Les Membranes à Matrices Mixtes (MMM’s) sont des matériaux prometteurs pour la capture de CO2 en comparaison aux technologies actuelles telles que l’absorption par solvants aminés (monoéthanolamine). Les ‘Metal-Organic Frameworks’ (MOFs) sont des matériaux poreux cristallins envisagés pour être intégrés sous forme de nanoparticules aux polymères des MMM’s. Ils résultent de la combinaison de nœuds métalliques et de ligands organiques pour former des structures tridimensionnelle (3D) organisées. Ils possèdent divers avantages : des aires spécifiques et des volumes poreux élevés, des tailles de pores contrôlables, et pour certains une stabilité à l’eau. Les MOFs ont une chimie adaptable aux applications souhaitées contrairement aux adsorbants classiques tels que les charbons actifs, les zéolithes.D’une part, ce travail a eu pour objectif l’évaluation des performances de séparation du CO2 par des MOFs microporeux en vue des séparations CO2/N2 et CO2/CH4. Les interactions ‘gaz-adsorbant’ sont favorisées au sein des MOFs par : (1) une réduction de la taille de pores et du volume poreux pouvant engendrer des effets de confinements, de tamis moléculaire ou (2) par la présence de groupements de surface. En conséquence, ces paramètres peuvent contribuer à l’amélioration de la sélectivité du CO2 et ont été étudiés pour divers systèmes de MOFs microporeux. D’autre part, les paramètres texturaux (aire spécifique, volume poreux) et thermodynamiques (enthalpies d’adsorption) ont été corrélés aux quantités maximales de CO2 adsorbées au travers d’une approche quantitative de relation de structure-propriété pour établir des tendances linéaires. / Mixte Matrix Membranes (MMM’s) are promising materials for CO2 capture compared to current technologies as absorption using amines solvents (monoéthanolamine). Metal-Organic Frameworks (MOFs) are crystalline porous materials which can be integrate under nanoparticles shape to polymer phase of MMM’s. They are built from metal nods and organic ligand to yield well-defined tridimensional structure (3D). They possess various advantages: high specific surface area and pore volume, tunable pore size and some of them are stable in presence of water. MOFs have a sustainable chemistry to targeted applications unlike traditional adsorbents as activated carbons, zeolites.On the one hand, this work aimed the assessment of CO2 separation performances of microporous MOFs for CO2/N2 and CO2/CH4 gas separations. The ‘gas-adsorbent’ interactions are favored in MOFs by: (1) a decrease of pore size, pore volume which can involve confinement effects, molecular sieve effects or (2) the presence of surface groups. Therefore, these factors can contribute to the CO2 selectivity improvement and have been studied for various microporous MOFs. On the other hand, textural (specific surface area, pore volume) and thermodynamic (adsorption enthalpy) parameters have been correlated to CO2 maximum excess uptakes through a quantitative structure-property approach to establish some linear trends.

Growing concerns regarding chemical weapons and toxic chemicals require the development and testing of robust materials and methods to capture and destroy these harmful chemicals. This dissertation discusses the fundamental properties (e.g., structure, stability and activity) of metal oxyhydroxide based 3-dimensional porous materials, such as metal organic frameworks (MOFs), and covalent organic frameworks (COFs), and their applications for gas capture and degradation, especially for toxic gases and chemical warfare agent simulants. We report and verify that the active sites in UiO-67 MOFs are the metal nodes (oxyhydroxides) and developed a paradigm which correlates the activities of the MOFs, the metal oxyhydroxides and their precursors. This new understanding can help researchers choose the optimum metal for the intended applications by avoiding the tedious and time-consuming procedures of MOF synthesis and purification. In addition, to characterize and understand the structures of active sites in UiO-67 MOFs, temperature programmed desorption mass spectrometry (TPD-MS) and in