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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
51

Base-metal catalysis for the hydrogenation of acetic acid

Lynch, Ailsa S. January 2014 (has links)
Increasing global ethanol consumption has revived research into a variety of route for the synthesis of ethanol. One such route is via the hydrogenation of acetic acid, for which a catalyst with significant acid tolerance is required. The objective of finding an active, acid tolerant base metal catalyst was central to this project. In this study, a commercial methanol synthesis catalyst was initially investigated for its viability as an acid hydrogenation catalyst, following the production of ethanol when acetic acid was passed over it in a different study [1]. The methanol synthesis catalyst was not a viable option due to deactivation, but the use of a copper based system was shown to be active, in line with other studies [2]. Copper based catalysts were tested in both integral and differential reactor systems. The copper catalysts, with metal loadings of 5 wt.% and 10 wt.%, showed some activity towards the production of ethanol, but not in comparable quantities to those observed with the high copper content methanol synthesis catalyst. The effect of higher acetic acid concentrations, up to 20 mol.%, within an atmospheric fixed bed system were investigated, and showed that copper based catalysts were physically compromised by the presence of acetic acid. Deactivation and degradation of this catalyst upon exposure to acetic acid, especially at higher concentrations, meant that it was not appropriate for this process. The propensity of the copper catalysts to degrade in the presence of acetic acid led to other base metal systems being investigated, in the form of nickel and cobalt catalysts. All three base metal systems were investigated within a differential reactor to show direct comparisons of each catalyst at 10 wt.% and 20 wt.% metal loadings. This research showed that cobalt based systems were the most active of the metals tested at the two separate loadings. A study into the effect of the catalyst support using an 10 wt.% cobalt loading, on a range of supports, showed that alumina was the superior support for the selective hydrogenation of acetic acid to ethanol. The other supports investigated were silica, titania and zinc oxide. Comprehensive testing of the catalysts prepared with cobalt, copper and nickel, identified that the 20 wt.% cobalt on alumina was the most stable, in terms of activity and catalyst integrity, and active catalyst of those investigated at an optimal reaction temperature. 1. Blain, S., Ditzel, E., and Jackson, S. D., A mechanistic study into the effect of acetic acid on methanol synthesis. Catal. Sci., 2012. 2(4): p. 778-783. 2. Cressely, J., Farkhani, D., Deluzarche, A., and Kiennemann, A., The Evolution of Carboxylate Species in the Framework of CO-H2 Synthesis - Reduction of Acetic-Acid on the Co,Cu,Fe System. Mat. Chem. Phys., 1984. 11(5): p. 413-431.
52

Utilising high work function metal oxides as hole extracting layers for organic photovoltaic cells

