The work reported in this thesis describes the successful preparation of three classes of polymer that were designed to possess intrinisic microporosity from a range of aromatic tetrahydroxy and diamine monomers. The tetrahydroxy family of monomers were used to prepare a number of polybenzodioxane polymers and co-polymers using the chemistry developed for the archetypal PIM-1. Two co-polymers formed films suitable for gas permeability measurements indicating that they transport gases at high selectivity but lower permeability as compared to PIM-1. The diamino-containing monomers were used to prepare a number of polyimides (PIM-PIs) using well-established polymerisation chemistry and also some Troger’s base polymers (PIMTBs) using a recently developed polymerisation method. A series of TB-PIMs with different substituents next to the amino group (H and CH3) and containing various pendant groups were prepared in order to establish structure-property relationships. Some of these polymers proved microporous with surface areas ranging from 22-510 m2/g. Unfortunately, none were suitable for film formation or gas permeation measurements. PIM-PIs were prepared from diamino monomers based on bulky 1,4-ditritylbenzene (BAB), adamantane (AD) and trifluorodiaminoaryl (TFA) units by reaction with commercial 4,4′- (hexafluoroisopropylidene)diphthalic anhydride (6FDA). Some of these polymers also demonstrated microporosity with surface areas ranging from 8-560 m2/g. Two polymers (PIM-AD5- PI and PIM-AD6-PI), exhibited good solubility, excellent thermal stability and intrinsic microporosity, with the introduction of highly rigid and bulky groups adjacent to the imide group. PIM-AD5-PI and PIM-AD6-PI demonstrate a very good combination of high permeability and good selectivity for CO2/CH4, H2/N2 and H2/CH4 gas pairs with data that lie close to the Robeson 2008 upper bounds, which is the benchmark for the evaluation of the potential of a new polymer for making gas separation membranes. Finally, a series of trifluoromethyl (CF3) containing PIM-PIs were prepared. Again, it was found that by increasing the rigidity of the polymers by increasing the number of methyl substituents a greater amount of intrinsic microporosity is generated by the polymer. Seven polymers of this series formed robust films suitable for gas permeability measurements and demonstrated good selectivity for CO2/CH4, O2/N2, H2/N2 and H2/CH4 gas pairs with data that lie near the 2008 upper bounds.

Microporous materials have received much attention and offer new opportunities in electrochemistry because of their interesting properties. Compared with the corresponding nonporous materials, the highly porous structure may facilitate internal mass transport process, provide accessibility to binding sites and provide size selectivity. A new class of microporous materials, polymers of intrinsic microporosity (PIMs) emerged about ten years ago. They combine the microporosity generated from the rigid and contorted backbones and the processibility of linear molecular polymers, which make them particularly attractive for the applications in gas storage, membrane separations and also in electrochemistry. PIM-EA-TB containing ethanoanthracene (EA) and Tröger’s base (TB) is one of the most interesting PIMs and has a high BET surface area around 1000 m2 g-1. Most of the work in this thesis are based on PIM-EA-TB. Results chapters focus on catalysis in PIM films, ion flux in free-standing PIM membranes and carbonization of PIM-EA-TB. Electrochemical oxidation of glucose is important due to the practical applications in glucose sensing and in biological fuel cells. However, the practical application of many catalysts is limited by the poisoning by interferences such as proteins and chloride. Here, PIM-EA-TB was spin-coated onto the surface of supported gold nanoparticles to protect the catalysts from poisoning. It was demonstrated that the PIM-EA-TB film would not negatively affect the catalytic performance of gold nanoparticles for glucose oxidation. Also, it provided effective protection against protein poisoning because of its rigid backbone and rigid molecular structure preventing protein access. Chloride poisoning was reduced but not surpressed. In addition to nanoparticle catalysts, water-insoluble molecular catalysts were investigated. PIM-EA-TB was used as a rigid host for model catalyst, tetraphenylporphyrin (FeTPP). FeTPP was immobilised in the PIM-EA-TB film and then deposited on the electrode to create a high density heterogenised catalysts. Different compositions of PIM and FeTPP and different scanrates were investigated to reveal the catalytic mechanism. The PIM hosted FeTPP catalysts showed facile electron transfer and effective electrocatalytic reduction of oxygen and peroxide. The 4-(3-phenyl-propyl)-pyridine was applied to the PIM-FeTPP film to give an organogel in 12 order to investigate the liquid-liquid interface. The PIM immobilisation method could offer a new opportunity to the immobilisation of a wide range of the molecular catalysts. The understanding of transport processes in PIM-EA-TB membranes is important for the development of further applications in the electrochemistry. Different types of anions were investigated to see the anion uptake and charge transport in PIM-EA-TB films. Three cases were investigated, including the oxidation of ferrocene, the reduction of protons and the transport of anions and protons in the PIM-EA-TB thick films. In all three cases, the diameter and hydrophobicity of anions are important in the competing effects. The pKa of PIM-EA-TB was determined and novel ionic diode effects were observed. Nanofluidic devices are used to regulate the flow of ions to one preferential direction and they have great importance because of the similarity to biological ion channels and the application in biochemical fields. PIMs were explored to the possibility to establish an artificial ion channel with the gate function. A thin film preparative method was introduced to produce thin free-standing polymer films. The 300 nm PIM-EA-TB films supported on a poly-ethylene-terephthalate (PET) film with a 20 m diameter microhole exhibited ionic diode behaviour. Only when the cation and anion had different mobility, the current rectification effects were observed. Different pH values of the electrolyte were also investigated and resulted in a gradual change in rectification effects. Porous carbon materials have wide applications in different fields such as gas separation, water purification, catalyst supports, and fuel cells. One of the common methods to produce the porous carbon is the carbonization of polymers. However, the challenge is that it is difficult to control the pore size and pore distribution. PIM-EA-TB was carbonized at 500 °C in vacuum to produce a novel type of microporous carbon. The microporosity and morphology of the PIM precursor remained after carbonization. The new material exhibited relatively low electrical conductivity and low activity in the electrochemical oxygen reduction. The capacitance of the new carbon material was investigated and found to vary with pH depending on the protonation status of micropores. 13 Finally, the carbonized PIM films were used to control the formation of platinum nanoparticles. Platinum nanoparticles are important catalysts in many areas but may suffer from high costs and lack of reproducibility. Therefore, it is important to reduce the amount of platinum, increase the utilization of platinum as well as control the particle size. The carbonized PIM films still have the microporosity and offer an ideal substrate for platinum nanoparticles. The platinum nanoparticles were formed at the same time with the carbonization of PIM, which helped to control the size of platinum nanoparticles. Compared with bare platinum, the platinum nanoparticles produced by PIM-EA-TB showed a high electrochemically active surface area and good catalytic performances for oxygen reduction, methanol oxidation and glucose oxidation. Much less platinum (1μg per cm2) was needed to achieve the same catalytic performance compared to the bulk platinum.

