本研究主要分為兩部分，第一、二章說明光觸媒與離子摻雜的二氧化鈦製備等基本原理，第三章採用四丁基鈦為前驅物，尿素等不同氮來源，三嵌段高分子P123為模板，採溶凝膠法合成含氮摻雜的球形二氧化鈦，在可見光下對亞甲基藍具有降解效果。第四章在此基礎上再嘗試加入鎢酸銨以合成鎢氮共摻雜的球形二氧化鈦，進行X光繞射分析、氮氣吸脫附、掃瞄式電子顯微鏡、電子能譜儀等綜合分析顯示，其結構為中孔洞結構銳鈦礦球形二氧化鈦，氮的鍵結屬γ-N2型鍵結，鎢則以O-W-N 或WO3的結晶附於二氧化鈦表面，適量摻雜的鎢氮共摻雜的二氧化鈦在可見光下對羅丹明B的降解反應優於商用二氧化鈦P25。第二部分第五、六章以商用二氧化鈦P25為鈦的前驅物，與不同重量比例的尿素進行共水熱反應，合成一系列含氮摻雜的鈦酸管，進行X光繞射分析、氮氣吸脫附、掃瞄式電子顯微鏡、電子能譜儀等綜合分析顯示，共水熱方式可成功的以一步驟合成出具高比表面積的含氮摻雜鈦酸管，而隨著尿素添加量的增加，鈦酸管的表面形貌會由管狀逐漸轉變成顆粒狀，氮在鈦酸管中是以Ti-O-N 或 Ti-N-O 的方式鍵結，屬於間隙型化學吸附方式的摻雜。各不同尿素添加量所合成鈦酸管對羅丹明B的降解反應均優於商用二氧化鈦P25，其反應機構推論為脫乙基反應(Deethylation) 與氮摻雜鈦酸管後降低二氧化鈦能階在可見光下產生電子電洞對所引發的礦化 (Mineralization) 兩種機構的加成效果(Synergistic effect)。

This dissertation consisits of two sections regarding the visible light driven photocatalysts based upon nitrogen doped and nitrogen tungsten codoped titania. The first Chapter 1 to Chapter 3 emphasized relvent backround of photocatalysis and metal or non-metal doped titania. Within Chapter 4, a sphere-like W,N-codoped TiO2 photocatalysts were prepared by a simple one-pot synthesis route. The morphology and microstructure characteristics of W,N-codoped titania photocatalysts with different amount of tungsten doping were characterized by means of XRD, BET, SEM, XPS, DRS and UV–vis. The metal and nonmetal codoped W,N-TiO2 sample shows the photocatalytic activity, which is much superior to the commercial titania P25 and undoped titania under visible light irradiation. The probable mechanism of codoping effect is proposed. The tungsten ions with changing valences in the W,N-TiO2 samples are considered to act as trapping sites, which will effectively decrease the recombination rate of photo-induced electrons and holes and then increase the photo-oxidation efficiency of the catalysts. The second section in Chapter 5 and Chapter 6 regards a facile one-step cohydrothermal synthesis via urea treatment has been adopted to prepare a series of nitrogen-doped titanate nanotubes with highly efficient visible light photocatalysis of rhodamine B, in an effect to identify the effect of nitrogen doping on the photodegradation efficiency. The morphology and microstructure of the thus-prepared N-doped titanates were characterized by nitrogen adsorption/desorption isotherms, transmission electron microscopy, and scanning electron microscopy. With increasing urea loadings, the N-doped titanates change from a porous multi-layer and nanotube-shaped to a dense and aggregated particle-shaped structure, accompanied with reduced specific surface area and pore volume and enhanced pore diameter. Interstitial linkage to titanate via Ti-O-N and Ti-N-O is confirmed by X-ray photoelectron spectroscopy. Factors governing the photocatalytic degradation such as the specific surface area of the catalyst and the degradation pathway are analyzed, a mechanistic illustration on the photodegradation is provided, and a 3-stage degradation mechanism is identified. The synergistic contribution due to the enhanced deethylation and chromophore cleavage on rhodamine B molecules and the reduced band gap on the catalyst TiO2 by interstitial nitrogen-doping has been accounted for the high photodegradation efficiency of the N-doped titanate nanotubes.