situ Fourier-transform infrared (FTIR) spectroscopy were performed under ultra-high vacuum (UHV) and revealed unconventional binding sites and assisted in the successful characterization of missing linker defects. Here, our research helped in identification of a new class of binding sites, via NH-π interactions, in UiO-67 MOFs will assist researchers working in the areas of gas storage/release in developing better materials. This study should facilitate the structural understanding of MOFs, their important attributes such as defects and their chemistry in the presence of toxic gases. After successful identification of active species in MOFs, with the ultimate goal of isolating andii depositing the active sites on porous carbonaceous materials, e.g., COFs, we have engineered a facile technique to synthesize robust nanoparticle-COF and evaluated the reasons for its improved catalytic properties over other materials. The discoveries and their implications discussed in this thesis address fundamental knowledge gaps and should aid the rational design of superior materials for in operando applications. / Chemistry

[pt] Materiais bidimensionais apresentam possibilidades de funcionalização que os tornam versáteis para diversas aplicações, tais como em dispositivos eletrônicos. A presença de poros nesses materiais pode trazer novas funções, como adsorção de gases, liberação controlada de fármacos e catálise. Os covalent organic frameworks (COFs) são uma nova classe de materiais orgânicos porosos cristalinos que têm recebido destaque em química reticular. O objetivo dessa dissertação é apresentar a síntese e caracterização de quatro novos COFs baseados em carbazóis, que constitui uma classe de compostos utilizada na obtenção de polímeros condutores. O bloco de montagem principal utilizado foi o 3,6-diamino-9H-carbazol e as fontes de aldeído foram triformilfloroglucinol, triformilfenol, 1,3,5-tri(4-formilfenil)benzeno e triformilbenzeno para a síntese do RIO2, RIO3, RIO5 e RIO6, respectivamente. RIO2 e RIO3 apresentaram-se sob a forma ceto enamina e imina, respectivamente, além de pouca cristalinidade e baixa área específica. Através de cálculos baseados na Teoria do Funcional da Densidade (DFT), foi verificado que esses COFs apresentam suas folhas deslocadas e rotacionadas devido às interações eletrostáticas e para minimizar os momentos de dipolo das ligações N-H dos carbazóis. RIO5 e RIO6 também se apresentaram pouco cristalinos e com áreas específicas baixas. Apesar desses resultados, esses materiais ainda podem ser aplicados em eletrônica orgânica por apresentarem estrutura química compatível com tal aplicação. / [en] Two-dimensional materials have functionalization possibilities that make them versatile for various applications such as in electronic devices. The presence of pores in these materials can give new features to them, such as gas adsorption, drug delivery and catalysis. The covalent organic frameworks (COFs) are a new class of crystalline porous organic materials that have been prominent in reticular chemistry. The purpose of this work is to present the synthesis and characterization of four new COFs based on carbazoles, which are a class of compounds used to obtain conductive polymers. The main building block used was 3,6-diamine-9H-carbazole with the aldehyde sources were triformylphloroglucinol, triformylphenol, 1,3,5-tri(4 formylphenyl)benzene and triformylbenzene to obtain RIO2, RIO3, RIO5 and RIO6, respectively. RIO2 and RIO3 are in keto-enamine and imine form, respectively, as well as have low crystallinity and low specific area. Calculus based on Density Functional Theory (DFT) found that these COFs present their sheets displaced and rotated due to electrostatic interactions and to minimize the dipole moments of the N-H bonds of carbazoles. In an attempt to avoid the absence of pores, RIO5 and RIO6 materials were synthesized, however these COFs also performed poorly crystalline and with low specific areas. Despite these results, these materials can also be applied in organic electronics by presenting chemical structure compatible with such application.

