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.

Zinc oxide (ZnO) is a II-VI semiconductor material that offers tremendous potential as a light emitter in the blue-to-UV range. It has a wurtzite structure, and a direct band gap that can be tuned from 3.0 to 4.0 eV by alloying with Cd or Mg, respectively. In this work, ZnO thin films were grown by metalorganic chemical vapor deposition (MOCVD) on n-Si 2 ° off (100), amorphous glass, n-GaAs (100), and c-plane sapphire substrates. Diethyl zinc (DEZn) and tert-butanol (TBOH) were chosen as precursors. For the first time, Second Harmonic Generation Imaging was applied to the mapping of ZnO epilayers. The images obtained highlighted the polycrystalline character of the thin films, and provided insight as to the growth mode of ZnO on Si. The influence of substrate temperature on the structural properties of the epilayers was investigated by X-ray diffraction and optical microscopy. Grain sizes as high as 54 nm were measured. The optimum temperature range for this system proved to be 450 – 500 °C. The influence of the VI:II ratio during growth on the optical properties of the epilayers was studied by UV-vis-near IR spectroscopy. The lowest Urbach tail E0 parameter was measured for material grown at a VI:II ratio of 18:1. The films’ free electron concentration was shown to decrease by over two orders of magnitude, from 1019 to 1017 cm-3, as the VI:II ratio increased from 10 to 60:1. This decrease in carrier concentration with rising VI:II ratio was paralleled to the surge at 12 K of a photoluminescence (PL) emission band characteristic of p-type ZnO. The band gap energies extracted from room temperature transmission spectra ranged between 3.35 and 3.38 eV, in agreement with the value of 3.35 eV measured by room temperature PL. Moreover, variable temperature PL spectra were recorded between 12 and 298 K on ZnO grown on Si. The 12 K spectrum was dominated by a donor-bound exciton (D°X) at 3.36 eV, while the 298 K scan displayed strong free exciton emission (FX) at 3.29 eV. The width of the D°X band proved to be as narrow as 7 meV. The intensity ratio between the room temperature near-band edge emission and the defect-related green band was as high as 28:1, highlighting the optical quality of the layers deposited in this work. The electrical properties of the thin films were studied by Hall measurements (van der Pauw configuration), and a maximum room temperature mobility of 11 cm2/Vs was recorded. Furthermore, a palladium (Pd) Schottky barrier diode on ZnO was fabricated. The barrier height and ideality factor were calculated from current–voltage measurements to be 0.83 eV and 1.6, respectively. The capacitance–voltage curve of the diode yielded a carrier concentration in the depletion region of 8·1017 cm-3. This study has shown that the optical and electrical properties of ZnO depend strongly on the growth conditions employed. A suitable choice of growth parameters can yield high quality ZnO that may be used for various devices. Keywords: Hall, MOCVD, optical spectroscopy, photoluminescence, Schottky barrier diode, SH Imaging, X-ray diffraction, ZnO.

