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Kinetic assay of T7 activity on mutant promoters : method development and experimental designAdams, Jonathan Weldon 08 1900 (has links)
No description available.
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Synthesis and functionalization of gallium nitride nanostructures for gas sensing and catalyst supportKente, Thobeka 10 January 2014 (has links)
A thesis submitted to the Faculty of Science, University of the Witwatersrand,
Johannesburg, in fulfilment of the requirements for the degree of Doctor of
Philosophy. October 2013.
Johannesburg, South Africa. / We report the role of a double step heat treatment process in the synthesis of
novel GaN nanostructures (NSs) using a two stage furnace following a catalyst
free vapour-solid growth mechanism. Morphological analysis revealed that GaN
NSs were composed of rod-like structures with average diameter of 250 nm and
accumulated particulates of GaN with diameter of ~ 12 – 16 nm providing
enhanced surface area. The wurtzite phase of GaN nanorods of agglomerated
nanoclusters was synthesized at temperatures as low as 750 °C. An X-ray
photoelectron spectroscopic study confirmed formation of GaN. The surface areas
of the GaN NSs were high at ~20 m2/g with respect to that expected for solid
nanorod structures. The GaN NSs were of high crystallinity and purity as revealed
by structural studies. Raman spectral analysis showed stronger intensity of the
A1(LO) mode with respect to that for E2(high) mode indicating the high electronic
quality of the sample. A photoluminescence study revealed the dominant presence
of a defect band around 1.7-2.1 eV corresponding to nitrogen di-vacancies.
Subsequent annealing in NH3 has demonstrated a compensation of the defect state
and evolution of a band edge peak with possible hydrogen compensation of
surface states.
We also report the role of activated carbon on Ga2O3 to make GaN/C
nanostructure composites using a single stage furnace. TEM analysis showed that
GaN/C nanostructures gave different morphologies with different ratios of
GaN/C. The surface areas of these materials showed an increase as the ratio of
activated carbon was increased. PXRD showed that a ratio of Ga2O3: C of 1:0.5
(w/w) was sufficient to form GaN. TGA revealed that the ratios of Ga2O3: C of
1:0.5 – 1:2 gave materials that were thermally stable. Raman spectra showed that
the material had excellent electronic properties. The material with a Ga2O3/C 1:2
ratios showed a poor gas response due to the change in reference value of
resistance with the variation of hydrogen concentration.
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This study also provides the first investigation of GaN as a catalyst support in
hydrogenation reactions. The GaN NSs were synthesized via chemical vapour
deposition (CVD) in a double stage furnace (750 ºC) while nitrogen doped carbon
spheres (NCSs) were made by CVD in a single stage furnace (950 ºC). TEM
analysis revealed that the GaN NSs were rod-like with average diameters of 200
nm, while the NCSs were solid with smoother surfaces, and with diameters of 450
nm. Pd nanoparticles (1 and 3% loadings) were uniformly dispersed on acid
functionalized GaN NSs and NCSs. The Pd nanoparticles had average diameters
that were influenced by the type of support material used. The GaN NSs and
NCSs were tested for the selective hydrogenation of cinnamaldehyde in
isopropanol at 40 and 60 °C under atmospheric pressure. A comparative study of
the activity of the nanostructured materials revealed that the order of catalyst
activity was 3% Pd/GaN >3% Pd/NCSs > 1% Pd/NCSs > 1% Pd/GaN. However,
100% selectivity to hydrocinnamaldehyde (HCALD) was obtained with 1%
Pd/GaN at reasonable conversion rates.
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Novel hybrid organic/inorganic single-sited catalysts and supports for fine chemical and pharmaceutical intermediate synthesisGill, Christopher Stephen. January 2009 (has links)
Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Jones, Christopher; Committee Member: Agrawal, Pradeep; Committee Member: Teja, Amyn; Committee Member: Weck, Marcus; Committee Member: Zhang, John.