A Graphical User Interface (GUI) is defined by its appearance and its behavior. A GUI’s behavior determines how it reacts to user and system events such as mouse, keyboard, or touchscreen presses, or changes to an underlying data model. Although many tools are effective in enabling designers to specify a GUI’s appearance, defining a custom behavior is difficult and error-prone. Many of the difficulties developers face in defining GUI behaviors are the result of their reactive nature. The order in which GUI code is executed depends upon the order in which it receives external inputs. Most widely used user interface programming frameworks use an event-callback model, where developers define GUI behavior by defining callbacks—sequences of low-level actions—to take in reaction to events. However, the event-callback model for user-interface development has several problems, many of which have been identified long before I started work on this dissertation. First, it is disorganized: the location and order of event-callback code often has little correspondence with the order in which it will be executed. Second, it divides GUI code in a way that requires writing interdependent code to keep the interface in a consistent state. This is because maintaining a consistent state requires referencing and modifying the same state variables across multiple different callbacks, which are often distributed throughout the code. In this dissertation, I will introduce a new framework for defining GUI behavior, called the stateconstraint framework. This framework combines constraints—which allow developers to define relationships among interface elements that are automatically maintained by the system—and state machines—which track the status of an interface. In the state-constraint framework, developers write GUI behavior by defining constraints that are enforced when the interface is in specific states. This framework allows developers to specify more nuanced constraints and allows the GUI’s appearance and behavior to vary by state. I created two tools using the state-constraint framework: a library for Web developers (ConstraintJS) and an interactive graphical language (InterState). ConstraintJS provides constraints that can be used both to control content and control display, and integrates these constraints with the three Web languages—HTML, CSS, and JavaScript. ConstraintJS is designed to take advantage of the declarative syntaxes of HTML and CSS: It allows the majority of an interactive behavior to be expressed concisely in HTML and CSS, rather than requiring the programmer to write large amounts of JavaScript. InterState introduces a visual notation and live editor to clearly represent how states and constraints combine to define GUI behavior. An evaluation of InterState showed that its computational model, visual notation, and editor were effective in allowing developers to define GUI behavior compared to conventional event-callback code. InterState also introduces extensions to the state-constraint framework to allow developers to easily re-use behaviors and primitives for authoring multi-touch gestures.

In recent years, metal-organic frameworks (MOFs) have been identified as promising adsorbents in a number of industrially relevant, yet challenging, separations, including the removal of propane from propane/propylene mixtures and the separation of mixtures of xylene isomers. The highly tuneable nature of MOFs - wherein structures may be constructed from a variety of diverse building blocks – has resulted in the publication of a staggering number of frameworks incorporating a wide range of network topologies, pore shapes and pore diameters. As a result, there are a huge number of candidate adsorbents to consider for a given separation. Molecular simulation techniques allow the identification of those structural features and characteristics of a MOF which exert the greatest influence on the adsorption and separation of the compounds of interest, providing insights which can both guide the selection and accelerate the development of adsorbents for a specific application. The separation of propane/propylene mixtures via adsorption has typically focused on selective adsorption of the olefin, propylene, via specific olefin-adsorbent interactions. These propylene-selective MOFs result in processes which selectively remove the most abundant species in the process stream and are typically characterised by high heats of adsorption, resulting in large adsorption units and adsorbents which are difficult to regenerate. In this work, the capability of MOFs to selectively adsorb propane over propylene is explored, potentially allowing for the design of smaller and more energy-efficient adsorption units. By studying a range of different MOFs as well as carbon-based model pores, it was found that the low-pressure selectivity of the structure is determined by the strength of the electrostatic interaction between propylene and the framework, while the adsorptive preference at industrially-relevant pressures is dominated by the enhanced packing efficiency of propylene over propane. The confinement of C3 molecules, however, may be employed to negate this entropic advantage and guide the development of materials which selectively adsorb propane over propylene. It has recently been reported that the adsorptive preference of a MOF for one xylene isomer over another may be predicted based solely on the pore size distribution of the structure. In this work, the impact of pore size on selectivity was studied systematically in both one-dimensional model pore systems of varying geometries and analogous published MOF structures. The ability of the framework to discriminate between xylene molecules in these systems was found to be determined primarily by the different packing arrangements available to the different isomers – while small pores were found to favour the slimmest of the isomers, larger pores were found to favour the more compact ortho- isomer. Finally, the adsorption and diffusion of xylene isomers in a more complex MOF, UiO-66(Zr), was studied in depth. Simulations were able to correctly predict the previously-reported preference of the MOF for ortho-xylene (oX). The smaller volume of the oX molecule compared to the other isomers was found to be responsible both for an enhanced entropic contribution and higher guest-host interaction energies. The importance of framework flexibility in the diffusion of xylene isomers in UiO-66(Zr) was also explored, with distortion of the structure in response to interaction with adsorbed molecules found to be essential in allowing xylenes to diffuse through the pore space.