Metal organic frameworks (MOFs) are a class of nanoporous materials composed through self-assembly of inorganic and organic structural building units (SBUs). MOFs show great promise for many applications due to their record-breaking internal surface areas and tunable pore chemistry. This thesis work focuses on gas separation applications of MOFs in the context of carbon capture and storage (CCS) technologies. CCS technologies are expected to play a key role in the mitigation of anthropogenic CO2 emissions in the near future. In the first part of the thesis, robust machine learning quantitative structure-property relationship (QSPR) models are developed to predict CO2 working capacity and CO2/H2 selectivity for pre-combustion carbon capture using the most topologically diverse database of hypothetical MOF structures constructed to date (358,400 MOFs, 1166 network topologies). The support vector regression (SVR) models are developed on a training set of 35,840 MOFs (10% of the database) and validated on the remaining 322,560 MOFs. The most accurate models for CO2 working capacities (R2 = 0.944) and CO2/H2 selectivities (R2 = 0.876) are built from a combination of six geometric descriptors and three novel y-range normalized atomic-property-weighted radial distribution function (AP-RDF) descriptors. 309 common MOFs are identified between the grand canonical Monte Carlo (GCMC) calculated and SVR-predicted top-1000 high-performing MOFs ranked according to a normalized adsorbent performance score. This work shows that SVR models can indeed account for the topological diversity exhibited by MOFs. In the second project of this thesis, computational simulations are performed on a MOF, CALF-20, to examine its chemical and physical properties which are linked to its exceptional water-resisting ability. We predict the atomic positions in the crystal structure of the bulk phase of CALF-20, for which only a powder X-ray diffraction pattern is available, from a single crystal X-ray diffraction pattern of a metastable phase of CALF-20. Using the predicted CALF-20 structure, we simulate adsorption isotherms of CO2 and N2 under dry and humid conditions which are in excellent agreement with experiment. Snapshots of the CALF-20 undergoing water sorption simulations reveal that water molecules in a given pore adsorb and desorb together due to hydrogen bonding. Binding sites and binding energies of CO2 and water in CALF-20 show that the preferential CO2 uptake at low relative humidities is driven by the stronger binding energy of CO2 in the MOF, and the sharp increase in water uptake at higher relative humidities is driven by the strong intermolecular interactions between water. In the third project of this thesis, we use computational simulations to investigate the effects of residual solvent on Ni-BPM’s CH4 and N2 adsorption properties. Single crystal X-ray diffraction data shows that there are two sets of positions (Set 1 and 2) that can be occupied by the 10 residual DMSO molecules in the Ni-BPM framework. GCMC simulations of CH4 and N2 uptake in Ni-BPM reveal that CH4 uptake is in closest agreement with experiment when the 10 DMSO’s are placed among the two sets of positions in equal ratio (Mixed Set). Severe under-prediction and over-prediction of CH4 uptake are observed when the DMSO’s are placed in Set1 and Set 2 positions, respectively. Through binding site analysis, the CH4 binding sites within the Ni-BPM framework are found to overlap with the Set 1 DMSO positions but not with the Set 2 DMSO positions which explains the deviations in CH4 uptake observed for these cases. Binding energy calculations reveal that CH4 molecules are most stabilized when the DMSO’s are in the Mixed Set of positions.

Some of the challenges faced when developing novel functional materials, cannot be resolved without the correct understanding of their structure‐property relationships. Metal‐organic frameworks (MOFs) constitute a representative example where in-depth structural knowledge can greatly help improve and optimise their application into industrially relevant settings. Fortunately, the inherent crystalline nature of MOFs allows for analysis using the wide range of crystallographic experimental techniques that are currently available. This work covers the study of the structural properties of a particular family of MOFs, which have shown significant potential as molecular sieves and for gas storage. Sc-based MOFs first attracted attention for their particularly robust and inert nature, bypassing some of the physical challenges many MOFs have when undergoing industrial implementation. After an initial review of the state of the art in the field of MOFs and the techniques utilised to analyse their properties, this work then focuses on the mechanical properties of a series of functionalised and unfunctionalised Sc‐dicarboxylate MOFs. Using nano‐indentation techniques and high‐pressure crystallography, the hardness and elasticity of these materials are correlated to their different structural features, confirming their relative robustness when compared to other MOFs in the literature. An interesting property of Sc2BDC3 is its selective uptake of CO2 over other fuel-related gases such as CH4 and CO. In this context, the in situ adsorption crystallographic analysis of Sc2BDC3 and its amino‐functionalised derivative Sc2(BDC‐NH2)3 (BDC‐NH2 = 1,4‐amino‐2‐benzenedicarboxylate) is described, as performed using the gas cell set up of beamline I19 at the Diamond Light Source synchrotron. This study is the first example of a mixed gas atmosphere experiment using single‐crystal diffraction, which in conjunction with in silico, adsorption and breakthrough experiments, provides direct insight into the interactions that drive the selective behaviour of both frameworks. Following this, the MOF Sc2BDC3 (BDC = 1,4‐benzenedicarboxylate), is selected as a case study for branched and unbranched alkane separation. Here, high‐pressure crystallography shows how these relatively oversized guest molecules, can be forced at thousands of atmospheres of pressure inside the narrow triangular channels (< 4 Å diameter) of the framework. It is also possible to resolve the structural changes the framework undergoes upon uptake of the different guests, as well as locate the adsorption sites of the hydrocarbons in the pores of Sc2BDC3, which can be then correlated to the gas adsorption behaviour of the different guests. To conclude, the high‐pressure inclusion study of both CO2 and CH4 inside Sc2BDC3 shows how combining cryoloading techniques and molecular crystallography for the first time, can provide improved models of the adsorbed gaseous guests inside Sc2BDC3. This example not only provides a novel alternative in which to study more easily the adsorption sites in MOFs via diffraction techniques, but also reveals some of the interesting structural behaviour MOFs can have in these extreme conditions.

