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Soluble molecular siloxane complexes of the lanthanidesAnnand, Judith January 1999 (has links)
No description available.
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Strong metal-support interactions in titania-supported metal catalystsAnderson, J. B. F. January 1986 (has links)
No description available.
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Synthesis and characterization of Ag, Au and Cu dendrimer-encapsulated nanoparticles as well as their application in catalysis05 November 2012 (has links)
M.Sc. (Chemistry) / In this dissertation the synthesis, characterization and the application of Ag, Au and Cu dendrimer encapsulated nanoparticles (DENs) in catalysis are described. Ag, Au and Cu-DENs were synthesized using G4-G6 PAMAM-OH and G4-G6 PAMAM-NH2 dendrimers as templates as well as stabilizers. NaBH4 was used as a reducing agent for the synthesis of DENs. Binding studies were carried out in order to determine the maximum capacity of the dendrimer to which the metal ions can be added. These binding studies were performed using UV-vis spectroscopy. The synthesis of these nanoparticles (NPs) was carried out at room temperature. For the synthesis of Ag and Au-DENs with PAMAM-NH2 dendrimers, the pH of the aqueous dendrimer solution was first adjusted to acidic condition (~pH 2) using HCl before the addition of the respective metal ion precursor to the dendrimer. This is done to avoid coordination of the metal ions to the primary amine groups on the periphery of the dendrimer, which might lead to particle agglomeration. These prepared DENs were characterized by UV-vis spectroscopy and high resolution transmission (HRTEM) microscopy. The synthesized DENs were evaluated as catalysts in the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. This reaction was monitored by UV-vis spectroscopy by following the absorbance at 400 nm These DENs were all found to be active catalysts for the afore-mentioned process. The rate constant for the reduction process was observed to decrease as the concentration of 4-nitrophenol increased. As the concentration of NaBH4 is increased, the rate constant was also found to increase, however this increase was only observed to a maximum concentration of NaBH4. The Au-DENs prepared using G4 PAMAM-NH2 dendrimers were subsequently immobilized onto a titania support via the sol-gel (Ti-Au-s) and wetness impregnation (Ti-Au-w) methods. The titania supported Au NPs were characterized using HRTEM, powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), inductive coupled plasma-optical emission spectroscopy (ICP-OES) and Brunauer Emmett Teller (BET) surface area analysis. The dendrimer template was removed by calcining at 500 oC. The catalytic activity of these supported Au NPs was investigated in the oxidation of styrene using tert-butyl hydroperoxide (TBHP) as an oxidant. Benzaldehyde and styrene oxide were observed as the major products. The catalyst prepared by wetness impregnation method was found to give the highest styrene conversion as compared to the one prepared via sol-gel method. At 60 oC, the catalyst prepared by sol-gel method was found to selectively produce benzaldehyde while on the other hand, the catalyst prepared by wetness impregnation selectively produce styrene oxide. The highest conversion of styrene was observed at 70 oC for both catalysts. Ti-Au-w catalyst was generally found to give the highest styrene conversion.
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Synthesis and characterisation of gold- and platinum-based multimetallic catalystsFraser, Adam Earl January 2016 (has links)
No description available.
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The sintering and redispersion of supported metal catalystsDevgon, Vinay Kumar January 2010 (has links)
Digitized by Kansas Correctional Industries
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Tantalum oxide-based catalysts : synthesis, molecular structures and catalysis /Chen, Yongsheng, January 2003 (has links)
Thesis (Ph. D.)--Lehigh University, 2003. / Includes vita. Includes bibliographical references (leaves 127-144).
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Transition metal catalysed photo-induced oxidative C-H bond functionalization and water oxidationTo, Wai-pong, 杜偉邦 January 2012 (has links)
A series of cyclometalated gold(III) complexes with N-heterocyclic carbine (NHC) or alkynyl as auxiliary ligand were synthesized and characterized. Complexes [AuIII(R1
–C^N^C)(NHC)](OTf) and [AuIII(C^N^C)(C≡CR2)] (HC^N^CH = 2,6-di(naphthalene-2-yl)pyridine; R1 = H or 4-methoxyphenyl; R2 =aryl) are emissive in solution at room temperature with quantum yields in the range of 0.65–11.4% and lifetimes ranging from 98 to 506 s. [AuIII(4-(4-OMePh)–C^N^C)(NHC)](OTf) showed prominent photochemical properties. This complex effectively catalyses photo-induced oxidation of secondary amines (to the corresponding imines) and -functionalization of tertiary amines in good to excellent yields; it also acts as a photosensitizer for hydrogen generation in a water/acetonitrile mixture, producing more than 350 turnovers of hydrogen after 4 hours of irradiation.
Palladium(II) meso-tetrakis(pentafluorophenyl)porphyrin was found to be an efficient and robust catalyst for the photo-induced oxidative C–H bond functionalization reactions. Several kinds of -functionalized tertiary amines were obtained in good to excellent yields by irradiating a mixture of palladium(II) catalyst, corresponding tertiary amine and nucleophile under aerobic conditions. The nucleophiles for these reactions include cyanide, nitromethane, dimethyl malonate, diethyl phosphite and acetone. Two examples of novel intramolecularly cyclized amines were also described. Comparison of the UV-vis absorption spectra before and after reaction indicated that the palladium catalyst was highly robust. The practical potential of this catalyst was shown by the success in reactions at a low catalyst loading and on a large scale. The palladium(II) catalyst could also sensitize photo-induced oxidation of sulfide to sulfoxide and photo-induced hydrogen production in a water/acetonitrile mixture with up to 240 turnovers.
[FeIII(L-N4Me2)Cl2][FeCl4] (L-N4Me2 = N,N’-dimethyl-2,11-diaza[3,3] (2,6)pyridinophane) was demonstrated to be an active catalyst for water oxidation. When cerium ammonium nitrate (CAN) was used as the oxidant, the iron(III) catalyst oxidized water to oxygen with up to 93 turnovers after 30 minutes in 0.1 M nitric acid, whereas changing the oxidant to sodium periodate (NaIO4) resulted in only 44 turnovers of oxygen after 30 minutes. The mechanism of the reaction was explored by high resolution electrospray ionization mass spectrometry (ESI-MS), 18O labeling, UV-vis absorption spectroscopy, kinetic plots and DFT calculations. In the case of using CAN, an FeIV-oxo species was detected by ESI-MS and UV-vis absorption spectroscopy. The rate of oxygen evolution was found to be linearly dependent on both concentrations of catalyst and oxidant. 18O labeling studies confirmed that the origin of oxo ligands was from water and was irrespective of the choice of oxidant. This reaction was proposed to involve a coupling between an FeIV-oxo species and a hydroxocerium(IV) radical. In the case of using NaIO4, an FeV-dioxo species was detected by ESI-MS as a major species, and a small amount of FeIV-oxo species was detected by UV-vis absorption spectroscopy. As the rate of oxygen evolution was found to be linearly dependent on the concentration of catalyst only, the reaction was proposed to involve a cis-FeV-dioxo species. DFT calculations showed that the cis-FeV-dioxo species was capable of oxidizing water to oxygen through the formation of an [FeIII(L-N4Me2)(OO?)(OH)]+ intermediate. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Syntheses, structures and support interactions of potential metal oxide catalyst precursorsVenable, Margaret Hamm 08 1900 (has links)
No description available.
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Syntheses, structures, and catalysis of polynuclear metal complexesLiu, Hongying 05 1900 (has links)
No description available.
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Preparation, characterization and performance of non-uniform metal catalystsShyr, Yen-Shin 12 1900 (has links)
No description available.
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