The democratic decentralization of government administration in Indonesia from 1999 represents the most dramatic shift in governance in that country for decades. In this dissertation I explore how health managers in one kabupaten (regency) are responding to the new political environment. Kabupaten health managers experience decentralization as incomplete, pointing to the tendency of central government to retain control of certain health programs and budgets. At the same time they face competing demands for autonomy from puskesmas (health center) heads. Building on Scott's (1985) idea of a "moral economy" I delve beneath the political tensions of competing autonomies to describe a moral landscape of underlying beliefs about how government ought to behave in the health sector. Through this analysis certain failures and contradictions in the decentralization process emerge, complicating the literature that presents decentralization as a move in the direction of "good governance" (Mitchell and Bossert 2010, Rondinelli and Cheema 2007, Manor 1999). Decentralization brings to the fore the internal divisions within government, yet health workers present a united front in their engagements with the public. Under increasing pressure to achieve global public health goals such as the Millennium Development Goals, health managers engage in multiple translations in converting global health discourses into national and local health policies and in framing these policies in ways that are comprehensible and compelling to the general public. Using the lens of a "cultural theory of state" (Corrigan and Sayer 1985) I describe how health professionals and volunteers draw on local cultural forms in order to render global frameworks compatible with local moralities. I introduce the term "moral pluralism" to describe how individual health workers interrelate several moral frameworks in their health promotion work, including Islam, evidence based medicine and right to health. My conclusion is that kabupaten health managers are engaging in two balancing acts. The first is between decentralization and (re)centralization and deals with the proper way to manage health programming. The second is between global health discourses and local cultural forms and concerns the most effective way to convey public health messages in order to bring about behavior change in line with national and global public health goals. This is the first anthropological study of how government officials at different levels negotiate the process of health decentralization in the face of increasing international pressure to achieve global public health goals.

Thesis (PhD)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The first part of this study describes the synthesis of new porous materials from basic building blocks. Five structurally related ligands namely: N,N'-bis(3-pyridylmethyl)-naphthalene diimide (L1), N,N'-bis(4-pyridylmethyl)-naphthalene diimide (L2), N,N'-bis(4-pyridylmethyl)- pyromellitic diimide (L3), N,N'-bis(3-pyridylmethyl)-pyromellitic diimide (L4) and 2-(pyridin-4- ylmethyl)-benzene tricarboxylic anhydride (L5) were synthesised. Ligands L1 and L2 were reacted with metal nitrates and carboxylates as co-ligands in a systematic manner with a view to obtaining potentially porous 3–D coordination polymers. Ten structurally diverse coordination polymers were obtained and they were characterised by single-crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analysis. Four of these compounds absorb moderate amounts of CO2 and, in addition, show sorption selectivity towards CO2 over N2. The reaction of L3 and L4 with transition metal halides yielded two 1–D chains, while the reaction of L5 with transition metal nitrates yielded seven coordination polymers of which four are 2–D and three are 1–D. Of the 2–D structures three are isostructural. The second part of this work describes a variable pressure study of a flexible metal-organic