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Dehydroaromatization of methane (MDA) reaction was investigated over platinum modified Mo/H-ZSM-5 catalysts which were pre-carbided at 750 oC. The influence of platinum on the catalytic performance and product selectivity of Mo/H-ZSM-5 catalysts for the MDA reaction at 700 oC was studied. The presence of platinum led to a slight decrease in methane conversion. As the platinum loading increased, the methane conversion decreased further and the catalytic stability increased with time-on-stream (TOS) during the MDA reaction. Aromatic selectivities above 90% were obtained with catalysts containing low platinum loadings (0.5 and 1.0 wt.%), with benzene being the most prominent product. A decrease in coke selectivity and coke deposits was noted with the platinum modified Mo/H-ZSM-5 zeolite catalysts. A comparative study was performed to compare platinum, palladium and ruthenium promoted Mo/H-ZSM-5 zeolite catalysts with un-promoted Mo/H-ZSM-5. The ruthenium promoted catalyst proved to be superior in catalytic performance, with a higher methane conversion obtained than found for platinum promoted and palladium promoted Mo/H-ZSM-5 catalysts. Benzene selectivity of about 60% was obtained for ruthenium and palladium promoted Mo/HZSM- 5 catalysts and the total aromatic selectivity was maintained at 90%. TGA results showed a total reduction of 50% by weight of carbon deposited on the promoted Mo/H-ZSM-5 catalyst. Dehydroaromatization of methane was studied over tin modified Pt/Mo/HZSM-5 catalysts and compared to Pt/Mo/H-ZSM-5 catalyst at 700 oC. Addition of tin decreased the activity towards methane aromatization. However, the formation of aromatic compounds was favoured. The CO FT-IR adsorption and CO chemisorption techniques showed that the catalyst preparation method had an effect on the catalytic performance of tin modified Pt/Mo/H-ZSM-5 catalysts. High aromatic selectivity and low coke selectivity were obtained with co-impregnated and sequentially impregnated Pt/Sn catalysts. While a decrease in the formation rate of carbonaceous deposits is mainly dependent on the availability of platinum sites for the hydrogenation of carbon. The order of sequentially loading platinum and tin has an effect on the electronic and structural properties of platinum as shown by XPS and FT-IR studies. CO chemisorption and the FT-IR adsorption studies showed that addition of tin decreased the adsorption capacity of the platinum surface atoms. Catalyst preparation methods and successive calcination treatments affected the location of both tin and platinum atoms in the catalyst. Catalysts prepared by the coimpregnation method showed a good platinum dispersion, better than found for the sequentially impregnated catalysts. The MDA reaction was carried out at 800 oC over manganese modified H-ZSM-5 zeolite catalysts prepared by the incipient wetness impregnation method. The effect of a number of parameters on the catalytic performance and product selectivity was investigated, such as reaction temperature, manganese precursor-type, tungsten as promoter, manganese loading and use of noble metals. The study of the effect of reaction temperature showed that the methane conversion increased linearly with increase in reaction temperature from 700 to 850 oC. The selectivity towards aromatic compounds (of about 65%) was attained for the reactions performed at 750 and 800 oC. Formation rate of carbonaceous deposits increased linearly with increase in reaction temperature. The use of different manganese precursors to prepare Mn/H-ZSM-5 catalysts had an effect on both the catalytic behaviour and the product distribution. High catalytic activities were obtained for the catalysts prepared from Mn(NO3)2 and MnCl2 salts. However, the product distribution was significantly different, with the Mn(NO3)2 catalyst being more selective towards aromatic compounds while the MnCl2 catalyst was more selective toward coke. The effect of manganese loading was studied at 800 oC and an optimum catalyst activity was obtained at 2 and 4 wt.% manganese loadings. The aromatic selectivity above 70% and coke selectivity of 20% were obtained for a 2 wt.% loaded catalyst. Addition of tungsten as a promoter onto the 2 wt.% loaded catalyst (2Mn/H-ZSM-5) lowered the catalytic activity but the catalyst remained fairly stable with increase in TOS. Tungsten modified catalysts favoured the formation of carbonaceous deposits over aromatic compounds. TGA results showed a coke deposit of 164 mg/g.cat, an 88% increase in coke deposit when tungsten was used a promoter. Noble metals were added to reduce the total amount of coke on the tungsten modified Mn/H-ZSM-5 catalysts. The presence of a noble metal favoured the formation of aromatic compounds and suppressed the formation of coke. Platinum and ruthenium promoted catalysts were the active catalysts and aromatic selectivity increased from 12% to 55% and 46% respectively. A reduction in the total amount of coke deposit on the platinum promoted catalyst (42%) and the ruthenium promoted catalyst (31%) was noted.