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Growth of carbon nanotubes on model and supported catalystsMedhekar, Vinay S. January 2004 (has links)
Dissertation (Ph.D.)--Worcester Polytechnic Institute. / Keywords: supported catalyst; spin coating; atomic layer deposition; carbon nanotubes; model catalyst; ferrocene; thin film coating. Includes bibliographical references. (p.256-258)
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Synthesis and characterisation of zirconia supported molybdenum oxide and molybdenum carbide catalysts for hydroconversion of n-heptaneOloye, Femi Francis January 2016 (has links)
The current upgrading catalysts are mainly based on the use of expensive noble metals, which are subject to deactivation due to sintering and coking. An alternative would be to introduce a non-noble metal-based catalyst. In this work, supported molybdenum carbide based systems have been assessed for this purpose. These catalysts were formed by impregnation of zirconia (and zirconium hydroxide) and sulfated zirconia (and zirconium hydroxide) with different loadings of MoO3, with an aim of finding a balance between acid sites and metal-like sites (a site capable of performing dehydrogenation and hydrogenation function without necessarily being a metal). The synthesised catalysts were carburised between 823 and 1123 K using a mixture of methane and hydrogen (4:1) in an attempt to obtain β-Mo2C/ZrO2 or β-Mo2C/S ZrO2. Carburisation at 923 K and above resulted in molybdenum carbide with minimal or no oxygen contents. The conversion and specific rate increased with temperature. Conversion was inversely proportional to space velocity. Analysis of the products distribution as a function of conversion implies that the reaction did not simply follow a consecutive reaction pathway, but that other parallel routes were involved. Conversion increased the research octane number (RON) to ca. 66 due to the increased fraction of pentane isomers. Catalyst carburised at 823 K was approximately four times more active compared to those carburised at 923 K and above, but were of similar activity with Pt/sulfated zirconia. The non-noble metal based catalysts were stable at the reaction temperature while the Pt/sulfated zirconia catalyst deactivates.
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Flow Through, 2D/3D Nanoplatelet Supports for Packed Beds and ColumnsMeng, Xuewei 19 November 2018 (has links)
High performance catalyst supports and packing materials are playing an increasing role in many reactions and separations. The dispersion in packed bed reactors and separation columns can be reduced by the development of new packing structures having open and connected pore geometries. The application of new materials in High Performance Liquid Chromatography (HPLC) with sub 5 micron particle sizes are growing. These small particles offer better performance and improved bed and column efficiencies. Recently developed, twinned Alumina Nanosheets (TAN) are 2D/3D nanomaterials that offer promising open geometries for use as column packings and catalysts supports. They have a small particle size (4 um in length, 1 um in width and 0.1 um in thickness) and excellent flow-through capabilities. TANs have recently been used to successfully produce high throughput dynamic membranes.
However, their resistance to compaction is unknown and thought to be limited. A technique was developed to reinforce the TAN nanomaterial. Two binder materials were tested as reinforcing agents; SiO2 and AlH6O12P3. The binder-reinforced TANs were then packed into columns. Eleven columns having a 4 cm initial packing length were assembled. Tracer injection studies were performed to investigate the flow behavior and dispersion in these columns. SEM images were also taken to characterize the particles before and after compaction. The best results were obtained using a binding solution containing 7.5 (wt%) SiO2. The binder SiO2 offered a better resistance to compaction than the AlH6O12P3. The Peclet (Pe) number for the columns ranged from 22 to 648. When the content of SiO2 increased from 0 to 7.5 (wt%), the columns showed an increase in the Pe number. When SiO2 increased from 7.5 to 20 (wt%), the columns showed a decrease in the Pe number. However, AlH6O12P3 did not present any relation between the binder content and the Pe number.
The results of this work demonstrate that reinforced TANs, are a new type of material that offers a packing with an open pore structure and improved channel connectivity. The new reinforced material offers considerable potential in many applications such as catalysis and separations over conventional materials. If they are used as packing materials in HPLC columns or packed bed reactors, they can contribute to a higher separation efficiency or an enhanced conversion rate or productivity, bringing more advantages and benefits than ordinary packing materials.
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Effect of promoter loading for supported silver catalysts used for the epoxidation of 1,3-butadiene with dioxygen /Mueller, Gregory M., January 2004 (has links)
Thesis (M.S.)--University of Missouri-Columbia, 2004. / Typescript. Includes bibliographical references (leaves 61-63). Also available on the Internet.