framework [Zn2(BDC)2(BPY)] (BPY = 4,4 -bipyridine and BDC = 1,4-benzene dicarboxylic acid). [Zn2(BDC)2(BPY)] is one of the few examples of a flexible metal-organic framework that undergoes phase transformations in response to gas pressure. The high pressure sorption recorded for this metal-organic framework displays two inflection steps in the pressure range 0 to 30 bar, possibly indicating two phase transformations. The gas-loaded structures for each phase transformation were determined by means of single-crystal X-ray diffraction. High-pressure differential scanning calorimetry was also carried out on the system in order to determine accurate gate-opening pressures, as well as the energies involved with each phase transformation. The results correlate with those obtained from single-crystal X-ray diffraction and high-pressure sorption. The final section reports the mechanochemical synthesis of two Werner complexes [NiCl2(4- PhPy)4] (1), [CoCl2(4-PhPy)4] (2) and their corresponding solid solution [Ni0.5Co0.5Cl2(4-PhPy)4] (3) (PhPy = phenyl pyridine). The solid solution could only be formed by mechanochemical synthesis and not by conventional solution crystallisation methods. The solid solution exhibits sorption properties that differ from those of the pure compounds. / AFRIKAANSE OPSOMMING: Die eerste deel van hierdie studie beskryf die sintese van nuwe poreuse stowwe uit basiese boublokke. Vyf struktureel verwante ligande naamlik: N,N'-bis(3-piridielmetiel)-naftaleen diimied (L1), N,N'-bis(4-piridielmetiel)-naftaleen diimied (L2), N,N'-bis(4-piridielmetiel)- piromellitien diimied (L3), N,N'-bis(3-piridielmetiel)-piromellitien diimied (L4) en 2-(piridiel-4- ielmetiel)benseen trianhidried (L5) is gesintetiseer. Ligande L1 en L2 is gereageer met metaal nitrate en karboksielsure as mede-ligande in 'n sistematiese wyse met 'n oog op die verkryging van potensieel poreuse 3–D koördinasie polimere. Tien struktureel diverse koördinasie polimere is verkry en hulle is gekarakteriseer deur enkel-kristal X-straal-diffraksie, poeier X-straal diffraksie en termo-analise (thermal analysis). Vier van hierdie verbindings het matige hoeveelhede CO2 geabsorbeer en, bykomend, wys sorpsie selektiwiteit van CO2 oor N2. Die reaksie van L3 en L4 met oorgangsmetaalhaliede het twee 1–D kettings gevorm, terwyl die reaksie van L5 met oorgangsmetaal nitrate sewe koördinasie polimere opgelewer het, waarvan vier 2–D en drie 1–D polimere is. Van die 2–D polimere het drie vergelykbare strukture. Die tweede deel van hierdie werk beskryf 'n veranderlike druk studie van 'n buigsame metaalorganiese raamwerk [Zn2(BDC)2(BPY)] (BPY = 4,4-bipiridien en BDC = 1,4-benseen dikarboksielsuur). [Zn2(BDC)2(BPY)] is een van die min voorbeelde van 'n buigsame metaalorganiese raamwerk wat fase transformasies (phase transformations) ondergaan in respons op ‘n verandering in gas druk. Die hoë-druk sorpsie aangeteken vir hierdie metaal-organiese raamwerk vertoon twee infleksie stappe in die gebestudeerde druk gebied (0 tot 30 bar), wat moontlik op twee fase transformasies dui. Die gas-gelaaide strukture vir elke fase transformasie is bepaal deur middel van enkel-kristal X-straal-diffraksie. Hoë-druk differensiële skandeer kalorimetrie (differential scanning calorimetry) is ook uitgevoer op die stelsel ten einde dié akkurate hekopenings druk, sowel as die energie betrokke by elke fase transformasie te bepaal. Die resultate stem ooreen met dié verkry vanaf enkel-kristal X-straal diffraksie en hoë-druk sorpsie. Die finale afdeling bespreek die meganochemiese sintese van twee Werner komplekse [NiCl2(4-PhPy)4] (1) en [COCl2(4-PhPy)4] (2) en hul ooreenstemmende vaste oplossing (solid solution) [Ni0.5Co0.5Cl2(4-PhPy)4] (3). Die vaste oplossing kan slegs gevorm word deur meganochemiese sintese en nie deur konvensionele oplossing kristallisasie metodes. Die vaste oplossing vertoon sorpsie eienskappe wat verskil van dié van die suiwer verbindings.