MSc, School of Chemistry, Faculty of Science, University of the Witwatersrand, 2011 / In this work, a detailed study of the evaluation of gold-based catalysts supported on manganese oxides for the oxidation of volatile organic compounds (VOCs) has been undertaken. Model catalysts were prepared by deposition-precipitation methods to establish the effect of the support on the catalytic activity of the gold catalysts. The catalysts were characterised by X-ray diffraction, transmission electron microscopy, N2–physisorption measurements and temperature programmed reduction techniques. The activity of the catalysts for VOC oxidation reactions were tested in a continuous flow fix bed glass reactor. The products were analysed by GC/TCD and GC/FID. The catalysts Au/TiO2, Au/Al2O3, Au/ZnO and Au/MnO2 were used for the VOC oxidation reaction. 2-propanol, 2-butanol and toluene were used as VOCs for the study. These were chosen because they are important indoor pollutants given their wide laboratory use and high volatility. Toluene was found to be the most difficult to oxidise, followed by 2-propanol. The effect of calcination temperature and preparation procedure was evaluated for the gold/manganese oxide catalysts. Au/b-MnO2 catalysts prepared by deposition-precipitation showed some catalytic performance which was less than the performance shown by Au/MnOx, prepared by co-precipitation. g-MnO2 proved to be more efficient in the oxidation of 2-propanol than pyrosulite phase MnO2. The addition of gold to any metal oxide support was found to enhance the oxidation of VOCs. Gold-based catalysts were more active than the Ce/MnO2 catalyst. Catalytic tests showed that Au/CeO2 was the superior catalyst for the total oxidation of toluene, 2-propanol and 2-butanol. Ceria is a highly reducible oxide and the formation of gold–ceria interactions produced an even more easily reduced material. University of the Witwatersrand, Johannesburg ii

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the Degree of Doctor of Philosophy. J o h a n n e s b u r g , 2 0 1 3. / Structured carbon nanomaterials have attracted considerable interest because of their unique structures and outstanding properties. Among other structured carbon nanomaterials, carbon nanofibers (CNFs) have been the subject of study for several decades with particular interest having been paid towards their synthesis and application. However, control over the size and shape of these materials still remains a challenge. Three main components necessary for the synthesis of CNFs are the catalyst or template, the carbon source and the source of energy/power. It has been noted that catalyst morphology and the carbon source plays an important role in controlling CNF growth and morphology. As such one of the main challenges is to produce the catalyst particles that would yield the desired CNF morphology. In this study, we investigated methods for controlling the size and morphology of CNFs by synthesizing Ni and Cu catalysts of particular morphology, while using C2H2 and trichloroethylene (TCE) as a carbon source for the synthesis of CNFs. A mixture of TCE/C2H2 was also employed as a carbon source for comparison. The catalysts and synthesized CNFs were characterized by different techniques such as TEM, XRD, TPR, TGA, Raman spectroscopy, IR spectroscopy, etc. The synthesis of Ni nanoparticles (NPs) was achieved by reduction of Ni(acetate)2 with hydrazine (35%). CNFs were synthesized by deposition of TCE, C2H2 and their mixtures using a chemical vapor deposition technique (CVD) in the temperature range 400-800 oC. N2 and CO2 were used as carrier gases. TEM analysis of the Ni particles as a function of time revealed that the Ni underwent a morphological change with time. Further, as the temperature of the reaction changed, so did the shape of the carbon materials. The shapes changed from structures showing bilateral growth at T = 400 oC to tripod-like structures and multipod-like structures at T = 450 oC and T = 500 oC respectively. Irregular shaped materials were observed at T > 500 oC. It was also found that when acetylene or an acetylene/trichloroethylene mixture was used at T = 450 oC, helical (> 80%) and linear fibers were produced respectively. It was also demonstrated that the flow rate of H2, N2 and CO2 had a dramatic influence on the morphology of CNFs. CO2/TCEwas found to produce linear fibers with controlled sizes at 800 oC. The results demonstrated that the formation of tripod CNFs only occurs in a very narrow parameter regime. Manoko S. Maubane The preheating of the TCE prior to its deposition over a Ni particle catalyst was achieved using a double stage CVD reactor. TCE was subjected to high temperatures prior to its deposition at low temperatures. Results showed that the decomposition temperature was the key parameter in the synthesis of CNFs. It was found that during the decomposition, TCE breaks down into different species/radicals which then adsorb onto the catalyst particle to give CNFs of different morphology. Raman studies revealed that the synthesized CNFs showed an increase in graphitic nature when the temperature in the first reactor of a two stage reactor was increased. Decomposition of C2H2 was also performed over Cu NPs, and Cu modified catalysts (Cu@SiO2 and Cu/SiO2) with different silica coatings at 300 oC. These catalysts were prepared by reduction of Cu(acac)2 with hydrazine (35%). TEM images revealed that coiled CNFs were only produced from Cu/SiO2 grown in the presence of H2 (> 90 %; d = 60-70 nm). IR spectra of all the CNFs indicated the presence of surface C=C, C=O, CH3 and CH2 moieties, and that the ratios of peak intensities of C=O/CHx and C=C/CHx species indicated the variable CNF surface that was produced by the gases and the Cu particles used. It was thus revealed that the CNFs produced by different Cu catalysts have different chemical and physical properties and that these properties correlate with catalyst particle size and the gas mixtures used. CuO and SrO modified Cu catalysts (with different Cu/Sr ratios) were also employed using the CVD method for the synthesis of CNFs at 300 oC. These catalysts were prepared by a coprecipitation method. The TEM images of the CNFs revealed a mixture of straight and coiled CNFs with a broad diameter distribution (50-400 nm) dependent on the Cu/Sr ratio of the catalyst used. IR and TGA analysis revealed that the chemical composition of the CNFs changed as the SrO content changed. The SrO content also affected the Cu particle size and influenced the morphology of the Cu particles from which the CNFs grew.