Hancox, Ian January 2013 (has links)
A substantial amount of research has already been undertaken towards creating commercially viable organic photovoltaics (OPVs). This is due to the potential use of OPV cells as an inexpensive source of renewable energy. There are many factors to consider in OPV cell design, including photo-active materials, cell architecture and electrode selection. However, additional interlayers for use between the photo-active materials and the electrodes were identified to be as important and need to be developed to optimise cell performance. The work presented here focuses on the influence of various metal oxide hole extracting layers in different OPV systems. Metal oxides such as molybdenum oxide (MoOx) have shown great promise in polymer cells as a hole extracting layer, and here we investigate their use in small molecule cells. An optimised MoOx layer thickness of 5 nm provides a ~ 60 % increase in overall power conversion efficiency (ηp) for chloroaluminium phthalocyanine (ClAlPc) / fullerene (C60) cells in comparison to those fabricated on bare ITO. A similar improvement of ηp is reported when using the MoOx layer in a boron subphthalocyanine chloride (SubPc) / C60 system. For both high ionisation potential donor materials, the cells containing MoOx achieve a significantly higher open circuit voltage (Voc). Conversely, cells utilising the lower ionisation potential donor materials such as copper phthalocyanine (CuPc) and pentacene produce similar Voc values when deposited on both ITO and MoOx. Hence, the ηp is marginally reduced with the MoOx layer. To attain a deeper understanding, the factors behind these performance differences were explored by UV-vis absorption spectroscopy, ultra-violet photoemission spectroscopy (UPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). Thermally evaporated vanadium oxide (V2Ox) was used as an alternative hole extracting layer to MoOx, achieving analogous performance to MoOx when used in SubPc / C60 and CuPc / C60 cells. The electronic properties of the V2Ox layer are investigated using UPS, and it is demonstrated to have substoichiometric n-type character in contrast to the p-type behaviour previously reported. Additionally, the in-situ fabrication and characterisation of organic layers using UPS indicate Fermi level pinning of the organic to the metal oxide. A solution processed vanadium oxide (V2Ox(sol)) layer was developed and characterised as an alternative method of layer fabrication. The atmospheric processing conditions are found to have a dramatic effect on cell performance, and are studied using x-ray photoelectron spectroscopy (XPS). Layers spin-coated under a nitrogen atmosphere exhibit a larger composition of V4+ states. Kelvin probe and UPS experiments indicate the V2Ox(sol) is also a high work function, n-type layer, with the V2Ox(sol) hole extracting layer producing similar cell performance to the thermally evaporated metal oxide layers. Cells deposited on the V2Ox(sol) layer demonstrate good operational stability characteristics, outperforming a commonly used solution processable hole extracting layer.
53

Extractives from Sitka spruce

Caron-Decloquement, Annabelle January 2010 (has links)
The term extractives defines chemical compounds of different classes that can be extracted from wood or bark by means of polar or non-polar solvents. Extractives are derived mostly from the metabolic processes of the tree, particularly the sapwood to heartwood transformation. The first objective of the research was to study the distribution of extractives within Sitka spruce trees at different heights in the trunk, as well as the distribution between bark, rootwood, knotwood, heartwood and sapwood. The second aim of the work was to learn about the influence of yield class, site elevation, North/East location and thinning on the extractives content and composition of Sitka spruce across Scotland. The samples were sawdust obtained in different ways from either discs, knots or roots sawn from Sitka spruce trees freshly cut in the forest, or collected during the coring of trees from 64 sites all around Scotland and northern England. The extraction was carried out on Soxhlet extractors using acetone as solvent. Two analytical techniques were used: gas chromatography and Fourier transform infrared spectroscopy. The results of the research showed that the extractive content and composition of Sitka spruce differed according to the type of wood studied with the largest amount detected in bark and the lowest in heartwood and sapwood. The last two types of wood were studied in more detail, showing that the difference in extractive content between heartwood and sapwood was consistent at all heights in the trunk. The chromatographic analysis of heartwood, sapwood, knotwood, rootwood and bark showed that their compositions differed slightly from published data on Norway spruce.
54

The structure/activity relationship of nitrobenzene hydrogenation over Pd/alumina catalysts

Morisse, Clément January 2015 (has links)
The hydrogenation of nitrobenzene to form aniline is a large-scale industrial process performed using a variety of heterogeneous catalysts. One variant of the process involves the application of alumina-supported Pd catalysts. Although several 0.3 wt% Pd/alumina formulations exhibit high aniline selectivity (ca. 98%), different grades of these catalysts favour different impurities. It is observed that the impurities arise from different reaction pathways depending on the provenance of the catalyst. In order to investigate whether the origins of impurity formation are connected to catalyst structure, a series of Pd catalysts active for this reaction have been characterised by a variety of techniques: chemisorption measurements, X-Ray Diffraction, Transmission Electron Microscopy, Temperature-Programmed Desorption and Infrared spectroscopy. The low metal loading industrial grade catalysts are challenging to characterise and required a degree of analytical refinement. Temperature-programmed infrared measurements of the probe molecule carbon monoxide revealed morphological and energetic information that could be correlated with catalytic performance. This information constitutes part of a valuable feedback loop that enables specifications for the next generation of ultra-selective nitrobenzene hydrogenation catalysts to be determined.
55