Polymers of Intrinsic Microporosity (PIMs) combine the desirable processability of polymers with a significant degree of microporosity generated from the inefficient packing of their rigid and contorted structures. They are attracting attention for a variety of applications including as membrane materials for gas separations. Over the last 30 years, membranes have become an established technology for separating gases and are likely to play key role in reducing the environmental impact and costs of many industrial processes such as O2 or N2 enrichment from air, natural gas upgrading and hydrogen recovery from ammonia production. This thesis describes the synthesis of a series of novel PIMs, primarily PIM-polyimide structures (PIM-PI) and investigates their potential in such applications. In particular, it focuses on the design and synthesis of solution processable PIMs in order to study how structural differences affect the gas permeability. The first section describes the synthesis of a variety of PIM-PIs using large bulky diamines derived from spirobisindane (SBI) and biphenylfluorene (BPF) structures which are useful monomers for achieving high BET (Brunauer-Emmett- Teller) surface areas (> 650 m2 g-1). The second section describes a whole series PIs based on novel and literature based Tröger’s base (TB) diamine monomers. Most of these exhibited good solubility, excellent thermal stability and intrinsic microporosity, with apparent BET surface areas in the range 450-739 m2 g-1. Notably, a polyimide derived from Me2TB and pyromellitic anhydride demonstrates gas permeability data above the 2008 upper bounds for important gas pairs such as O2/N2, H2/N2 and H2/CH4. The third section aims to enforce rigidity within the polymers further by incorporating differently substituted monomers based on rigid ethanoanthracene (EA) units. This includes the formation of a novel EA-EA based PI with an exceptionally rigid polymeric structure, possessing a BET surface area of 694 m2 g-1. In addition to very high permeability, this polymer demonstrates improved gas selectivity due to its enhanced performance as a molecular sieve, placing it amongst some of the highest performing polymers to date. The final section looks at other ways in which rigidity can be enforced including the formation of TB-polymers and thermally rearranged (TR) polymers and assesses their potential for future investigations.

No description available.

