued instead of conventional molecular sieves (zeolites and carbon molecular sieves) to form mixed-matrix membrane due to their intrinsic compatibility with high Tg glassy polymers. A systematic study of adsorption and diffusion in zeolitic imidazolate framework-8 (ZIF-8) suggests that this material is remarkably kinetically selective for C3 and C4 hydrocarbons and therefore promising for membrane-based gas separation and adsorptive separation. As a result, ZIF-8 was used to form mixed-matrix dense film membranes with polyimide 6FDA-DAM at varied particle loadings and it was found that ZIF-8 significantly enhanced propylene/propane separation performance beyond the “permeability-selectivity” trade-off curve for polymeric materials. Eventually, this research advanced ZIF-based mixed-matrix membrane into a scalable technology by successfully forming high-loading dual-layer ZIF-8/6FDA-DAM asymmetric mixed-matrix hollow fiber membranes with attractive propylene/propane selectivity.

This thesis presents the synthesis, properties, and applications of two important classes of metal-organic frameworks (MOFs); lanthanide MOFs and hierarchical porous zeolitic imidazolate frameworks (ZIFs). The materials have been characterized using a wide range of techniques including diffraction, imaging, various spectroscopic techniques, gas sorption, dynamical light scattering (DLS) and thermogravimetric analysis (TGA). In Chapter 1, the unique features of MOFs and ZIFs as well as their potential applications are summarized. In Chapter 2, different characterization techniques are presented. Chapter 3 describes a family of new isoreticular lanthanide MOFs synthesized using tri-topic linkers of different sizes, H3L1-H3L4, denoted SUMOF-7I-IV (Ln) (SU; Stockholm University, Ln = La, Ce, Pr, Nd, Sm, Eu and Gd, Paper I). The SUMOF-7I-III (Ln) contain permanent pores and exhibit exceptionally high thermal and chemical stability. The luminescence properties of SUMOF-7IIs are reported (Paper II). The influences of Ln ions and the tri-topic linkers as well as solvent molecules on the luminescence properties are investigated. Furthermore, the potential of SUMOF-7II (La) for selective sensing of Fe (III) ions and the amino acid tryptophan is demonstrated (Paper III).  Chapter 4 presents a simple, fast and scalable approach for the synthesis of hierarchical porous zeolitic imidazolate framework ZIF-8 and ZIF-67 using triethylamine (TEA)-assisted approach (Paper IV). Organic dye molecules and proteins are encapsulated directly into the ZIFs using the one-pot method. The photophysical properties of the dyes are improved through the encapsulation into ZIF-8 nanoparticles (Paper IV). The porosity and surface area of the ZIF materials can be tuned using the different amounts of dye or TEA. To further simplify the synthesis of hierarchical porous ZIF-8, a template-free approach is presented using sodium hydroxide, which at low concentrations induces the formation of zinc hydroxide nitrate nanosheets that serve as in situ sacrificial templates (Chapter 5, Paper V). A 2D leaf-like ZIF (ZIF-L) is also obtained using the method. The hierarchical porous ZIF-8 and ZIF-L show good performance for CO2 sorption. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Manuscript.</p>

L'objectif de cette thèse était d'évaluer quelques Metal-Organic Frameworks (MOFs), choisis en fonction de leur taille de pores, de leur volume poreux et de leur stabilité thermique, en adsorption et séparation des hydrocarbures. Pour étudier le comportement général des MOFs nous avons choisi des MOFs avec des centres métalliques insaturés, des MOFs à charpente anionique et des ZIFs neutres et avons étudié leur sélectivité en séparation de trois familles d'hydrocarbures, à savoir alcanes, alcènes, aromatiques. Les MOFs à centre métallique insaturé se comportent généralement comme des zéolithes polaires, les ZIFs comme des zéolithes apolaires et/ou comme des tamis moléculaires. Les adsorbants les plus prometteurs sont testés sur des séparations d'intérêt industriel telles que la séparation des isomères de xylène, la séparation des paraffines linéaires, monobranchées et di-branchées et l'adsorption sélective du thiophène en vu de l'évaluation de ces adsorbants en désulfuration des essences.

L'objectif de cette thèse était d’évaluer quelques Metal-Organic Frameworks (MOFs), choisis en fonction de leur taille de pores, de leur volume poreux et de leur stabilité thermique, en adsorption et séparation des hydrocarbures. Pour étudier le comportement général des MOFs nous avons choisi des MOFs avec des centres métalliques insaturés, des MOFs à charpente anionique et des ZIFs neutres et avons étudié leur sélectivité en séparation de trois familles d'hydrocarbures, à savoir alcanes, alcènes, aromatiques. Les MOFs à centre métallique insaturé se comportent généralement comme des zéolithes polaires, les ZIFs comme des zéolithes apolaires et/ou comme des tamis moléculaires. Les adsorbants les plus prometteurs sont testés sur des séparations d’intérêt industriel telles que la séparation des isomères de xylène, la séparation des paraffines linéaires, monobranchées et di-branchées et l’adsorption sélective du thiophène en vu de l’évaluation de ces adsorbants en désulfuration des essences. / The aim of this thesis was to evaluate several Metal Organic Frameworks (MOFs), selected based on criteria of pore size, pore volume and thermal stability, in adsorption and separation of hydrocarbons. For studying the general behavior of MOFs in hydrocarbon adsorption, we have chosen MOFs with open metal sites, MOFs with anionic frameworks and neutral ZIFs. The MOFs with open metal sites behave similar to polar zeolites, the ZIFs behave like apolar zeolites and/or like molecular sieves. Finally we selected the most interesting MOFs and tested them in several separations with industrial interest: xylene isomers, paraffin isomers and selective adsorption of thiophene for the purpose of fuel desulfuration.

This thesis uses solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to study local structure and disorder in inorganic materials. Initial work concerns microporous aluminophosphate frameworks, where the importance of semi-empirical dispersion correction (SEDC) schemes in structural optimisation using DFT is evaluated. These schemes provide structures in better agreement with experimental diffraction measurements, but very similar NMR parameters are obtained for any structures where the atomic coordinates are optimised, owing to the similarity of the local geometry. The ³¹P anisotropic shielding parameters (Ω and κ) are then measured using amplified PASS experiments, but there appears to be no strong correlation of these with any single geometrical parameter. In subsequent work, a range of zeolitic imidazolate frameworks (ZIFs) are investigated. Assignment of ¹³C and ¹⁵N NMR spectra, and measurement of the anisotropic NMR parameters, enabled the number and type of linkers present to be determined. For ¹⁵N, differences in Ω may provide information on the framework topology. While ⁶⁷Zn measurements are experimentally challenging and periodic DFT calculations are currently unreliable, calculations on small model clusters provide good agreement with experiment and indicate that ⁶⁷Zn NMR spectra are sensitive to the local structure. Finally, a series of pyrochlore-based ceramics (Y₂Hf₂₋ₓSnₓO₇) is investigated. A phase transformation from pyrochlore to a disordered defect fluorite phase is predicted, but ⁸⁹Y and ¹¹⁹Sn NMR reveal that rather than a solid solution, a significant two-phase region is present, with a maximum of ~12% Hf incorporated into the pyrochlore phase. The use of ¹⁷O NMR to provide insight into the local structure and disorder in these materials is also investigated. Once the different T₁ relaxation and nutation behaviour is considered it is shown that quantitative ¹⁷O enrichment of Y₂Sn₂O₇ is possible, and that ¹⁷O does offer a promising future tool for study.