The synthesis and separation properties of organic cage compounds

Kewley, Adam January 2014 (has links)
Microporous materials play an important role in a variety of industrial and domestic applications. While a diverse range of microporous materials have been identified, this thesis focuses on porous organic cages (POCs) because they have received much attention as synthetically tunable, solution processable, microporous materials. After introducing the latest developments in POC synthesis and the general application of microporous materials as selective sorbents, this thesis presents three developments in organic cage chemistry: a high-throughput workflow for the discovery of POCs, which yielded a novel organic cage compound; the measurement of selective adsorption by POCs, wherein the first instance of chiral selectivity by a POC was recorded; and the first instance of applying POCs as stationary phases for gas chromatography, which produced columns that separate racemic mixtures, alkylaromatic isomers, and alkane isomers. Chapter 2, discovering novel organic cages, presents attempts to use high-throughput and in-silico techniques to accelerate the discovery of novel organic cages. These methods were utilised to isolate a novel organic cage, CCX-S, which is characterised and discussed. Chapter 3, organic cages as selective sorbents, presents the development of approaches for measuring selective adsorption. These methods were used to identify the first reported instance of enantioselective adsorption by an organic cage. Further measurements to explain this separation behavior are also presented. Chapter 4, chromatographic separations with organic cages, presents one method of practically leveraging the presented separation behavior. In Chapter 4, the coating of capillary columns with CC3 is presented. These columns were used to successfully perform gas chromatographic separations, the first recorded instance of using a POC to do so. The columns were further improved by modifying the coating method and using prefabricated CC3 nanoparticles. This modification enabled difficult separations to be performed using the column; for example, the separation of hexane’s five isomers.
56

Understanding the effects of high-pressure, high-temperature processing on the key quality parameters of green beans (Phaseolus vulgaris) with a view to assessing the potential quality benefits of the approach relative to conventional thermal processing

Leadley, Craig Edward January 2012 (has links)
Studies were conducted to explore whether high pressure (up to 700 MPa) could be used in combination with elevated temperatures (up to 90°C initial temperature) to produce ambient stable green beans (Phaseolus vulgaris) with improved quality compared with conventionally heat processed samples. Colour changes, texture change and chlorophyll retention were explored at a range of pressures, temperatures and times using a surface response methodology. Texture changes were essentially related to temperature effects; higher temperatures resulted in a greater loss in texture. Significant improvements in texture retention were possible using High Pressure Sterilisation (HPS) but sample colour was negatively affected. Colour parameters were predicted primarily by time and pressure so deterioration in green vegetable quality for a commercially sterile products appears inevitable when using HPS. The use of ohmic heating as a pre-heating method greatly reduced cook values (T\(_{ref}\) = 100°C, z = 39C°) for colour degradation (down to 0.24, 0.12, 0.35 from 3.02, 2.50, 3.70 minutes for ohmically heating and water bath heated samples respectively) which yielded significant benefits in terms of colour retention of raw materials at the start of the HPS cycle; values of a* and b* for ohmically pre-heated samples were close to that of blanched beans.
57

Design of photo-switchable self-assembled monolayers for the study of protein-receptor interactions

Charlesworth, Scott January 2012 (has links)
Nano-biotechnology combines recent advances in nanotechnology with biology. It is a relatively new discipline and full of promise. One such promise is the elucidation of complex bio-molecular reactions and interactions, the elucidation of which requires the development of reliable in-vitro models. Such models could be developed through the use of self-assembled monolayer’s (SAMs). Research into this competitive field has already started and there is currently a call to develop SAMs which present specific bio-molecules in a switchable fashion; switchable SAMs can have their surface properties switched between two states, i.e. they can be switched ‘on’ or ‘off’. Such switch-ability would help such models mimic the real time changes of the bodies’ bio-chemistry and is a vital development. This thesis addresses this current research need, through the employment of azobenzene based SAMs. Currently the switch-ability (isomerisation) of numerous azobenzene SAMs has been shown to be hindered by a lack of inter-surfactant space. This hindrance to isomerisation is addressed in Chapter 4. While Chapter 5 explores the design of an azobenzene based photo-switchable SAM, for use as in-vitro model for the study of bio-molecular interactions. The two chapters are not directly related and future work would aim to bring the findings together.
58

