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TiO2 supported MoO3 catalysts were prepared by aqueous impregnation of low area anatase (10 m2g-1) with solutions of (NH4)6Mo7024,4H20 (MT/C series), and H2[Mo03(C204)].H20 (MOT /C series), Three series of CoOx/Ti02 catalysts were fabricated by aqueous impregnation of the same support with solutions of Co(N03)2,6H20 (CT/C series), and Co(CH3COO)2.4H20 (CAT/C series), and by homogeneous precipitation using Co(N03)2,6H20 (CT/HP series), CoO and Mo03 were deposited on Degussa P-25 (55 m2g-1) by aqueous impregnation using (NH4)6Mo7024,4H20 and Co(N03)2,6H20 in three ways: ( i) CoO impregnated first, Mo03 second (CMT series); (ii) Mo03 impregnated first, CoO second (MCT series); and (iii) CoO and Mo03 together (CMTg series). The catalysts were characterized by laser Raman spectroscopy (LRS) , temperature-programmed reduction (TPR) , X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), Monolayer coverage by XPS was independent of the precursor for the MoOx/Ti02 catalysts, but a function of the method of preparat ion and the precursor for the CoOx /Ti02 catalysts. XPS results for the CMTg series differed from those for the CMT and MCT series, suggesting different surface species had been formed by varying the mode of impregnation, Phase diagrams relating semiquantitatively to the oxide contents are presented. 2-propanol decomposition was studied to probe the acid-base properties of the catalysts, Ti02 and Mo03 exhibi ted dehydration activity, whereas CoO showed dehydrogenation activity, All the supported catalysts gave activation energies for dehydration higher than dehydrogenation. In the sub-monolayer region, the catalytic activity for dehydration was in the order: MCT > CMTg > CMT > MT/C > CT/C, while the selectivity remained almost unchanged, In the monolayer region, the activity was: MT/C > CMT > CMTg > MCT > CT/C and the selectivity increased compared with the sub-monolayer region. In the four-monolayer reg ion, the activity decreased compared with the sub-monolayer and monolayer regions, but the selectivity increased relative to the previous two regimes. "Compensation effect 0, plots revealed different types of active centres responsible for dehydration and dehydrogenation processes in the MoOx /Ti02 and CoO-Mo03/Ti02 catalysts, while active centres were almost identical with the CoOx /Ti02 system.

Biodiesel is a renewable and biodegradable alternative green fuel for petroleum-based diesel. The major obstacle for the production of biodiesel at an industrial scale is the high production cost, which is related to the relative high price of the conventional ???1st generation feedstocks??? (refined vegetable oils) used. This problem can be addressed by using low cost feedstocks such as waste oils and fats. However, these feedstocks contain high amounts of free fatty acids (FFA) which cannot be used for the production of biodiesel using a traditional homogeneous alkali-catalyzed transesterification process. Furthermore, there is a great need to develop a green process which can be used for multiple feedstocks. This shows the universal ability of the process to be adopted as per availability of local feedstock. In this study, a single-step second generation heterogeneous-catalyzed process is developed to produce biodiesel from multi-feedstocks. Due to an increase in the commercial use of biodiesel and biodiesel blends, both ASTM D6751 and EN 14214 include the acid number (AN) as an important quality parameter. Currently, ASTM D974 and D664 analytical methods for acid number analysis of biodiesel are time consuming, expensive, and environmentally not friendly. Therefore, ASTM D974 has been modified and a green analytical method has been developed. This extensive study has demonstrated that this new method is a reliable method for the determination of AN and could be used for establishing the specifications of AN for biodiesel and biodiesel blends ranging from B1 to B20 in quality standards. The ASTM reference standard method D664, has major problems such as the use of excess toxic solvents, large sample size, mediocre reproducibility, tedious process for cleaning electrodes, and relatively long analysis time. Therefore, a new proposed method based on green chemistry approaches, has been developed to determine the acid number of biodiesel and biodiesel blends using small sample size and reduced toxic titration solvent. This proposed green analytical method could be used for the determination of AN of biodiesel and biodiesel blends in R&D as well as industrial quality control laboratories as a simple, time-efficient, cost effective and environmentally friendly method.

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Thesis (Master)--İzmir Institute of Technology, İzmir, 2006. / Keywords:Suzuki reactions, palladium, NaYzeolite, heterogeneous catalyst, C-C coupling. Includes bibliographical references (leaves. 71-81).

This thesis is based on experiments applying synchrotron based X-ray Absorption Spectroscopy(XAS) and Resonant Inelastic X-ray Scattering (RIXS) in the soft X-ray region to energy related systems. The main work of this thesis has been to develop a reaction cell that allowed for in situ XAS and RIXS investigations of the partial epoxidation of ethylene over a Ag catalyst at 1 atm and up to 250C. The developed in situ cell can be used in two sample modes: 1) the Ag catalyst is deposited directly onto the vacuum separating membrane with the reaction gases flowing beneath it or 2) a slightly compressed Ag powder sample is at a distance to the vacuum membrane with the reaction gases flowing between the Ag powder sample and the membrane.Both sample modes offers the total florescence yield, TFY, and the total electron yield, TEY, to be recorded simultaneously. By means of the developed in situ cell a number of oxygen species, residing in/on the Ag surface or in the Ag bulk, have been detected. We claim to detect adsorbed O2 under epoxidation conditions, as well as Ag–O–H groups. We are also able to monitor changes of the absorbed oxygen as we change the composition of the reaction gas feed. The first charging cycle of Li-ion batteries have been investigate by ex situ measurements on the cathode Li2-xMnSiO4 and the anode composite LixNi0:5TiOPO4/C . The initial crystalline material becomes amorphous due to lithiation during the first first charging. We find that the redox behaviors of these two states are significantly different. Sulfidation of natural copper oxides are is found to be strongly promoted when it is grown on the host metal by a disproportionation.

This thesis concerns the preparation and use of diaryliodonium salts. In Project I various unsymmetrical diaryliodonium salts were reacted with three different nucleophiles in order to study the chemoselectivity of the reactions of the salts. The main focus of this project was to gain a deeper understanding of the underlying factors that affect the chemoselectivity in transition metal-free arylation reactions. They were found to be very nucleophile-dependent. Some nucleophiles were very sensitive to electronic effects, whereas others were sensitive to steric factors. Ultimately, some arenes are never transferred. A very interesting scrambling reaction was also observed under the reaction conditions, where unsymmetrical diaryliodonium salts form symmetrical salts in situ. Project II details the preparation of N-heteroaryliodonium salts via a one-pot procedure. The salts were designed so that the N-heteroaryl moiety was selectively transferred in applications both with and without transition metals. The chemoselectivity was demonstrated by selective transfer of the pyridyl group onto two different nucleophiles. The third project in the thesis discusses the synthesis of alkynyl(aryl)iodonium salts and alkynylbenziodoxolones from arylsilanes. This protocol could potentially be a very useful complement to the existing procedures, in which boronic acids are used. The last part of the thesis (Project IV) describes a C-2 selective arylation of indoles where diaryliodonium salts were used in combination with hetero-geneous palladium catalysis. This transformation was performed in water at ambient temperature to 50 °C, and tolerated variations of both the indole and the diaryliodonium salt. Importantly, several N-H indoles could be arylated. The MCF-supported Pd-catalyst showed very little leaching and it was demonstrated that the main part of the reaction occurred via heterogeneous catalysis. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Accepted.</p>

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

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