>Magister Scientiae - MSc / Due to the rapid depletion of fossil fuel reserves and the production of environmentally harmful by-products such as carbon dioxide, there is an urgent need for alternate sustainable clean energy. One of the leading candidates in this endeavour is hydrogen, which can be used as an energy carrier since it has a high energy density, zero emissions and is produced from non-depletable resources such as water. The major challenge hindering a hydrogen economy is the lack of safe and effective storage technologies for mobile applications. A prospective solution to this problem lies in the use of porous powdered materials, which adsorb the hydrogen gas. However, the integration of these powdered materials into a storage tank system, results in the pipelines being contaminated during filling cycles. This necessitates the shaping of the porous powdered materials. Among the many shaping techniques available, the electrospinning technique has been proposed as a promising technology since it is a versatile process that is easily scaled-up making it attractive for the applications of the study. Furthermore, the electrospinning process enables the synthesis of nano-sized fibres with attractive hydrogen sorption characteristics. In this regard, the current study employs the electrospinning technique to synthesise electrospun composite fibres for mobile hydrogen storage applications. After electrospinning three polymers, polyacrylonitrile (PAN) was selected as the most suitable polymer because it yielded bead-free electrospun fibres. However, the diameter of the PAN fibres was large/thick which prompted further optimisation of the electrospinning parameters. The optimised electrospinning conditions that yield unbeaded fibres within the desired diameter range (of 300-500 nm) were a PAN concentration of 10 wt%, a flow rate of 0.4 mL/h, a distance of 10 cm between the needle tip and collector plate, and an applied voltage of 8 kV. The study then progressed to the synthesis and characterisation of the pristine porous powdered materials which adsorb hydrogen gas. The porous powdered materials investigated were commercial zeolite 13X, its synthesised templated carbon derivative (ZTC) and Zr (UiO-66) and Cr (MIL-101) based metal-organic frameworks (MOFs). ZTC was synthesised via liquid impregnation coupled with chemical vapour deposition (CVD), and the MOFs were synthesised by the modulated solvothermal method. Analysis of the ZTCs morphology and phase crystallinity show that the carbon templated process using zeolites was successful, however, ZTC was amorphous compared to crystalline zeolite template. The BET surface area was assessed with the aid of nitrogen sorption isotherms for both zeolite 13X and ZTC, and values of 730 and 2717 m²/g, respectively were obtained. The hydrogen adsorption capacity for zeolite 13X was 1.6 wt% and increased to 2.4 wt% in the ZTC material at 77 K and 1 bar. The successful synthesis of well defined, crystalline MOFs was evident from X-ray diffraction and morphological analysis. The BET surface area and hydrogen adsorption for Zr MOF were 1186 m²/g and 1.5 wt%, respectively at 77 K and 1 bar. Cr MOF had a BET surface area of 2618 m²/g and hydrogen adsorption capacity of 1.9 wt% at 77 K and 1 bar. The main focus of the study was to synthesise electrospun composite fibres that can adsorb hydrogen gas and thus provide significant insight in this field of research. As such it examined composite fibres that incorporates porous powdered materials such as zeolite 13X, ZTCs, UiO-66 (Zr) MOF and MIL-101 (Cr) MOF and investigated their ability to adsorb hydrogen gas, which have not been reported previously. The synthesis of composite fibres was achieved by incorporating the porous powdered materials into the PAN resulting in a polymeric blend that was then electrospun. Morphological analysis illustrated that the porous powdered materials were successfully supported by or incorporated within the PAN fibres, forming composite fibres. The BET surface area of the 40 wt% zeolite-PAN and 12.5 wt% ZTC-PAN composite fibres were 440 and 1787 m²/g respectively. Zr MOF and Cr MOF composite fibres had a BET surface area