The synthesis of a scandium aluminium methylphosphonate ScAl₃(CH₃PO₃)₆ isostructural to the aluminium methylphosphonate AlMePO-α and with permanent microporosity is reported here for the first time. Structural characterisation of three lanthanide bisphosphonate structures (I,II,III) with the light lanthanides and N,N'-piperazine bis-(methylenephosphonic acid) and its 2-methyl and 2,5-dimethyl derivatives is described. The framework of structure type I shows considerable flexibility upon dehydration with a symmetry change from C2/c, a = 23.5864(2) Å, b = 12.1186(2) Å, c = 5.6613(2) Å, β = 93.040(2)˚) in the hydrated state to P2₁/n, a = 21.8361(12) Å, b = 9.3519(4) Å, c = 5.5629(3) Å, β = 96.560(4)˚ after dehydration. This cell volume reduces by 27% on dehydration and is accompanied by a change in the conformation of the piperazine ring from chair to boat configuration. The structures of type I (hydrated and dehydrated) were refined against synchrotron powder X-ray diffraction data. Despite the reversible hydration and flexibility, the structures possess no permanent porosity. Investigation of the solvothermal chemistry of scandium carboxylates identified routes to 7 framework structures 5 of which were previously unreported in the scandium system. Lower temperature solvothermal reactions using terephthalic acid (80 - 140°C using dimethylformamide and diethylformamide) yielded two scandium terephthalates, MIL-88B(Sc) and MIL-101(Sc), identified by laboratory X-ray powder diffraction. Whereas higher temperature (160 – 220°C), reactions gave MIL-53(Sc) and Sc₂BDC₃. Further study with the tri- and tetra-carboxylate linkers, trimesic acid, 3,3',5,5'-azobenzenetetracarboxylic acid and pyromellitic acid yielded MIL-100(Sc), Sc-ABTC and Sc₄PMA₃ respectively. Structural identification of MIL-100(Sc) and Sc-ABTC was performed by means of X-ray powder diffraction analysis and of Sc₄PMA₃ by single crystal X-ray diffraction. The structure of a small pore scandium terephthalate Sc₂BDC₃ was investigated as a function of temperature and of functionalization. In situ synchrotron X-ray diffraction data, collected on a Sc₂BDC₃ in vacuo, enabled a phase change from orthorhombic Fddd to monoclinic C2/c and the associated structural effects to be observed in detail. The orthorhombic structure displayed a negative thermal expansivity of 2.4 × 10⁻⁵ K⁻¹ over the temperature range 225 – 523 K which Rietveld analysis showed to be derived from carboxylate group rotation. Motion within the framework was studied by ²H wide-line and MAS NMR on deuterated Sc₂BDC₃ indicating π flips can occur in the phenyl rings above 298 K. The effects of functionalization on the Sc₂BDC₃ framework were investigated by reactions using the 2-amino- and 2-nitroterephthalic acid and gave evidence for a strong structural effect resulting from inclusion of the functional groups. The structure of Sc₂BDC₃ and the functionalised derivatives were solved using Rietveld analysis on synchrotron X-ray powder diffraction data. Sc₂(NH₂-BDC)₃ was solved using the orthorhombic Sc₂BDC₃ framework starting model and, over the temperature range studied, stayed orthorhombic Fddd. Sc₂(NO₂-BDC)₃, was shown to be monoclinic C2/c over the same temperature range, a result of the steric effects of the bulky –NO₂ group in a small pore framework. Partial ordering of the functional groups was observed in both Sc₂(NH₂-BDC)₃ and Sc₂(NO₂-BDC)₃. The strength of interaction for the Sc₂(NH₂-BDC)₃ with CO₂ was higher than that of the parent Sc₂BDC₃ due to the strong –NH₂•••CO₂ interaction. Despite the inclusion of a relatively large –NO₂ group along the walls of a channel ~4 Å in diameter the Sc₂(NO₂-BDC)₃ still showed permanent microporosity to CO₂ (2.6 mmol g⁻¹) suggesting that there must be some motion in the -NO₂ group to allow the CO₂ molecules to diffuse through the channels. The scandium analogue of the flexible terephthalate MIL-53, a competitive phase in the synthesis of Sc₂BDC₃, was prepared and characterised by Rietveld analysis on synchrotron X-ray powder diffraction data using a combination of literature structural models and models obtained from single crystal X-ray diffraction experiments. Experimental solid state ⁴⁵Sc, ¹³C and ¹H NMR data combined with NMR calculations on the structural models produced from diffraction analysis were used to identify the hydrated (MIL-53(Sc)-H₂O), calcined (MIL-53(Sc)-CAL) and high temperature (MIL-53(Sc)-HT) structures of MIL-53(Sc). Further to this the 2-nitroterephthalate derivative, MIL-53(Sc)-NO₂, was prepared and characterised using single crystal X-ray diffraction. The adsorptive properties of the parent terephthalate and the functionalised derivative were compared and in both cases showed a breathing behaviour, exemplified by steps in the adsorption isotherms. MIL-53(Sc)-CAL was found to possess a closed pore configuration in the dehydrated state, a previously unreported structural form for the MIL-53 series, and its presence can be observed in the low pressure region of the CO₂ adsorption isotherm as a non-porous plateau. The selectivity and separation properties of two MOFs, the nickel bisphosphonate, STA-12(Ni) and the scandium carboxylate, Sc₂BDC₃ were measured using breakthrough curves on mixtures of CH₄ and CO₂. The results showed both materials to be highly selective in the adsorption of CO₂ over CH₄. Column testing using a PLOT column of STA-12(Ni) and a packed column of Sc₂BDC₃ showed promising preliminary results with STA-12(Ni) displaying effective, baseline separation on low boiling point hydrocarbon mixtures (C1 – C4) while the smaller pore channels of Sc₂BDC₃ were effective in the size selective separation of higher boiling point branched and straight-chain hydrocarbons (C5 – C7).