Gas mixing in anaerobic digestion

Dapelo, Davide January 2016 (has links)
Mesophilic anaerobic digestion is one of the most used and successful technologies to treat the sludges resulting from wastewater treatment. However, traditional approaches to digester design are firmly rooted in empiricism and rule of thumb rather than science. Mixing is an energy-intensive operation, and therefore the need to lower the wastewater process carbon footprint requires searching how to lower the input mixing energy without compromising–and indeed enhancing–biogas production. In particular, the literature on gas mixing is still particularly poor. For the first time, an Euler-Lagrangian CFD model was developed for gas mixing in anaerobic digestion. The model was validated against laboratory experiments with PIV and PEPT techniques. Full-scale simulations reproducing a real digester were performed with the validated model, and different scenarios were reproduced. Shear rate distribution was used as a parameter to assess the most appropriate value of input mixing power. The simulations also low-viscosity flow patterns for the first time. This phenomenon is intrinsically linked to the non-Newtonian nature of sludge, and leads to short-circuited mixing. Switching biogas injection between two different nozzle series was found to be an effective strategy to mitigate the issue of the low-viscosity flow patterns. Final recommendations on input mixing power and switching time were given to improve mixing efficiency in the full-scale design taken into consideration. A journal paper published in Water Research and a conference paper presented at the Fifteenth International Conference on Civil, Structural and Environmental Engineering Computing (Civil-Comp) were produced. Two other papers are currently in preparation.
59

Multi-component crystallisation approaches to controlling crystalline forms of active pharmaceutical ingredients

Wales, Craig January 2013 (has links)
Multi-component crystallisation is investigated as a route to controlling crystalline forms of selected materials that possess pharmaceutical properties. This includes investigating the use of co-crystallisation methodology to selectively crystallise metastable polymorphs and solvated forms of these materials. This differs from the conventional use of co-crystallisation, as the aim of this aspect of the investigation is not to obtain a molecular complex of the two components, but instead for them to crystallise independently, while one component perturbs the solution environment to direct the crystallisation of the second component towards a different, often metastable, polymorph (or solvate). This co-crystallisation methodology is used as a route to crystallising new or elusive polymorphs (or solvates) of the active pharmaceutical ingredients paracetamol, piroxicam, gallic acid monohydrate and piracetam. It is also demonstrated that the use of this method can lead to crystal forms with otherwise unobtainable structural features. Co-crystallisation is also investigated as a route to controlling the ionisation state of piroxicam in the formation of molecular complexes. Molecular complexes were formed with a number of mono-substituted benzoic acids as well as with nitrogen-heterocycles and strong acids. In the molecular complexes formed, piroxicam was found to adopt the non-ionised, zwitterionic, anionic or cationic form, depending on the co-former used. Attempts are made to rationalise the occurrence of each ionisation state by consideration of the relative pKa values of piroxicam and the co-formers. The hydrogen bonded supramolecular synthons in these molecular complexes are also investigated. Co-crystallisation is also used as a route to obtaining molecular complexes of paracetamol and its derivative, 4-acetamidobenzoic acid, with nitrogen-heterocycles as co-formers. Molecular complexes of the two, with similar co-formers, are compared in terms of their hydrogen bonded supramolecular synthons. Despite having otherwise similar structural features, the phenolic hydroxyl group in paracetamol and carboxylic acid group in 4-acetamidobenzoic acid result in the formation of very different synthons and in some cases different component ratios. The susceptibility of 4-acetamidobenzoic acid to deprotonation is found to play a major role in the differences observed. Molecular complexes of paracetamol with co-formers containing multiple carboxylic acid groups are also investigated, with a view towards further crystal engineering approaches for molecular complexes of paracetamol. Piracetam complexes with carboxylic acids are investigated in a similar manner. The potential for transfer of a range of these multi-component crystallisations into a non-evaporative environment, with a view to implementing continuous crystallisation approaches, is also investigated. This transfer is found to be challenging for the systems investigated.
60