of 815 and 1134 m²/g, respectively. The BET surface area had reduced by 40, 34, 31 and 57% for zeolite 13X, ZTC, Zr MOF and Cr MOF, respectively after these porous powdered materials were incorporated into PAN. The hydrogen adoption capacity for 40 wt% zeolite-PAN, 12.5 wt% ZTC-PAN, 20 wt% Zr MOFPAN and 20 wt% Cr MOF-PAN composite fibres was 0.8, 1.8, 0.9 and 1.1 wt%, respectively. This decrease was attributed to the limited amount of porous powdered materials that could be incorporated into the fibres since only 40 wt% of zeolite 13X, 12.5 wt% of ZTC and 20 wt% of the MOFs were loaded into their respective composite fibres. This was due to the fact that incorporation of greater amounts of porous powdered materials resulted in a viscous polymeric blend that was unable to be electrospun. It is evident from the study that electrospinning is a versatile process that is able to produce composite fibres with promising properties that can potentially advance the research in this field thus providing a practical solution to the problem of integrating loose powdered materials into an on-board hydrogen storage system. / CSIR Young Researchers Establishment Fund (YREF)

This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.

In this thesis computational chemistry has been used to accelerate experimental discovery in the fields of ice recrystallization inhibitors for cryopreservation and ultra-microporous MOFs for carbon dioxide capture and storage. Ice recrystallization is one of the leading contributors to cell damage and death during the freezing process. This occurs when larger ice crystal grains grow at the expense of smaller ones. Naturally occurring biological antifreeze molecules have been discovered but only operate up to -4oC and actually exasperate the problem at temperatures lower than this. Recently, the group of Dr. Robert Ben have been successful in synthesizing small organic molecules which are capable of inhibiting the growth of ice crystals during the freezing process. They have built a library of diverse compounds with varying functionalities and activity. Chemical intuition has been unsuccessful in finding a discernible trend with which to predict activity. Herein we present work where we have utilized a quantitative structure activity relationship (QSAR) model to predict whether a molecule is active or inactive. This was built from a database of 124 structures and was found to have a positive find rate of 82%. Proposed molecules that had yet to be synthesized were predicted to active or inactive using our method and 9/11 structures were indeed active which is strikingly consistent to the 82% find rate. Our efforts to aid in the discovery of these novel molecules will be described here. Metal organic frameworks (MOFs) are a relatively new class of porous materials which have taken the academic community by storm. These three-dimensional crystalline materials are built from a metal node and an organic linker. Depending on the metals and organic linkers used, MOFs can possess a vast range of topologies and properties that can be exploited for specific applications. Ultra-microporous MOFs possess relatively small pores in the range of 3.5 Å to 6 Å in diameter. These MOFs have some structural advantages compared to larger pored MOFs such as molecular sieving, smaller pores which promote strong framework-gas interactions and cooperative effects between guests, and longer shelf-life due to small void volumes and rigid frameworks. Here we present newly synthesized ultra-microporous MOFs based on isonicotnic acid as the organic linker with Ni and Mg as the metal centre. Despite having such small pores, Ni-4PyC exhibits exceptionally high CO2 uptake at high pressures. Furthermore, Mg-4PyC exhibits novel pressure dependent gate-opening behaviour. Computational simulations were employed to investigate the origin of high CO2 uptake, predict high pressure (>10bar) isotherms, quantify CO2 binding site positions and energies, and study uptake-dependent linker dynamics. This work hopes to provide experimentalists with some explanation to these interesting unexplained phenomena and also predict optimal properties for new applications.

