Thesis (PhD)--Stellenbosch University, 2000. / ENGLISH ABSTRACT: Please refer to fulltext for abstract / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming

This dissertation reports on the study of black molybdenum, a new cermet consisting of small Mo particles embedded in MoO₂. As with most two-phase materials, the optical properties of black molybdenum are significantly different from those of either constituent, and can be adjusted within wide limits through modifications of composition and microstructure due to variations of the fabrication process parameters. The subject of this work is to understand the exact relationships, to allow reproducible production of films with chosen optical properties. Theoretical interpretation of the optical properties of two-phase materials has in the past been hampered by insufficient microstructural characterization. Recent theoretical work by others has lifted the requirements of detailed microstructural knowledge, leaving only two required parameters for characterization of cermet reflectance: the optical properties of the constituent phases and their volume fractions in the cermet. Better characterization is obtained when structural considerations, such as film topology, surface texture and the presence of a possible amorphous phase, are taken into account. We adopted this approach to the study of black molybdenum, and accomplished satisfactory agreement between theoretical and observed reflectances. Black molybdenum films were prepared using two separate chemical vapor deposition (CVD) techniques, involving deposition from either Mo(CO)₆ or MoO₂Cl₂. We found the influence of composition through a comparison of films with different Mo:MoO₂ ratios, while the influence of structure on film reflectance was determined by comparing films from these two deposition techniques. During this investigation we produced black molybdenum films which display a spectrally selective profile--low visible reflectance combined with high infrared reflectance, and which may be applied to photothermal solar energy conversion. The versatility of CVD in adjusting film composition and structure resulted in another film of interest in photothermal conversion--black tungsten, a tungsten-tungsten oxide composite material. The black molybdenum and black tungsten systems studied here establish the utility of CVD for the production of high temperature thin film optical devices.

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Nanoparticles of MoS2 and WS2 were synthesized by decomposing the appropriate metal hexacarbonyl in the presence of sulfur dissolved in decalin at 140°C. A significant fraction of the nanoparticles was ≤ 15 nm in diameter as verified by Transmission Electron Microscopy. The process was repeated in the presence of silica and then titania to produce supported metal sulfides. The unsupported nanoparticles were found to exhibit a size-dependent shift in their threshold UV-visible absorption due to quantum confinement. Photocatalytic properties of each sulfide from synthesis in decalin were explored by using each as a catalyst in the photodegradation of methylene blue by visible light. These sulfides were also used to catalyze the photodegradation of acetone. Unsupported MoS2 and WS2 nanoparticles catalyzed the photodegradation of acetone under visible light of ≥ 400 nm wavelength. This is the first study reporting the photocatalytic properties of the unsupported WS2 nanoparticles. Photodegradation of methylene blue under ≥ 435 nm irradiation was detected using unsupported WS2 but not unsupported MoS2, likely because activity was masked by the likely photobleaching of the dye. When deposited on silica or titania, the nanosized MoS2 and WS2 could be uniformly distributed in aqueous solutions to maximize the photocatalytic efficiency. Correcting the absorbance measurements for light scattering by solids proved to be beneficial for extracting kinetic information. Both silica deposited sulfides were found to significantly increase the rate of methylene blue photodegradation, and deposited WS2 increased this rate significantly more than deposited MoS2. Similarly, both titania deposited sulfides significantly increased the rate of methylene blue photodegradation, and the deposited WS2 increased this rate significantly more than the deposited MoS2 / Synthesis of the sulfide photocatalysts -- Characterization of synthesized nanoparticles -- Photocatalytic degradation tests : setup and protocols -- Photocatalytic degradation tests : results. / Department of Chemistry

