Gold used to be regarded as catalytically inert until about 20 years ago when it was shown that supported gold clusters < 5 nm in diameter exhibited some unique catalytic properties. Based on this revelation, several studies have demonstrated the feasibility of reactions previously thought of as impossible on gold. The ability of gold to oxidize CO below ambient temperatures at rates higher than conventional CO oxidation catalysts (Pd and Pt) has been shown to hold potentials for technological applications. Extensive past and on-going research are geared towards elucidating the mechanistic details of this reaction. The nature of the active sites, the effect of the supports and the effect of moisture are still debated in literature. I therefore present some experimental results supported with density functional theory calculations to shed additional light on some of the issues concerning gold catalysis in general, and low temperature CO oxidation in particular. Previous studies of the effect of moisture on oxide-supported gold reported that although water promotes CO oxidation on this surface by as much as two orders of magnitude, it is only a spectator molecule on the surface. I present here evidence for strong water-oxygen interactions when water is co-adsorbed with atomic oxygen on Au(111). Impinging a CO beam on the surface co-adsorbed with oxygen and water produces water-enhanced CO oxidation. Based on these results, I propose that CO reacts with hydroxyls formed from water-oxygen interactions to form CO₂, similar to a previous observation on Pt(111). Exposing a Au(111) surface pre-covered with ¹⁶O to isotopically labeled carbon dioxide (C¹⁸O₂) showed that ¹⁶O¹⁸O (m/e = 34) was produced from carbonate formation and decomposition. Estimates of reaction probability and activation energy gave ~ 10⁻⁴ - 10⁻⁵ and -0.15 eV respectively. The effect of annealing on the reactivity of oxygen pre-covered Au(111) was investigated using water, carbon monoxide and carbon dioxide as probe molecules. Precovering Au(111) with atomic oxygen followed by annealing resulted in surfaces that were less reactive towards water, CO and CO₂. Annealing is believed to stabilize the reactive metastable oxygen thereby increasing the barrier to reaction similar to what is reported on other surfaces. / text

The effect of acoustic and hydrodynamic cavitation on the precipitation of inorganic catalytic materials was investigated. The overall objective was to understand the fundamental factors involved in synthesizing nanometer-size catalytic materials in the 1-10 nm range in a cavitating field. Materials with grain sizes in this range have been associated with enhanced catalytic activity compared to larger grain size materials. A new chemical approach was used to produce titania supported gold by coprecipitation with higher gold yields compared to other synthesis methods. Using this approach, it was determined that acoustic cavitation was unable to influence the gold mean crystallite size compared to non-sonicated catalysts. However, gold concentration on the catalysts was found to be very important for CO oxidation activity. By decreasing the gold concentration from a weight loading of 0.50% down to approximately 0.05%, the rate of reaction per mole of gold was found to increase by a factor of 19. Hydrodynamic cavitation at low pressures (6.9-48 bar) was determined to have no effect on gold crystallite size at a fixed gold content for the same precipitation technique used in the acoustic cavitation studies. By changing the chemistry of the precipitation system, however, it was found that a synergy existed between the dilution of the gold precursor solution, the orifice diameter, and the reducing agent addition rate. Individually, these factors were found to have little effect and only their interaction allowed gold grain size control in the range of 8-80 nm. Further modification of the system chemistry and the use of hydrodynamic cavitation at pressures in excess of 690 bar allowed the systematic control of gold crystallite size in the range of 2-9 nm for catalysts containing (2.27 ± 0.17)% gold. In addition, it was shown that the enhanced mixing due to cavitation led to larger gold yields compared to classical syntheses. The control of gold grain size was gained at the loss of CO activity, which was attributed to the formation of non-removable sodium titanate species. The increased mixing associated with cavitation contributed to the activity loss by partially burying the gold and incorporating more of the sodium titanate species into the catalysts. This work produced the first evidence of hydrodynamic cavitation influencing the gold crystallite size on titania supported gold catalysts and is the only study reporting the control of grain size by simple mechanical adjustment of the experimental parameters. Despite the low activity observed due to sodium titanate, the methodology of adjusting the chemistry of a precipitating system could be used to eliminate such species. The approach of modifying the chemical precipitation kinetics relative to the dynamics of cavitation offers a general scheme for future research on cavitational processing effects.