This thesis will describe the magnetic behavior found in a scaling array of magnetic nanomaterials that have been uniquely designed, synthesized and characterised in order to better understand their properties with regards to potential future applications. Within Chapter 1 will be a detailed, yet accessible, introduction to nanomagnetism and the fundamental principles and practical techniques essential to the study of this unique mélange of physics and chemistry. This chapter will be designed to give the reader the necessary tools to understand key literature concepts found in Chapter 2, as well as the work presented in the following chapters. Chapter 2 will provide an overview of relevant literature in the field of magnetic nanomaterials, including: nanoparticles, single-molecule magnets, single-chain magnets and metal-organic frameworks. Chapter 3 will describe work performed on nanoparticles doped with lanthanide ions in order to explore their resulting size, shape, crystallinity and magnetic properties. The relevance of the chosen particles (NaYF4) pertains to their proposed use in a variety of applications due to their known luminescent properties, which we sought to hybridize with interesting magnetic properties, thus creating multimodal imaging capabilities. Doping with a variety of desired ratios of lanthanide ions (GdIII, TbIII, DyIII, ErIII and YbIII) was successful, producing crystalline nanoparticles with tunable size and shape. Magnetic measurements displayed a clear absence of superparamagnetic behavior, indicating that these materials have the potential to be well-suited to applications in biomedicine as multimodal imaging probes and MRI contrast agents. Chapter 4 will build on the previously explored doped nanomaterials through creating a hybrid nanomaterial by tethering lanthanide-based magnetic molecules to the surface of nanoparticles. This is performed through the synthetic design of a SMM with two anisotropic DyIII ions, which was synthesized and designed to bear terminal S-groups in order to promote the binding of the magnetic molecule to capping agent free gold nanoparticles. Upon confirmation of the successful surface attachment of the molecules, magnetic measurements displayed that the magnetic molecules maintained their static properties, however, their dynamic properties were altered. This system was the first example of this type of novel approach to the study of magnetic molecules on surfaces for data storage, spintronics, and quantum computing applications. Chapter 5 will expand on the previous study of ordering arrays of magnetic molecules on the surface of nanoparticles by tethering them into 1D chain networks. We successfully synthesized chain networks with YIII, EuIII, GdIII, TbIII and DyIII lanthanide ions. Magnetic characterisation revealed slow relaxation of the magnetization with no significant interactions between magnetic ions, thus these are discrete magnetic molecules in 1D. Rather surprisingly, the isotropic GdIII analogue displayed field induced slow relaxation of the magnetisation, necessitating the use of ab initio calculations in order to shed light on the potential causes of this unexpected behavior. Overall, through the formation and study of these structures, we observed a new potential method of SMM assembly for the study of ordered arrays of molecular magnets. Chapter 6 will focus on ordering of discrete magnetic systems in 3D. With this in mind, we successfully isolated the first Co8 cuboctahedron MOF. Magnetic measurements displayed that each SBU was well-isolated, with significant antiferromagnetic coupling between CoII ions, leading to an S = 0 ground state. These interactions were then modelled using density functional theory. This type of study promotes the future development of novel high-nuclearity MOF structures with interesting and tuneable magnetic properties, as well as the potential for assembly of discrete molecular magnetic units in 3D using MOFs. Chapter 7 utilizes the principles of Chapter 3, wherein magnetic ions are doped into a diamagnetic material; in this case, MOF-5. We sought to isolate one CoII ion in each SBU, and build upon this by adding additional magnetic ions and probing their interactions. Through magnetic measurements we observed a scaling magnetic moment with CoII content, and with higher dopant percentages we began to observe magnetic interactions occurring within the SBUs. Interestingly, we also observed a change in coordination environment with higher