by Lai Chi Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 63-68). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Chapter 1 --- General introduction / Chapter 1.1 --- Background of phosphines and arsines ligands in metal catalysis --- p.1 / Chapter 1.2 --- Electronic effect of phosphines and arsines ligands in metal catalysis --- p.2 / Chapter 1.3 --- Synthesis of Aryl Phosphines --- p.7 / Chapter 1.4 --- Synthesis of Aryl Arsines --- p.9 / Chapter 1.5 --- The objective of this work --- p.11 / Chapter Chapter 2 --- Palladium catalyzed phosphination of aryl triflates / Chapter 2.1 --- Synthesis of aryl triflates --- p.12 / Chapter 2.2 --- Palladium catalyzed phosphination of aryl triflates --- p.15 / Chapter 2.3 --- Mechanistic studies of phosphination --- p.19 / Chapter Chapter 3 --- Palladium catalyzed arsination of aryl triflates --- p.22 / Chapter 3.1 --- Solvent and catalyst screening in palladium catalyzed arsination --- p.23 / Chapter 3 2 --- Stoichiometry of triphenylarsine --- p.24 / Chapter 3.3 --- Temperature effect of arsination --- p.25 / Chapter 3.4 --- Results of palladium catalyzed arsination --- p.26 / Chapter 3.5 --- Mechanistic studies of arsination --- p.28 / Chapter Chapter 4 --- Green chemistry approach 一 solventless phosphination and arsination / Chapter 4.1 --- Introduction to green chemistry --- p.30 / Chapter 4.2 --- Results of solventless phosphination --- p.31 / Chapter 4.3 --- Results of solventless arsination --- p.33 / Conclusion --- p.36 / Experimental --- p.37 / Reference --- p.63

D. Tech. Chemistry.

No description available.

Thesis (M.S.)--State University of New York at Binghamton, Department of Chemistry and Materials Science & Engineering, 2006. / Includes bibliographical references (leaves 49-53).

Thesis (Master)--İzmir Institute of Technology, İzmir, 2006. / Keywords:Cooper, zinc oxide, silica. Includes bibliographical references (leaves. 46-48).

Thesis (Ph.D.)--University of Ottawa, 2008. / Includes bibliographies. Also available via the World Wide Web.