This thesis addresses corporate approaches to CSR stakeholder engagement in the pharmaceutical industry in the UK and Germany. Its objective is to undertake mainly exploratory qualitative research to investigate how the selected sample manages CSR. The data was primarily accessed and collected from senior executives within major pharmaceutical companies. Multiple research methods were employed to gather rich new empirical evidence which focuses on the CSR practices and perceptions of CSR managers in both countries. To examine how this 'sensitive' sector responds to what could be termed the 'CSR Challenge', a critical realist perspective and six codes were chosen to map the practices and to compare similarities and differences between the two countries. This research contributes to the academic literature in this field by filling significant gaps in an area which was previously under-investigated. Ultimately, the findings are employed to examine a prespecified framework which was originally developed by the author based on secondary data in separate research. Overall, the results inform, re-examine, and improve this recently published framework. The updated explanatory framework which results from the research is the main conceptual contribution of the thesis. It serves as a management tool which includes the contextual factors which influence decision-makers' practices and perceptions portrayed as a set of inter-related management steps. This new conceptualisation is designed to be of practical use for decision-makers when managing their stakeholder engagement activities. As a result, this research is essentially applied and normative in nature. In addition, this work presents an original contribution to the literature in its field which should be of interest to academics.

Metal-Organic Frameworks (MOFs) are nanoporous framework materials with tunable pore size and functionality, and hence attractive for gas separation membrane applications. Zeolitic Imidazolate Frameworks (ZIFs), a subclass of MOFs, are known for their high thermal and chemical stability. ZIF-8 has demonstrated potential to kinetically separate propane/propene in powder and membrane form. ZIF-8 membranes propane-propene separation performance is superior in comparison to polymer, mixed matrix and carbon membranes. The overarching theme of my research is to address challenges that hinder fabrication of MOF membranes on a commercial scale and in a reproducible and scalable manner. 1. Current approaches, are specific to a given ZIF, a general synthesis route is not available. Use of multiple steps for surface modification or seeding causes reproducibility and scalability issues. 2. Conventional fabrication techniques are batch processes, thereby limiting their commercialization. Here we demonstrate two new approaches that can potentially address these challenges. First, we report one step in situ synthesis of ZIF-8 membranes on more commonly used porous α-alumina supports. By incorporating sodium formate in the in situ growth solution, well intergrown ZIF-8 membranes were synthesized on unmodified supports. The mechanism by which sodium formate promotes heterogeneous nucleation was investigated. Sodium formate reacts with zinc source to form zinc oxide layer, which in turn promotes heterogeneous nucleation. Sodium formate promotes heterogeneous nucleation in other ZIF systems as well, leading to ZIF-7, Zn(Im)2 (ZIF-61 analogue), ZIF-90, and SIM-1 films. Thus one step in situ growth using sodium formate provides a simplified, reproducible and potentially general route for ZIF film fabrication. One step in situ route, although advantageous; is still conventional in nature and batch process with long synthesis time. This limits commercialization, due to scalability and manufacturing cost issues. Taking advantage of coordination chemistry of MOFs and using temperature as driving force, continuous well-intergrown membranes of HKUST-1 and ZIF-8 in relatively short time (15 min) using Rapid Thermal Deposition (RTD). With minimum precursor consumption and simplified synthesis protocol, RTD provides potential for a continuous, scalable, reproducible and commercializable route for MOF membrane fabrication. RTD-prepared MOF membranes show improved separation performances, indicating improved microstructure.