Nanoconfinement of complex hydrides in porous hosts for hydrogen storage applications

Segales, Marc January 2015 (has links)
The transition from a fossil fuel-dependent society to a cleaner, more sustainable society will not be possible without renewable energy sources. Hydrogen holds great potential as an energy carrier as an alternative to fossil fuels in such society. However, the compact and safe storage of hydrogen are still major challenges. Solid state hydrogen storage offers the possibility to store hydrogen in solids offering high volumetric and high gravimetric energy densities, while reducing the risks associated when handling hydrogen gas. However, no single system has fully achieved the required properties for on-board mobile applications. Various approaches can be adopted with the aims of improving the kinetics and thermodynamics of hydrogen sorption. The nanostructuring of materials is one of the more promising strategies to achieve these aims. Reduction of the particle size of hydrides by nanoconfinement in forms of porous matrix leads to an increased surface area of the active material, and shorter diffusion distances for hydrogen atoms or ions to travel in the solid state. Kinetic barriers can be overcome and thermodynamics manipulated. An enhanced dehydrogenation rate and a reduced dehydrogenation temperature can be achieved by impregnating metal hydrides into porous scaffolds. Two complex hydrides are selected for study in this work; LiAlH4 and LiNH2. LiAlH4, is the lightest of the alanates, with a theoretical hydrogen storage capacity of 10.5 wt.%, and 7.9 wt.% H2 evolved below 220 °C. LiNH2 mixed with LiH, as part of the Li-N-H system, can reversibly desorb/uptake 6.5 wt.% H2 at 300 °C. When LiNH2 is heated alone, it releases ammonia (which is decomposed to N2 and H2 at higher temperatures > 400 °C). In this work, LiAlH4 has been impregnated in different types of commercial and synthesised porous carbon scaffolds for the first time. Nanoconfinement of the active material was achieved using solution impregnation with diethyl ether as a solvent. Analogously, the confinement of LiNH2 in porous carbon was achieved “in-situ” using lithium-ammonia solutions. Both confined composites showed lower dehydrogenation temperatures in comparison with the respective bulk materials. The influence of the design of the carbon scaffold (as manifested for example, by the surface area and the pore volume and pore size distribution) on the dehydrogenation behaviour of the impregnated complex hydrides is demonstrated. By judicious selection of an appropriate porous host, we show how it is possible to induce faster H2 desorption and substantially reduce the desorption temperature. The onset of hydrogen release for confined LiAlH4 decreased significantly in temperature, being reduced by 51 °C (in both porous hosts used, AX-21 and FDU-15) in comparison with pristine LiAlH4. The temperature at which the hydrogen release was maximised was also lowered (by 16 °C in FDU-15 and by 26 °C in AX-21) in comparison with as-received LiAlH4. The confined LiNH2 showed a much earlier release of hydrogen compared with as-received LiNH2. Normally LiNH2 would thermally decompose to Li2NH with ammonia evolution, but ammonia release was eliminated for the confined sample. Reaction with carbon led to irreversible Li2CN2 formation and hydrogen evolution. A set of experiments to establish the formation of Li2CN2 with physically mixed samples were performed. The physically mixed samples showed hydrogen release between 400 - 450 °C, producing a mixture of Li2NH and Li2CN2, suggesting two decomposition pathways were followed. In contrast, confined LiNH2 released hydrogen ca. 220 °C lower than the physically mixed sample, with no detectable trace of ammonia release.

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