Ho Chun Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references. / Abstracts in English and Chinese. / ABSTRACT --- p.iv / DECLARATION --- p.vi / ACKNOWLEDGEMENT --- p.vii / TABLE OF CONTENTS --- p.viii / LIST OF TABLES --- p.xi / LIST OF FIGURES --- p.xii / Chapter Chapter One: --- Introduction --- p.1 / Chapter 1.1 --- Overview --- p.1 / Chapter 1.2 --- Fundamental of CeO2 --- p.2 / Chapter 1.3.1 --- Synthesis and Modification of Ceria-based Materials --- p.5 / Chapter 1.3.1 --- Synthetic Method --- p.5 / Chapter 1.3.2 --- "Mesoporous Structure of Ce02, CexZr1-x02" --- p.6 / Chapter 1.3.3 --- Doped Ce02 Materials --- p.6 / Chapter 1.3.4 --- Fabrication of Ceria and Cerium-based Nanoparticles --- p.7 / Chapter 1.4 --- Scope of work --- p.8 / Chapter 1.5 --- References --- p.11 / Chapter Chapter Two: --- Meso- and Macro-porous Pd/CexZr1-x02 as Carbon Monoxide Oxidation Catalysts --- p.16 / Chapter 2.1 --- Introduction --- p.16 / Chapter 2.2 --- Experimental Section --- p.18 / Chapter 2.2.1 --- Sample Preparation - Synthesis of the Catalyst Support --- p.18 / Chapter 2.2.2 --- Addition of Pd to the Catalyst Support --- p.19 / Chapter 2.2.3 --- Characterization --- p.20 / Chapter 2.2.4 --- Carbon monoxide oxidation measurement --- p.21 / Chapter 2.3 --- Results and Discussion --- p.22 / Chapter 2.3.1 --- XRD analysis --- p.22 / Chapter 2.3.2 --- SEM and TEM --- p.25 / Chapter 2.3.3 --- N2-Soprtion --- p.32 / Chapter 2.3.4 --- X-ray Photoelectron Spectroscopy --- p.40 / Chapter 2.3.5 --- Thermal Catalysis Study --- p.45 / Chapter 2.4 --- Conclusion --- p.52 / Chapter 2.5 --- References --- p.54 / Chapter Chapter Three: --- Morphology-Controllable Synthesis of Ce02 Nano and Meso-structures --- p.60 / Chapter 3.1 --- Introduction --- p.60 / Chapter 3.2 --- Experimental Section --- p.62 / Chapter 3.2.1 --- Materials and Experimental Conditions --- p.62 / Chapter 3.2.2 --- Characterization --- p.64 / Chapter 3.3 --- Results and Discussion --- p.67 / Chapter 3.3.1 --- SEM and TEM Analysis --- p.67 / Chapter 3.3.2 --- XRD Analysis --- p.75 / Chapter 3.3.3 --- N2-Soprtion --- p.78 / Chapter 3.3.4 --- X-ray Photoelectron Spectroscopy --- p.84 / Chapter 3.3.5 --- FT-IR Analysis --- p.87 / Chapter 3.3.6 --- GC-MS Analysis --- p.89 / Chapter 3.3.7 --- Proposed Formation of Ce02 nanospheres and their transformation to microrods --- p.95 / Chapter 3.3.8 --- UV absorption spectra and band gap energies --- p.97 / Chapter 3.3.9 --- Thermal Catalysis Study --- p.100 / Chapter 3.4 --- Conclusion --- p.103 / Chapter 3.5 --- References --- p.105 / Chapter Chapter Four: --- Conclusion --- p.110 / LIST OF PUBLICATIONS --- p.112