dopant percentages, likely as a result of the previously suggested capability of one ZnII ion within the MOF-5 SBU to become hexacoordinate, allowing CoII doping up to a maximum of 25%. Consequently, this study points to the cause of the structural instability that plagues MOF-5 in the presence of air and moisture. We probed this system further in Chapter 8 using FeIII as a dopant ion, and were able to obtain the first crystallographic evidence of the coordination change of ZnII in MOF-5. Furthermore, the structure obtained with FeIII was the first example of metal ion addition within a MOF that bound two interpenetrated frameworks together. This new MOF was found to have the potential to be a more practical material for gas storage and separation, and/or for catalysis. Thus, this study was informative in regards to the inherent instability of the parent framework, as well as a new method of metal addition to a known MOF structure. Chapter 9 will conclude the work with a discussion of what was performed in, and learned from, each thesis section, as well as provide an outlook and perspective on the novel work that may be derived from these projects going forward.

An immediate reduction in global CO2 emissions could be accomplished by replacing coal- or oil-based energy sources with purified natural gas. The most important process involved in natural gas purification is the separation of CO2 from CH4, where Pressure Swing Adsorption (PSA) technology on porous materials has emerged as a less energy demanding technology. Among porous materials which are used or could potentially be used in PSA, Metal Organic Frameworks (MOFs) have attracted particular interest owing to their record-breaking surface areas, high-porosity, and high tunability. However, the discovery of optimal MOFs for use in adsorption-based CO2 separation processes is remarkably challenging, as millions of MOFs can potentially be constructed from virtually limitless combinations of inorganic and organic secondary building units. To overcome this combinatorial problem, this thesis aims to (1) identify important design features of MOFs for CO2/CH4 separation through the investigation of currently existing MOFs as well as the high throughput computational screening of a large database of MOFs, and to (2) develop efficient computational tools for aiding the discovery of new MOF materials. To validate the computational methods and models used in this thesis, the first work of this thesis presents the computational modeling of CO2 adsorption on an experimental CuBDPMe MOF using grand canonical Monte Carlo simulations and density functional theory. The simulated CO2 adsorption isotherms are in good agreement with experiment, which confirms the accuracy of the models used in our simulations throughout this thesis. The second work of this thesis investigates the performance of an experimental MIL-47 MOF and its seven functionalized derivatives in the context of natural gas purification, and compares their performance with that of other well-known MOFs and commercially used adsorbents. The computational results show that introducing polar non-bulky functional groups on MIL-47 leads to an enhancement in its performance, and the comparison suggests that MIL-47-NO2 could be a possible candidate as a solid sorbent for natural gas purification. This study is followed by the compactional study of water effects on natural gas purification using MOFs, as traces of water is present in natural gas under pipeline specifications. From the study, it is found that water has a marginal effect on natural gas purification in hydrophobic MOFs under pipeline specifications. Following the aforementioned studies, a database of 324,500 hypothetical MOFs is screened for their performance in natural gas purification using the general protocol defined in this thesis. From the study, we identify 'hit' materials for targeted synthesis, and investigate the structure-property relationships with the intent of finding important MOF design features relevant to natural gas purification. We show that layered sheets consisting of poly-aromatic molecules separated by a perpendicular distance of roughly 7 Å are an important structural-chemical feature that leads to strong adsorption of CO2. Following the screening study, we develop efficient computational tools for the recognition of high-preforming MOFs for methane purification using Machine Learning techniques. A training set of 32,500 MOF structures was used to calibrate