published_or_final_version / abstract / toc / Chemistry / Master / Master of Philosophy

Thesis (M. Phil.)--University of Hong Kong, 2005. / Title proper from title frame. Also available in printed format.

The research presented in this dissertation involved characterization of the Cu/ZnO solid catalyst system as applied to methanol/steam reformation. Thermogravimetry was used to investigate in-lab synthesized samples and a commercial product G66B (Cu/ZnO 33/67 wt. %). The 33% Cu sample contained Cu ions in the ZnO matrix. This phase required the highest temperatures (400°C) for H₂ reduction. The 50% Cu sample reduced at a lower temperature (220°C) but its complete reduction required the same maximum temperature. The higher temperature process was similar to the 33% case, while the lower one was due to the reduction of a amorphous CuO phase. The 66% Cu sample reduced in a fairly narrow low temperature (270°C) range. Therefore, its CuO phase has a amorphous structure. G55B reduced at lower temperatures than the in-lab samples. This difference is possibly due to different synthetic procedures used in the production of G66B and the in-lab samples. The CuO phase of G66B appears to be amorphous and well dispersed. Raman spectroscopy was used to identify the crystal phases of these solids. The complexity of the initial precipitate was monitored versus the Cu/Zn ratio of the system. The nature of the phases present under reduction conditions was determined. This information has provided insight into the active phases involved in methanol reformation. The role of the solids lattice oxygen was determined. The reaction was carried out on labelled ¹⁸O-containing Cu/ZnO. Incorporation of ¹⁸O into both CO₂ and H₂O clearly indicates the involvement of these oxygens in the reaction. Observation of C¹⁸O¹⁸O indicates that the C-O bond in methanol does not remain intact. XPS was used to determine the effects of oxidation, reduction, and reaction on the Cu component of G66B. Upon oxidation all Cu exists as Cu⁺². The catalyst always contains Cu⁺¹ and Cuᵒ after H₂ reduction. After methanol/steam reformation with a 50/50 vol% mxiture, all Cu is reduced to Cuᵒ. Changes in the Cu/Zn ratio of the surface are interpreted in terms of changes in surface morphology.

The experimental work described in this thesis is aimed at the elucidation of the speciation of the zinc and germanium 8-hydroxyquinoline systems. A knowledge of this speciation could aid in modelling the kinetics of solvent extraction of zinc and germanium with 7alkyl derivatives of 8-hydroxyquinoline. In this study the stability constants of the ligand 8hydroxyquinoline with the ions H+, Zn2+ and Ge4+ have been investigated by potentiometry at 25°C in a partially aqueous medium. A titration technique was used in which the hydrogen ion concentration was monitored using a glass indicating electrode. The partially aqueous medium comprised of O. 1 mol dm- 3 NaCl04 in 60% (v/v) dioxane and the concentration levels of the reagents were at least millimolar. The analysis of the potentiometric data was carried out with the aid of the computer programs HALTAFALL, ESTA and STATGRAPHICS. The results obtained for the systems involving the H+ and Zn2+ ions compare with those reported in the literature. The stability constant of a protonated species in the zinc-8-hydroxyquinoline system (ZnLH) was established for the first time. Precipitates obtained from the Zn2+ titrations were identified as zinc 8-hydroxyquinolate dihydrate. The germanium 8-hydroxyquinoline system has not been studied previously via potentiometry techniques. The complex hydrolysed species of germanium in aqueous solutions and the unusual features displayed in the formation curves increased the complexity of species selection. Although a suitable model of the species present could not be determined some evidence suggests the presence of protonated species. Hence, a prerequisite for resolving the germanium-8hydroxyquinoline system could be a more complete understanding of the hydrolysis of germanium in the partially aqueous medium used. / Thesis (M.Sc.)-University of Natal, Durban, 1991.