Chiu, Ka Lok = 多孔生物遺態氧化銅/氧化鈰/氧化鋁之複合物料的製作及其定性分析 / 趙家樂. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstract also in Chinese. / Chiu, Ka Lok = Duo kong sheng wu yi tai yang hua tong/yang hua shi/yang hua lu zhi fu he wu liao de zhi zuo ji qi ding xing fen xi / Zhao Jiale. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgment --- p.v / Table of contents --- p.vi / List of table captions --- p.x / List of figure captions --- p.xi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Carbon monoxide (CO) --- p.1 / Chapter 1.2 --- Production of hydrogen from methanol for fuel cell --- p.2 / Chapter 1.3 --- Catalysts for CO oxidation and methanol reforming --- p.5 / Chapter 1.4 --- Copper-based catalysts --- p.6 / Chapter 1.5 --- Mechanisms in the catalytic processes --- p.7 / Chapter 1.6 --- Synthesis of Cu-based catalysts --- p.10 / Chapter 1.7 --- Potential applications of the biomorphic CuO/CeO2/Al2O3 catalyst --- p.11 / Chapter 1.8 --- Objectives and the thesis layout --- p.12 / Chapter 1.9 --- References --- p.13 / Chapter Chapter 2 --- Methods and Instrumentation --- p.16 / Chapter 2.1 --- Sample preparations --- p.16 / Chapter 2.1.1 --- Syntheses of the biomorphic samples --- p.16 / Chapter 2.1.2 --- Syntheses of the control samples (R1 and R2) --- p.17 / Chapter 2.2 --- Characterization --- p.18 / Chapter 2.2.1 --- Scanning electron microscope (SEM) --- p.18 / Chapter 2.2.2 --- Transmission electron microscopy (TEM) --- p.19 / Chapter 2.2.3 --- X-ray powder diffractometry (XRD) --- p.20 / Chapter 2.2.4 --- Fourier transform infrared (FTIR) spectroscopy --- p.21 / Chapter 2.2.5 --- Raman scattering (RS) spectroscopy --- p.22 / Chapter 2.2.6 --- Differential thermal analysis (DTA) --- p.22 / Chapter 2.2.7 --- Thermogravimetric analysis (TGA) --- p.23 / Chapter 2.2.8 --- Gas sorption surface analysis (GSSA) --- p.24 / Chapter 2.3 --- Catalytic activity --- p.25 / Chapter 2.3.1 --- CO oxidation --- p.25 / Chapter 2.3.2 --- Partial oxidation of methanol (POMe) --- p.27 / Chapter 2.3.3 --- Steam reforming of methanol (SRMe) --- p.28 / Chapter 2.4 --- References --- p.29 / Chapter Chapter 3 --- "Results, discussions and characterization" --- p.31 / Chapter 3.1 --- Biomorphic samples --- p.31 / Chapter 3.1.1 --- Macrostructures --- p.31 / Chapter 3.1.2 --- SEM and TEM results --- p.32 / Chapter 3.1.3 --- XRD analysis and chemical compositions --- p.35 / Chapter 3.1.4 --- RS results --- p.41 / Chapter 3.1.5 --- FTIR results --- p.44 / Chapter 3.1.6 --- Thermal property --- p.46 / Chapter 3.1.7 --- Porosity analysis --- p.48 / Chapter 3.2 --- Control sample R1 --- p.52 / Chapter 3.2.1 --- Microstructures --- p.52 / Chapter 3.2.2 --- Surface area and porosity --- p.55 / Chapter 3.2.3 --- Thermal property --- p.56 / Chapter 3.2.4 --- "XRD, FTIR and RS results" --- p.58 / Chapter 3.3 --- Control sample R2 --- p.60 / Chapter 3.3.1 --- Microstructures --- p.60 / Chapter 3.3.2 --- Surface area and porosity --- p.61 / Chapter 3.3.3 --- "XRD, FTIR and RS results" --- p.62 / Chapter 3.3.4 --- Thermal property --- p.63 / Chapter 3.4 --- Formation mechanisms of the biomorphic samples --- p.64 / Chapter 3.5 --- Impacts of the Cu/Ce/Al ratios on the CuO dispersion --- p.66 / Chapter 3.6 --- Cotton biotemplate --- p.66 / Chapter 3.7 --- Formation mechanisms of R1 and R2 --- p.67 / Chapter 3.8 --- References --- p.69 / Chapter Chapter 4 --- Evaluations of Catalytic Activities --- p.71 / Chapter 4.1 --- CO oxidation --- p.71 / Chapter 4.2 --- POMe --- p.79 / Chapter 4.3 --- SRMe --- p.91 / Chapter 4.4 --- Physical properties of the biomorphic samples before and after the reactions --- p.97 / Chapter 4.5 --- Structure of the sample and its catalytic performance --- p.102 / Chapter 4.6 --- CuO dispersion and the catalytic performance --- p.103 / Chapter 4.7 --- Al2O3 and CeO2 and the catalytic performance --- p.105 / Chapter 4.8 --- Catalytic performance of the biomorphic samples and R2 --- p.108 / Chapter 4.9 --- References --- p.109 / Chapter Chapter 5 --- Conclusions and suggestions for further studies --- p.110 / Chapter 5.1 --- Conclusions --- p.110 / Chapter 5.2 --- Future works --- p.112 / Chapter 5.3 --- References --- p.114

The purpose of this study was to investigate the supported catalyst of the type CuO-Al₂O₃ which has been described by Lockwood and Frazer (13). This type of catalyst is unique in that it has a high activity at low temperatures, is suitable for use at high temperatures and has been reported to be truly catalytic in the oxidation of carbon monoxide. Lockwood and Frazer (15) have described the preparation of a catalyst of this type. Their description of the method of preparation and of the quantities of materials used is rather inadequate for an exact duplication of the catalyst which they prepared and studied. The method of procedure used in the study of this catalyst has been to vary both the composition and heat treatment of the catalysts and to observe the subsequent change in catalytic activity. 1. Increasing the copper oxide content of the copper oxide-aluminum catalysts increases the activity of the catalysts at least over the composition range studied. 2. Increasing the temperature to which the copper oxide-aluminum oxide catalysts are heated increases the activity. 3. The temperatures required for the catalysts to exhibit 100% activity are all above 270°C. 4. It was found impossible to reproduce the copper oxide-aluminum catalyst which was prepared by Lockwood and Frazer. 5. A catalyst prepared from pure copper oxide was more active than any of the catalysts which were studied. / M.S.

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