support vector machines (SVMs) classifiers that incorporate simple geometrical features including pore size, void fraction and surface area. The SVM machine learning classifiers can be used as a filtering tool when screening large databases. The SVM classifiers were tested on ~290,000 MOFs that were not part of the training set and could correctly identify up to 70% of high-performing MOFs while only flagging a fraction of the MOFs for more rigorous screening. As a complement to this study, we present ML classifier models for CO2/CH4 separation parameters that incorporate separately the Voronoi hologram and AP-RDF descriptors, and we compare their performance with the classifiers composed of simple geometrical descriptors. From the comparison, it is found that including AP-RDF and Voronoi hologram descriptors into the classifiers improves the performance of classifiers by 20% in capturing high-performing MOFs. Finally, from the screening data, we develop a novel chemiformatics tool, MOFFinder, for aiding in the discovery of new MOFs for CO2 scrubbing from natural gas. It has a user-friendly graphical interface to promote easy exploration of over 300,000 hypothetical MOFs. It enables synthetic chemists to find MOFs of interest by searching the database for Secondary Building Units (SBUs), geometric features, functional groups and adsorption properties. MOFFinder provides, for the first time the substructure/similarity query of porous materials for users and is publicly available on titan.chem.uottawa.ca/moffinger.

In this thesis, we aim to investigate the thermoresponsive behaviour, especially negative thermal expansion (NTE), in metal dicarboxylate metal organic frameworks (MOFs) using X-ray diffraction techniques. Four materials with the UiO-66 topology [Zr6O4(OH)4(bdc)12], [Zr6O6(bdc)12], [Zr6O6(bpdc)12] and [Zr6O6(2,6-ndc)12] (bdc = 1,4-benzenedicarboxylate, bpdc = 4,4’-biphenyldicarboxylate and 2,6-ndc = 2,6-napthalenedicarboxylate) were investigated, all of which contain a zero-dimensional inorganic cluster. All four members show NTE behaviour over the observed temperature ranges as a result of the twisting motion of the carboxylate groups of the organic linkers. This twisting motion introduces a concerted rocking motion within the inorganic cluster which causes an apparent decrease in the size of the cluster and hence overall volume contraction. Alteration of the structure of the organic linker has an effect on the magnitude of the expansivity coefficient which is believed to be related to the existence of specific vibrational modes of that particular organic linker. Four members of the MIL-53 family [Al(OH)(bdc)], [AlF(bdc)], [Cr(OH)(bdc)] and [VO(bdc)] were studied. All four materials show elements of NTE behaviour related to a “wine rack” thermo-mechanical mechanism which is determined by the connectivity of the framework. The thermoresponsive behaviour in these materials is dominated by the changes in the plane of the pore opening. These changes result from a combination of three distinct types of motion of the bdc linker including the rotation of the bdc linker about the chain of the inorganic octahedra, the “knee cap” bending mode of the carboxylate groups about the O-O vector and possibly the transverse vibrations within the bdc linker. The latter motion was not evident in this work due to the limitations of the structure refinements. The former two motions appear to be correlated and depend on the rigidity of the metal-centred octahedra which is determined by the constituent metal cation and anion types. The rigidity of the octahedra is also found to play an important role in determining whether the material undergoes a “breathing” phase transition at low temperature. [Sc2(bdc)3] shows NTE behaviour over the observed temperature range which is partially driven by a “wine rack” thermo-mechanical mechanism, but with an opposite framework compression direction when compared to the MIL-53 types MOFs. This is due to the presence of an additional bdc connecting linker in the plane of the pore opening. This extra connection inverses the compression direction and also impedes the structural changes in the plane of the pore opening. The contraction of the chain of inorganic octahedra is the main contributor to the overall unit cell contraction and is caused by the twisting motion of the carboxylate groups of the bdc linker while the magnitude of this contraction is determined by the flexibility of the chain of inorganic octahedra.