在本論文中，我們利用簡單的濕化學氧化鋅(ZnO)納米線陣列模板法成功地製備了一系列具有不同化學成份、晶體結構和形貌的準一維鋅-鐵-氧納米結構陣列。 / 垂直排列的ZnO納米線陣列首先生長在不同的襯底上，然后进一步被用作其他納米結構陣列的生長模板。ZnO納米線不僅僅起到骨架定型的作用，最終還可以为后續納米結構提供原料组分。通過控制ZnO和氯化鐵溶液的反應時間，在煅燒后，我們可以製備ZnO/鐵酸鋅(ZnFe₂O₄)納米線纜陣列，以及化學/非化學計量的ZnFe₂O₄、ZnFe₂O₄/α-三氧化二鐵(α-Fe₂O₃)和α-Fe₂O₃納米管陣列。ZnFe₂O₄和α-Fe₂O₃納米管陣列都表現出了對可見光的吸收，它們的帶隙經估算分別是2.3 eV和1.7 eV。 / 通過電子能量損失譜(EELS)，可以得到ZnFe₂O₄納米管陣列的一些細節的結構信息。我們分別研究了兩個不同系列(溫度和化學計量)的ZnFe₂O₄納米管。研究發現，樣品的磁性和它們的晶體結構有著非常緊密的關係。首先，對於溫度系列的樣品，當樣品的燒結溫度從600 °C降到400 °C時，更多的三價鐵離子(Fe³⁺)佔據了尖晶石結構中的A位置(四面體位置)而並非它們本應佔據的平衡B位置(八面體位置)。這種偏離了正常尖晶石結構的情況使得A和B位置上的Fe³⁺的超交換作用增加，進而增加了樣品的阻隔溫度(TB)，磁各向異性常數(K)，3K和300 K下的飽和磁化強度(MS)和3K下的矯頑力(HC)。同時使3K和300K下的MS的比值變小。其次，對於化學計量系列的樣品，通過比較在同一燒結溫度下製備的化學計量和非化學計量的ZnFe₂O₄納米管，我們發現在鐵鋅比大於2的納米管中，Fe³⁺佔據A和B位置的比例和化學計量的樣品是类似的。這些多出的Fe³⁺也會增加超交換作用，從而導致較大的TB, K, MS(3K和300 K)，HC(3K)和較小的MS(3 K)/MS(300 K)比值。最後，作為非化學計量的極端情況，α-Fe₂O₃納米管在小的外加磁場下表現出了典型的Morin相變，在大的外加磁場下出現了場致spin-flop轉變。 / 另一方面，我們發現，當使用羅丹明B(RhB)作為指示劑時，ZnO/ZnFe₂O₄納米線纜陣列表現出了優於纯ZnO和纯ZnFe₂O₄納米管陣列的可見光降解活性，但是它們的降解路徑各不相同。ZnO由於染料敏化機制而具有可見光降解能力，但是其降解活性最差。ZnO/ZnFe₂O₄納米線纜陣列和ZnFe₂O₄納米管陣列的基本降解原理是相同的，那就是，利用有可見光活性的ZnFe₂O₄中的光生電子和空穴所生成的活性自由基降解RhB。但是，ZnO/ZnFe₂O₄納米線纜陣列的降解能力明顯優於ZnFe₂O₄納米管陣列，這是由於ZnO與ZnFe₂O₄之間的II型能帶匹配顯著地促進了光生電子和空穴的分離。 / In the present thesis, several kinds of pseudo-one-dimensional Zn-Fe-O nanostructure arrays with tunable chemical compositions, crystal structures and morphologies are successfully synthesized via a simple wet-chemical ZnO-nanowire-array templating method. / Vertically-aligned ZnO nanowire arrays are firstly fabricated on several different substrates and then serve as templates for other nanostructured arrays growth. The ZnO nanowires not only act as morphology-defining skeleton but also contribute chemically to the final composition of the nanostructures. By controlling the reaction time between ZnO and FeCl₃ solution, ZnO/ZnFe₂O₄ nanocable arrays, stoichiometric ZnFe₂O₄ nanotube arrays, nonstoichiometric ZnFe₂O₄ nanotube arrays, ZnFe₂O₄/α-Fe₂O₃ nanotube arrays and α-Fe₂O₃ nanotube arrays can be synthesized in a controlled manner after calcination. Both ZnFe₂O₄ and α-Fe₂O₃ nanotube arrays exhibit visible light absorption and their bandgap are estimated to be ~2.3 eV and ~1.7 eV, respectively. / The detailed structural information of the ZnFe₂O₄ nanotube arrays are obtained by electron energy loss spectroscopy (EELS). In particular, EELS are carried out for two different series (i.e., temperature and stoichiometric series). The magnetic properties of these samples are found to closely correlate to their structural characteristics. Firstly, with the decrease of the calcination temperature from 600 °C to 400 °C, more Fe³⁺ions occupy A sites (tetrahedral sites in spinel structure) rather than their equilibrium B sites (octahedral sites in spinel structure). The deviation from the normal spinel structure leads to the enhancement of superexchange interactions between Fe³⁺ions in A and B sites, and thus results in an increase in blocking temperature (TB), magnetic anisotropic constant (K), saturation magnetization (MS, at 3 K and 300 K), coercivity (HC, at 3 K) and a decrease in MS(3 K)/MS(300 K) ratios. Secondly, by comparing stoichiometric and nonstoichiometric ZnFe₂O₄ nanotubes calcinated at the same temperature, we found that the nonstoichiometric nanotubes (Fe:Zn > 2) shows similar ratios of Fe³⁺in A and B sites to that of the stoichiometric one. The extra Fe³⁺in the crystal also enhances the superexchange interactions of Fe³⁺, which results in larger TB, K, MS(at 3 K and 300 K) and HC(at 3 K), and smaller MS(3 K)/MS(300 K) ratio. Lastly, α-Fe₂O₃ nanotubes, as an extreme case of the nonstoichiometric sample, show typical Morin-transition characterization under small external field, and field-induced spin-flop transition at large external field. / On the other hand, we found that the visible-light-driven photodegradation activities of ZnO/ZnFe₂O₄ nanocable arrays are superior to those of the ZnO nanowire arrays and ZnFe₂O₄ nanotube arrays using RhB as the probe molecules. All the three nanostructures show degradation of RhB molecules under visible light irradiation, but they take different degradation pathways. The degradation of RhB in the presence of ZnO nanowire arrays is attributed to the dye-sensitized mechanism, and the photodegradation activity is the worst. ZnO/ZnFe₂O₄ nanocable arrays and ZnFe₂O₄ nanotube arrays have the same degradation mechanism, that is, reactive radicals produced by photogenerated electron-hole pairs in the visible-light-active ZnFe₂O₄ are responsible for the photodegradation of RhB. However, the nanocable arrays show much higher degradation capability. This is owing to the type II band alignment between ZnO and ZnFe₂O₄, which greatly promotes the separation of photogenerated electronsand holes in ZnFe₂O₄. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Guo, Xuan = 準一維鋅-鐵-氧納米結構陣列 : 控制製備, 磁學性質以及光催化方面的應用 / 郭璇. / Thesis (Ph.D.) Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 107-117). / Abstracts also in Chinese. / Guo, Xuan = Zhun yi wei xin-tie-yang na mi jie gou zhen lie : kong zhi zhi bei, ci xue xing zhi yi ji guang cui hua fang mian de ying yong / Guo Xuan.