A range of adsorbents have been evaluated for the adsorption of selected herbicide compounds from aqueous solution. The adsorption performance of LF -1, a carbonised polymer produced in the laboratory, Amberlite XAD-4, a commercially available polymeric adsorbent produced by Rohm and Haas and MN-200, a HypersolMacronet polymer produced by Purolite, were compared with a commercial activated carbon, Chemviron F -400. The pore size distributions of the adsorbents have been investigated using nitrogen adsorption. F-400, LF-1 and MN-200 were found to contain similar microporous structures. The carbons also possess a significant degree of mesoporous structure, which may enhance the diffusion of organic species into the micropores. The pore size distribution for XAD-4 shows an almost exclusive meso/macroporosity with very little microporous structure. Spectroscopic analysis and titration of the adsorbents indicated a number of different oxygen functional groups. XPS and elemental analysis suggested higher oxygen concentrations than those obtained using direct titration, which was attributed to bound oxygen within the structure of the adsorbents. The adsorption capacity of phenol was assessed as a characterisation technique. The capacity of the carbons was much greater than the polymeric adsorbents. Analytical techniques were developed and validated for the determination of trace levels (0.1 parts per billion) of five herbicides; atrazine, benazolin, bentazone, imazapyr and tric1opyr. Single and multi-component adsorption isotherms are presented for trace concentrations of the herbicides in aqueous solution. The effect of pH and fulvic acid upon the adsorption was also investigated. Mini-column experiments were performed using multi-component mixtures. In all cases, the uptake of herbicides on F -400 is greater than on the other adsorbents. Regeneration of F-400 and MN-200 was investigated usmg solvent stripping techniques. Significant regeneration efficiencies were observed using ethanol at pH 12 and 50°C to make the technique a viable option.

No description available.

Microporous catalysts belong to a class of materials that exhibit pore networks in the molecular dimension, that is, channel diameters less than 2 nm. The industrially most important microporous catalysts are zeolites, which are crystalline aluminosilicates and consist of interlinked alumina (AlO4) and silica (SiO4) tetrahedra forming pores and cavities of molecular dimensions. Zeolites can act as very strong solid acids and function as heterogeneous catalysts in various industrial processes used to obtain polyethylene terephthalate (PET) or polyvinyl chloride (PVC). They are crucial for products with a significant market demand such as plastics used in bottles, packaging materials and household consumable goods as well as for coatings of pharmaceutical pills and detergents. Recently, zeolites have been found to have increased applications in aqueous and biphasic reactions that use reactants derived from biomass to arrive at petrochemical products. Thus, surface acidity in zeolites is crucial to understand to tune parameters such as activity and selectivity of zeolite catalysts to optimize product distributions. The objective of this dissertation was to validate the use of non-invasive nuclear magnetic resonance (NMR) techniques to characterise surface acidity in zeolites by benchmarking the NMR results to various more established zeolite characterisation techniques, such as Fourier transform infrared (FTIR) spectroscopy and temperature-programmed desorption (TPD). Furthermore, the use of the tapered element oscillating microbalance (TEOM) to characterise internal and external acidity in zeolites was explored. IR and TPD techniques were used to assess important acidity parameters such as type, number, location and strength of acid sites of ZSM-5 zeolites with varying silica-alumina ratio (SAR = SiO2/Al2O3). The use of NMR relaxation time analysis of pyridine adsorbed in ZSM-5 was then explored as a model system to study surface acidity in microporous materials. Correlation with pyridine TPD results suggested that NMR relaxation time analysis probes the effective strength of pyridine adsorption sites, which varies with SAR. NMR relaxation time analysis was then further shown to be applicable to characterise non-acidic surface properties such as the hydrophilic and hydrophobic surface character. Lastly, the NMR techniques developed at high magnetic field strength (300 MHz) were transferred to a portable, low-cost benchtop low-field (43 MHz) magnet and shown to be applicable for base probe molecules other than pyridine, that is, ammonia (NH3) as well as zeolite framework types other than ZSM-5, that is, chabazite (CHA).

In order to heighten the nickel content in mesoporous silica frameworks, a new direct synthesis method, called modified DS method, has been developed instead of the commonly used direct synthesis method. In addition, with the aim of incorporating a high amount of titania into SBA-15 mesoporous silica without blocking its mesopores, a multistep impregnation method, called the MSI method, has also been developed. By using the two developed methods, high nickel- and high titania-containing mesoporous silicas obtained werc synthesized. The nickel- and titania-containing mesoporous silicas were characterised by various techniques, i.e. XRD, TEM, EDX, SENI, N2-sorption, XPS, FTIR, UV-Vis-DRS, UV-VIS, TPR, and Raman spectroscopy. For nickel-containing mesoporous silicas synthesized by the modified DS method, satisfactory mesostructures were obtained and the nickel content was increased up to 14.7 wt.%. So far, no reports have been published on synthesis of mesoporous MCM-41-type silica with higher nickel content than 3.6 wt.% using DS method. Via our modified IDS method, high BET surface area (>840 rný/g) and pore volume (>-0.73 cm3/g were also achieved. Nickel was found to be incorporated into the silica frameworks. Formation of nickel phyllosilicates was also confirmed. After activation, mesostructurcs were still intact. Small nickel clusters embedded in the silica walls were found. A high amount of titania (up to 24.4 wt.%) was incorporated into the mesoporous SBA-15 silica via the multistep impregnation method. No damage to the SBA-15 silica mesostructures was caused. The existence of small titania nano-domins was confirmed to be present by Raman and UV-vis-DRS measurements. High dispersion of them was realized via this method according to the results of low-anglc XRD, TEM and N2-sorption measurements. Importantly, no blockage of mesopores was observed. Photo-activity tests showed the superiority of the materials synthesized by the MSI method to those by one-step impregnation method.

