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研究生：	阮光碧 Quang Bac Nguyen
論文名稱：	Synthesis, Structural Characterization and Properties of Organically Incorporated Transition Metal Germanates and Uranium Germanates
指導教授：	李光華 Kwang-Hwa Lii
口試委員:
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2012
畢業學年度：	101
語文別：	英文
論文頁數：	243
中文關鍵詞：	過渡金屬、鍺酸鹽、高溫高壓水熱合成、溶劑熱、離子熱、鈾金屬
外文關鍵詞：	Transition metal, uranium, germanate, solvothermal, ionothermal, high-temperature, high-pressure hydrothermal synthesis
相關次數：	點閱：16 下載：0
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Microporous materials have widespread applications including ion-exchange, selective sorption or separation, and catalysis processes. New microporous compounds with novel structures and interesting properties are extremely desired for growing demands in technology.
This thesis descrives the synthesis, crystal structures and properties of organically incorporated transition metal germanates (series A), and uranium germanates (series B), which are classified on the basis of their structural characteristics and the methods of preparation. These compounds are synthesized by solvothermal, ionothermal, and high-temperature, high-pressure hydrothermal methods, and characterized by various spectroscopic techniques.
In series A, a zinc germanate, A1, was synthesized by solvothermal method. Its structure contains neutral infinite chains with empty 18-membered ring channels. This is the first example in literature where the fluorine atoms in the germanate cluster are characterized by 19F NMR spectroscopy. A niobium germanate, A2, was synthesized by using a deep-eutectic solvent as the medium for the synthesis. Its layer structure consists of NbGe6X19 clusters with 10 membered-ring windows. This is the first example of organically templated niobium germanate where the structure was characterized by single-crystal X-ray diffraction. This compound displays an intense SHG response.
In series B, the synthesis, crystal structures, and properties of three novel uranium germanates with various valence states of uranium are discussed. B1 is a mixed-valence uranium(IV,VI) germanate, Cs8UIV(UVIO2)3(Ge3O9)3•3H2O. B2 is a tetravalent uranium germanate containing four- and five-coordinate germanium, Cs4U([5]Ge2O2)([4]Ge3O9)2. B3 is a pentavalent uranium germanate containing four- and six-coordinate germanium, Cs3U[6]Ge([4]Ge3O9)2. These compounds have been structurally synthesized under high-temperature, high-pressure hydrothermal conditions and characterized by single-crystal X-ray diffraction. The valence states of uranium have been confirmed by X-ray photoelectron spectroscopy, electron paramagnetic resonance, UV-visible, and photoluminescence measurements.

Abstract                            
List of Publications                        
Abbreviations
Table of contents                        
List of Figures                            
List of Tables
List of Schemes            
Chapter 1. Organically Incorporated Germanates and Transition Metal Germanates                    1
1 Organically Incorporated Germanates                1
2 Organically Incorporated Transition Metal Germanates    15
2.1 Zirconium Germanates                        15
2.2 Niobium Germanates                        17
2.3 Nickel Germanates                        18
2.4 Zinc Germanates                        20
2.5 Cobalt, and Cadmium Germanates                22
3 Uranium Silicates and Uranium Germanates            27
4 Overview of the Research and Outlook            38
5 References                            39
Chapter 2. Synthesis and Characterization Methods    42
1 Synthesis Methods                        42
1.1 High-Temperature Solid-State Reactions            42
1.2 Flux-Growth Synthesis                        43
1.3 Hydrothermal, Solvothermal, and Ionothermal Syntheses    43
2 Methods for Characterization of Materials            51
2.1 Single-Crystal X-ray Diffraction                52
2.2 Powder X-ray Diffraction                    56
2.3 Solid-State Nuclear Magnetic Resonance Spectroscopy    56
2.4 Energy-dispersive X-ray Spectroscopy                58
2.5 Electron Probe Microanalysis                    59
2.6 Total Reflection X-ray Fluorescence                59
2.7 Second-Harmonic Generation                    59
2.8 Fourier Transform Infra-Red Spectroscopy            61
2.9 Thermogravimetric Analysis                    61
2.10 Elemental Analysis                        61
2.11 X-Ray Photoelectron Spectroscopy                62
2.12 Electron Paramagnetic Resonance                70
2.14 Optical Absorption and Photoluminescence            76
3 List of Reagents                            79
4 List of Equipments                        80
5 List of Compounds                        81
6 References                            82
Chapter 3. Synthesis, Crystal Structures and Properties of Organically Incorporated Transition Metal Germanates                                    85
1 A One-Dimensional Zinc Germanate Containing Hollow Columns with an Extra-Large 18-Membered Ring Window                                    85
2 An Organically Templated Niobium Germanate        103
3 References                            115
Chapter 4. Synthesis, Crystal Structures, and Properties Of Uranium Germanates                    117
1 A Mixed-Valence Uranium(IV,VI) Germanate Containing 9-Ring Channels, Cs8UIV(UVIO2)3(Ge3O9)3•3H2O            117
2 A Tetravalent Uranium Germanate Containing Four- and Five-coordinate Germanium, Cs4U([5]Ge2O2)([4]Ge3O9)2        136
3 A Pentavalent Uranium Germanate Containing Four- and Six-Coordinate Germanium, Cs3U[6]Ge([4]Ge3O9)2        149
4 References                            166
Conclusions                            168
Appendice                        
        171

                                

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