M.Sc. / This study comprises the preparation and characterisation of new azolinylidene- and divinylcarbene complexes of chromium, molybdenum and tungsten, from 1- phenylpyrawle, 1-methylimidazole and 4,4-dimethyl-2,2-thienyloxazoline precursors. The reaction of 1-phenylpyrazolyllithium with (C0) 6M (M Cr, Mo or W) yields after alkylation with CH3S03CF3 in THE the two products (C0)5M[C(OCH3X(ONPhNCHC(H)] and (C0)5M[C(0{CH2}40C113)(aNPhNCH6H)]. A 'H NMR study indicates the existence of two isomers for each of the two tungsten CO'cli•lexes. 1-Methylimidazolyllithiura reacts with (CO)6M (M = Cr, Mo or W) to give the carbene complexes (C0)5MK'N(CH3)CHCH14(C I i 3)] after alkylation with CH3S03CF3, and the imine complexes (C0)5MOCHN(CH3)CH6H] after protonation with SO3CF3. Reaction of 1-methylimidazolyllithium with the anionic salt (C0)5 Cl = Cr or W), followed by alkylation with CH3S03CF3 affords both the mono- and bis(carbene) complexes, (CO)5M[CN(CH3)CHCHN(CH3)] and (C0)41v1[6N(CH3)CHCIRA(CH3)]2. The complex (C0)5W[C(0 {CH2 } 40C113)(t‘NPhNaldH)] reacts with phenylethynthiolate to furnish an anionic organometallic synthon that can either be alkylated or protonated. Protonation leads to two isomeric forms of the metal-coordinated thioaldehyde, (C0)5W4—SHC(Ph)=C(OCH3)(oNPhNCHell), whilst alkylation with various electrophilic reagents produces the metal coordinated dithio-esther (C0)5 W4--S=C [ SCH3] [C(Ph)=C(OCH3)(tNPhNaldH)]. The neutral divinylcarbene complexes (C0)5Cr{cC(a0CH2CMe2N)SC CH} (a) and (C0)5W{cC(COCH2CMe214)SCH9H} (19) are prepared by reaction of (C0)5MCr with the 3-lithiated thienyloxazoline, followed by alkylation with CH3S03CF3 . These complexes are the first examples of coordinated 'divinylcarbenes utilizing the group 6 transition metals, where the carbene carbon shows carbene character. They are also in another sense unique since the nucleopbutlic heteroatom where alkylation occurs, is situated outside the coordinated ring-system, and, therefore, more than two bonds removed fro the carbene carbon atom.

by Yee-Lok Wong. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Layered metal sulfides MoS2 and WS2 exhibit highly anisotropic surface chemistry. Adsorption of molecules is stronger on the atomic layer edges than on atomic planes. The edges are catalytically active in the petroleum hydrodesulfurization, while the layer planes are inert. Dispersing MoS2 and WS2 on the nanometer scale can also lead to the onset of photocatalytic properties due to the bandgap tuning by quantum confinement. In this work, we aim at determining how the adsorption on surface sites is altered for the nanoparticles compared to the bulk sulfides (micron-sized particles). A comparative study of the MoS2 and WS2 nanoparticles and bulk materials is done by attempting the adsorption of small molecules (N2, CO, acetone, and acetonitrile) to probe the surface sites. MoS2 and WS2 nanoparticles were synthesized by thermal decomposition of the metal hexacarbonyls in presence of sulfur in high-boiling solvents. The size range is 5-30 nm from Transmission Electron Microscopy. Transmission Infrared Spectroscopy was used to monitor the spectra of the probe molecules. A dedicated experimental setup has been constructed that consists of a high-vacuum chamber with a base pressure of 5×10-7 Torr. At the lowest achievable temperature of the sample (-145°C), N2, CO, and acetone were found to not adsorb strongly enough to be retained in vacuum on these materials. Acetonitrile was found to adsorb on these materials at -145°C and to desorb between -90°C and -50°C. The nanomaterial samples adsorbed significantly more acetonitrile than the corresponding bulk sulfides, as judged by the infrared signals intensity. Qualitatively, adsorbed acetonitrile species on nanodispersed and bulk sulfides are the same. It is likely that most of the adsorbed acetonitrile observed is physisorbed as ice or adsorbed on the sulfur-terminated terraces. At the final stages of desorprtion, distinctly different adsorbed species are seen whose CN stretching IR bands are shifted to higher frequencies. It is likely that these minority species are at monolayer or submonolayer coverages. The exact nature of the species requires further studies. / Department of Chemistry

Thesis (Ph.D.) -- McMaster University, 1998. / Includes bibliographical references (leaves 206-210). Also available via World Wide Web.

Thesis (Ph. D., Chemical Engineering)--University of Idaho, May 2006. / Major professor: Vivek Utgikar. Includes bibliographical references (leaves 99-107). Also available online (PDF file) by subscription or by purchasing the individual file.