The primary aim of this thesis is to investigate and quantify the self-diffusion processes of gaseous molecules adsorbed in industrially relevant microporous zeolite materials using Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). The main body of this work involves the use of weakly adsorbing hydrocarbon gases (CH4, C2H6 and C3H¬8) adsorbed in a large pore β-zeolite structure. This thesis describes the development of a solely PFG NMR based technique for measuring the molecular displacements of these species at varying length-scales. This enabled the characterisation of self-diffusion regimes across zeolite beds and within individual zeolite crystallites. The characterisation of self-diffusion processes within single zeolite crystallites was critical with respect to accounting for quantitative discrepancies reported in the literature between PFG NMR and alternative measurement techniques. This approach also revealed that the transitions in the Gaussian probability distributions of the molecular displacements in the aforementioned self-diffusion regimes could be recorded by varying the experimental time-scale for observing molecular motion. This technique was extended to characterise the self-diffusion processes of the aforementioned hydrocarbons in small (≤ 1 μm) and large (≥ 15 μm) zeolite crystallites to investigate the dependence of this technique on zeolite geometry. It was found that the self-diffusion coefficients within single crystallites were in good agreement with one another, despite their differing crystallite geometries. This technique was subsequently used to study the self-diffusion behaviour of two-component hydrocarbon gaseous mixtures with differing sorption properties co-adsorbed in β-zeolite. Excellent chemical shift resolution was obtained for chemically similar species using NMR spectroscopy, relaxometry and diffusometry without the use of Magic Angle Spinning (MAS). This connoted that conventional PFG NMR is capable of precisely characterising individual species in real world multi-component systems. This thesis also describes the self-diffusion of ammonia in small pore chabazite structures, which are typically used in Selective Catalytic Reduction (SCR) processes. It was found that the self-diffusion coefficient of this strongly adsorbing species increased with molecular loading up to a certain point. This peculiar behaviour implied a strong concentration and inter-molecular dependence within the zeolite structure. Lastly, the techniques which were developed at high magnetic field strengths (300 MHz) were transferred to a lower field strength (43 MHz) benchtop spectrometer at the Johnson Matthey Technology Centre (JMTC). This describes the first characterisation of mass transport behaviour of weakly interacting sorbates in zeolites using a portable spectrometer. This presents an excellent opportunity for future off-line molecular displacement measurements to be made for complex and real-world systems in a matter of minutes.

This thesis investigates the feasibility of producing activated carbon from polysaccharides. Activated carbons are high surface area solids with rich surface functionality and as a result, find use in a variety of industrial separation processes. The market for activated carbon is already established and growing but there is a huge push to find sustainable alternatives for the raw material used for its production, which is primarily coal. While there exists a significant amount of research on agricultural residues as potential replacements, there is minimal information on using polysaccharides as precursors for the production of activated carbon. Using the patented PGX process, two separate approaches were employed for the synthesis of activated carbon. The first method relied on the porous network of PGX materials to be maintained during pyrolysis while the second approach used a chemical agent to create porosity during the pyrolysis. Gas sorption analysis revealed that the PGX structure was not maintained during the pyrolysis stage hence losing all its pore network and extended surface area. Additionally, no significant variation between the PGX and non PGX variants of the chemically activated polymers was observed. However, it was revealed that the interaction between zinc chloride and pectin produced exceptionally high specific surface area (exceeding 2000 m2 g-1) activated carbon. The produced carbon had a high degree of microporosity (up to 100%) with some flexibility present in tuning the porosity. Elemental analysis revealed the carbon to have high surface functionality and preliminary adsorption test for removal of heavy metal ions from water (Pb2+ and Cd2+) showed promising results with the in-house carbon performing better than a representative commercial carbon. This study relies on statistical methods including multiple design of experiment studies and advanced characterization techniques to analyze the manufacturing process and the properties of carbon in an attempt to find the best conditions for producing activated carbon from polysaccharides. / Thesis / Master of Applied Science (MASc)