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Effect of promoter loading for supported silver catalysts used for the epoxidation of 1,3-butadiene with dioxygenMueller, Gregory M., January 2004 (has links)
Thesis (M.S.)--University of Missouri-Columbia, 2004. / Typescript. Includes bibliographical references (leaves 61-63). Also available on the Internet.
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Supported Perovskite-type Oxides: Establishing a Foundation for CO<sub>2</sub> Conversion through Reverse Water-gas Shift Chemical LoopingHare, Bryan J. 12 March 2018 (has links)
Perovskite-type oxides show irrefutable potential for feasible thermochemical solar-driven CO2 conversion. These materials exhibit the exact characteristics required by the low temperature reverse water-gas shift chemical looping process. These properties include structural endurance and high oxygen redox capacity, which results in the formation of numerous oxygen vacancies, or active sites for CO2 conversion. A major drawback is the decrease in oxygen self-diffusion with increasing perovskite particle size. In this study, the La0.75Sr0.25FeO3 (LSF) perovskite oxide was combined with various supports including popular redox materials CeO2 and ZrO2 along with more abundant alternatives such as Al2O3, SiO2, and TiO2, in view of its potential application at industrial scale. Supporting LSF on SiO2 by 25% mass resulted in the largest increase of 150% in CO yields after reduction at 600 °C. This result was a repercussion of significantly reduced perovskite particle size confirmed by SEM/TEM imaging and Scherrer analyses of XRD patterns. Minor secondary phases were observed during the solid-state reactions at the interface of SiO2 and TiO2. Density functional theory-based calculations, coupled with experiments, revealed oxygen vacancy formation only on the perovskite phase at these low temperatures of 600 °C. The role of each metal oxide support towards suppressing or enhancing the CO2 conversion has been elucidated. Through utilization of SiO2, the reverse water-gas shift chemical looping process using perovskite-based composites was significantly improved.
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Novel hybrid organic/inorganic single-sited catalysts and supports for fine chemical and pharmaceutical intermediate synthesisGill, Christopher Stephen 06 February 2009 (has links)
The study of catalysis is a fundamental aspect of chemical engineering, as its implications affect all chemical transformations. Traditionally, catalysis has been subdivided into two areas: homogeneous and heterogeneous catalysis. Homogeneous catalysis refers to single-sited catalysts that exist in the same phase as the reaction media. These catalysts tend to be highly active and selective but often difficult to recover and reuse. In contrast, heterogeneous catalysts are typically multi-sited catalysts that exist in a different phase from the reaction media. These catalysts tend to be less active and selective than their homogeneous counterparts. However, the vast majority of industrial scale catalysts are heterogeneous because they can be easily separated, making them easily implemented in continuous processes, allowing for efficient, large scale operations.
Due to the limitations of traditional homogeneous and heterogeneous catalysts, researchers have increasingly investigated hybrid catalysts that incorporate aspects of homogeneous and heterogeneous catalysis. This is accomplished via immobilization of homogeneous catalyst analogues onto solid-phase supports, thereby preserving the activity and selectivity of homogeneous catalysts while allowing for facile recovery and reuse from the insoluble, heterogeneous support.
A variety of systems is presented here including organic and organometallic catalysts immobilized on organic and inorganic supports. Five cases are included. The first discusses utilization of supported acid and base catalysts for use in one-pot cascade reactions. The second example illustrates use of silica-coated magnetic nanoparticle supported acid catalysts for organic transformations. The third case presents novel polymer brush supported Cobalt-salen catalysts for the enantioselective, hydrolytic kinetic resolution of epoxides. A fourth case presents novel, magnetic polymer brush supported organic and organometallic catalysts for organic transformations. The fifth example illustrates polymer and silica supported ruthenium-salen catalysts for the asymmetric cyclopropanation of olefins. The overall goal of this thesis work is to develop novel supports and immobilization techniques to advance the field of hybrid organic/inorganic catalysts for the production of fine chemical and pharmaceutical intermediates.
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