Methylzinc tetrahydroborate, [MeZnBH₄], has been prepared by two routes and the structure of the solid determined by X-ray crystallography to reveal helical polymers in which MeZn and BH₄ units alternate. The latter functions as a bidentate ligand with respect to each of the adjacent metal atoms. Investigation by mass spectrometry and matrix isolation shows that the vapour consists of an equilibrium mixture of monomeric and dimeric species. The pattern of infrared bands for the monomer is characteristic of a bidentate BH₄ group, a finding consistent with the results of DFT calculations. Disproportionation into [Me₂Zn] and [Zn(BH₄)₂] is a common feature of the chemistry of methylzinc tetrahydroborate, although it has been possible to isolate and characterize the adduct [MeZnBH₄.SMe₂]. The reaction between [B₄H₁₀ and [Me₂Zn] in the gas phase affords colourless acicular crystals of [(MeZn)₂B₃H₇] in yields of ca. 10%. This compound has been characterized by chemical analysis and by NMR and vibrational spectroscopy. X-ray crystallography reveals that the product is a dimer, [(MeZn)₂B₃H₇]₂, featuring two distinct zinc environments. Two B₃H₇ZnNe ligands, formally derived from B₃H₈ by replacement of a µ₂-H by a µ₂-ZnMe unit, each function in a bis(bidentate) manner linking together two other MeZn centres through pairs of Zn-H-B bridges. The structures of several aluminium tetrahydroborates in the solid phase have been investigated by X-ray diffraction. The structure of dimethylaluminum tetrahydroborate has been shown to consist of helical polymeric chains in which Me₂-Al and BH₄ units alternate. Here, too, the BH₄ groups exhibit bidentate ligation with respect to each of the adjacent metal atoms, although the degree of interaction between the metal centre and the BH₄ group is somewhat less than in [MeZnBH₄ ]. Solid aluminium tris(tetrahydroborate) exhibits two phases with a transition temperature in the range 180-195 K. Each phase is made up of discrete Al(BH ₄ )₃ units, the principal differences relating to the packing of the individual molecules. In the a phase the Al(BH ₄ )₃ molecules display an angle of 78.2° between the AlB₃ and Al(µ-H)₂ planes and are disposed about a 2₁ crystallographic screw axis; in the ß phase the molecular units conform to D_3h symmetry. Dimethylindium octahydrotriborate, [Me₂ lnB₃ H₈ ], has been synthesized by the reaction between trimethylindium and tetraborane(10) and characterized by chemical analysis and by NMR and vibrational spectroscopy. X-ray diffraction of a single crystal reveals that the solid consists of [Me₂ lnB₃ H₈] units, although there is evidence of charge separation in the sense [Me₂ln]⁺[B₃ H₈ ]^- and of secondary interaction between terminal hydrogen atoms and adjacent indium centres. The infrared spectrum of the matrix-isolated vapour is consistent with a monomeric structure similar to that of [Me₂ AlB₃ H₈].