Table of contents
論文審定書 i
Acknowledgement ii
摘要 iii
Abstract iv
Table of contents v
List of figures x
List of tables xiv
Chapter 1. Introduction 1
1.1 Introduction 1
1.2 Photoinduced Reactivity of Titanium Dioxide 3
1.3 Mesoporous Titanium Dioxide 8
1.4 Nitrogen Doped Mesoporous Titanium Dioxide 11
1.5 Rationale and Objective of this study 14
Chapter 2. Literature Review 19
2.1 Mesoporous Materials 19
2.2 Titanium-based Mesoporous Materials 23
2.3 Doping on Titania-based Mesoporous Materials 28
2.3.1 Metal Doped Titanium Dioxide 28
2.3.2 Non-metal Doped Titanium Dioxide 30
2.3.3 Nitrogen Doped Methods 31
2.3.4 XPS debate in Nitrogen Doped Titania 32
2.4 Photodegradation Application of Dye Pollutant over Nitrogen-doped Titania in Visible-light 38
2.4.1 Operational Parameters in Photocatalyst Efficiency 39
2.4.2 Direct and Indirect Photocatalysis 40
2.5 Photocatalysis Ability of Titanate Nanotube 43
Chapter 3. Synthesis and Characterization of N-doped Titanium Dioxide by Different N source 47
3.1 Experimental Scheme 47
3.1.1 Chemical Reagents 48
3.1.2 Synthesis of Mesoporous Titanium Dioxide 48
3.1.3 Nitrogen-Doped Mesoporous Titanium Dioxide 50
3.2 Characterization 53
3.3 Photocatalytic Activity Evaluation 55
3.4 Results and Discussion 56
3.4.1 Characterization of Mesoporous N-Doped Titanium Dioxide 56
3.4.2 Photocatalytic Activity 73
3.5 Conclusion 75
Chapter 4. Enhancement of Visible Light Photo- activity of Tungsten-Nitrogen Codoped Mesoporous Titania Sphere via a Facile One-pot Synthesis 76
4.1 Introduction 76
4.2 Experimental 79
4.2.1 Preparation of W-N Codoped Titania Spheres 79
4.2.2 Characterizations 80
4.2.3 Photocatalytic Activity 81
4.3 Results and Discussion 82
4.3.1. Morphological and Microstructural Characterizations 82
4.3.2 Photocatalytic Activity 95
4.4 Conclusions 98
Chapter 5. One Step Co-hydrothermal Synthesis of Nitrogen- doped Titanium Oxide Nanotubes with Enhanced Visible Light Photocatalytic Activity 100
5.1 Introduction 100
5.2 Experimental 103
5.2.1 Preparation of N-doped TiO2 Nanotubes 103
5.2.2 Characterizations 104
5.2.3 Photocatalytic Activity 104
5.3. Results and Discussion 105
5.3.1. Morphological and Microstructural Characterizations of N-doped TiO2 Nanotubes 105
5.3.2. Chemical Identification of N-doped TiO2 Nanotubes 112
5.3.3 Photocatalytic Activity 117
5.4 Conclusions 121
Chapter 6. Effect of Nitrogen Doping on the Micro- structure and Visible Light Photocatalysis of Titanate Nanotubes by a Facile Co- hydrothermal Synthesis via Urea Treatment 123
6.1. Introduction 123
6.2 Experimental 128
6.2.1 Preparation of N-doped Titanate Nanotubes 128
6.2.2 Characterizations 128
6.2.3 Photocatalytic Activity 129
6.3 Results and Discussion 130
6.3.1. Morphological and Microstructural Characterizations of N-doped Titanate Nanotubes 130
6.3.2. Chemical Identification of N-doped Titanate Nanotubes 137
6.3.3 Photocatalytic Activity 141
6.3.4 Nitrogen-doping Effect 145
6.4 Conclusions 149
Vitae 164

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