Thesis (Ph. D.)--University of Washington, 1990. / Vita. Includes bibliographical references (leaves [231]-242).

The experimental work described in this thesis is aimed primarily towards elucidation of the speciation of zinc-cyanide systems at elevated pH. In this study the formation and stability of H+-eN-, binary Zn2+-eN- and ternary Zn2+-CN--QH- complexes were studied by glass electrode potentiometry in aqueous solutions at 25.0°0 and in a medium of ionic strength of 0.1 mol dm-3. The solution pH was varied to cover the range 4 to 11. The study was undertaken with a view to establishing whether and under what conditions soluble binary zinc-cyanide complexes and ternary zinc-cyanide-hydroxide complexes form, and to determine formation constants for any such species that are found. This information would be useful in defining more precisely the speciation of solutions containing zinc and cyanide ions at elevated pH values. A titration method was used, in which hydrogen ion concentration was monitored by means of a glass indicating electrode. The cell was calibrated to allow measurements of hydrogen ion concentration rather than hydrogen ion activity. Owing to precipitation difficulties, the reagents were used at sub-millimolar concentration levels. The potentiometric data was interpreted with the aid of various formation function plots together with the use of various computer programs, such as HALTAFALL and ESTA. The results show that the ternary complex Zn(ON)3(OH)2- is formed in significant amounts in solutions of pH > 8.5. Some evidence was also obtained for the existence of the five coordinated species Zn(CN)3(OH)~- and Zn(CN)~- in these solutions, but existence of the latter two species cannot yet be regarded as firmly established. No polynuclear complexes were detected at the sub-millimolar concentrations used. Formation constants are reported for H+-eN- and both binary Zn2+-eN- and ternary Zn2+-eN--QH- species. / Thesis (M.Sc.)-University of Natal, Durban, 1990.

1H and 13C{1H} NMR spectra of all the new compounds and crystallographic data are given in the Appendix. / Chapter 1 presents an overview of phthalocyanines including their general synthesis, properties, and applications. Special attention has been placed on the unsymmetrical analogues, and those which are efficient photosensitizers in photodynamic therapy. A brief account on BODIPYs as another versatile class of functional dyes is also given. / Chapter 2 describes the synthesis, spectroscopic characterization, photophysical properties, and in vitro photodynamic activities of three novel amphiphilic zinc(II) phthalocyanines substituted with one or two 3,4,5-tris(3,6,9-trioxadecoxy)benzoxy group(s). These compounds exhibit significantly higher photodynamic activities toward HepG2 and HT29 cell lines. The alpha-substituted analogue is particularly potent with IC50 values as low as 0.02 microM. The higher photodynamic activity of this compound can be attributed to its lower aggregation tendency in the culture media as shown by absorption spectroscopy and higher cellular uptake as suggested by the stronger intracellular fluorescence, resulting in a higher efficiency to generate reactive oxygen species inside the cells. / Chapter 4 focuses on a related series of 1,4-disubstituted zinc(II) phthalocyanines. These compounds possess two oligoethylene glycol methyl ether chains with various length at the 1,4-di-alpha-positions. The effects of the chain length on their aggregation, photophysical properties, cellular uptake, and in vitro photodynamic activities have been explored. / Chapter 5 presents the synthesis, characterization, and photophysical properties of another series of zinc(II) phthalocyanines conjugated with one, two or four isopropylidene protected glucofuranose unit(s) through a tetraethylene glycol linker. With these hydrophilic substituents, these macrocycles are highly soluble in common organic solvents and biological media. Their in vitro photodynamic activities toward HT29 and HepG2 cells have also been evaluated. Compared with the tetra-glucosylated phthalocyanines, which are almost nonphotocytotoxic, the mono- and di-glucosylated analogues exhibit a higher photodynamic activity. The di-alpha-substituted analogue is particularly potent with IC50 values as low as 0.03 microM. / Chapter 6 reports the synthesis, characterization, and photophysical properties of two novel conjugates of subphthalocyanine substituted axially with a BODIPY or distyryl-BODIPY moiety. Both systems absorb over a broad range in the visible region. They also exhibit a highly efficient photo-induced energy transfer process either from the excited BODIPY to the subphthalocyanine core or from the excited subphthalocyanine to the distyryl-BODIPY unit. The energy transfer quantum yields are close to unity for both of these conjugates. / Chapter 7 describes the preparation and photophysical properties of another two BODIPY and monostyryl-BODIPY conjugates which are linked to a silicon(IV) phthalocyanine core. These conjugates serve as excellent artificial photosynthetic models for the study of energy and electron transfer processes. Depending on the axial substituents, these conjugates exhibit predominantly a photo-induced energy or electron transfer process in toluene. / The related studies of a series of novel di-alpha-substituted zinc(II) phthalocyanines having two biocompatible triethylene glycol methyl ether chains or glycerol moieties are described in Chapter 3. Compared with the unsubstituted analogue, these compounds have a red-shifted Q band, and exhibit a relatively weaker fluorescence emission and higher efficiency to generate singlet oxygen. As a result, these compounds are promising candidates for photodynamic therapy. In vitro studies on HepG2 and HT29 cells have shown that they are highly photocytotoxic with IC50 values as low as 0.06 microM. / This thesis describes my synthetic studies on several series of functional zinc(II) phthalocyanines and boron dipyrromethenes (BODIPYs). Their applications as efficient photosensitizers in photodynamic therapy and light harvesting systems have also been explored. / Liu, Jianyong. / Adviser: Dennis Keepui Ng. / Source: Dissertation Abstracts International, Volume: 71-01, Section: B, page: 0326. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

Han, Fangyuan. / Thesis submitted in: November 2007. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 68-72). / Abstracts in English and Chinese. / Title Page --- p.I / Thesis Committee --- p.II / Acknowledgements --- p.III / Abstract --- p.IV / 摘要 --- p.V / Table of Contents --- p.1 / List of Figures --- p.4 / List of Tables --- p.6 / Chapter Chapter 1 --- Introduction --- p.7 / Chapter Chapter 2 --- Fourier Transform Spectroscopy --- p.10 / Chapter A. --- The Michelson Interferometer and the Interferogram --- p.10 / Chapter B. --- The Link between the Interferogram and the Spectrum: the Fourier Transform --- p.12 / Chapter C. --- "Resolution, Apodization and Spectral Folding" --- p.13 / Chapter D. --- Advantages and Disadvantages of FTIR Spectroscopy --- p.17 / Chapter E. --- Time-resolved FTIR Spectroscopy --- p.18 / Chapter (1) --- Time-resolved Rapid Scan Scheme --- p.18 / Chapter (2) --- Step-scan Scheme --- p.19 / Chapter F. --- Several Considerations in Step-scan Time-resolved Spectroscopy / Chapter Chapter 3 --- Molecular Fluorescence --- p.24 / Chapter A. --- Transitions Between Electronic States --- p.24 / Chapter B. --- Absorption and Vibrational Relaxation --- p.26 / Chapter C. --- Internal Conversion and Fluorescence --- p.26 / Chapter D. --- Intersystem Crossing and Phosphorescence --- p.27 / Chapter E. --- Fluorescence Lifetime and Quantum Yield --- p.29 / Chapter Chapter 4 --- Fourier Transform Spectroscopy of Zinc Phthalocyanine and Derivatives --- p.32 / Chapter A. --- Introduction --- p.32 / Chapter B. --- Apparatus --- p.35 / Chapter (1) --- VERTEX 70 FTIR Spectrometer --- p.35 / Chapter (2) --- Excitation Source --- p.38 / Chapter (3) --- Detectors and the Transient recorder --- p.38 / Chapter (4) --- Samples and Sample Cells --- p.39 / Chapter C. --- Experimental Setup --- p.40 / Chapter (1) --- Absorption Experiments --- p.40 / Chapter (2) --- Emission Experiments --- p.42 / Chapter D. --- Results and Discussion --- p.45 / Chapter (1) --- Absorption and Fluorescence Spectra --- p.45 / Chapter (2) --- Fluorescence Lifetimes and Quantum Yields --- p.51 / Chapter (3) --- Time-resolved Fluorescence Spectra --- p.54 / Chapter E. --- Some Experimental Details --- p.60 / Chapter (1) --- Choice of Windows for Regular Tests of the Instrument Performance --- p.60 / Chapter (2) --- Configurations of the Transient Recorder in OPUS --- p.61 / Chapter (3) --- Configurations of Detectors in OPUS --- p.61 / Chapter (4) --- The Standard Method of Extracting Time Slices --- p.62 / Chapter (5) --- Parameters that Easily Cause Problems --- p.63 / Chapter (6) --- Elimination of Background Noises --- p.64 / Chapter Chapter 5 --- Concluding Remarks --- p.66 / Reference --- p.68