本研究主要探討紫外光結合探針型超音波產生器在雙夾套玻璃反應器中進行超音波光催化降解2,4-二氯苯氧乙酸。
使用四種合成方法製備TiO2 粉末。由XRD、SEM、UV-vis確定光觸媒樣品的化學與物理性質，使用BET測量所有樣品的比表面積。
光觸媒的光催化活性是使用UV-vis分光光度計以檢測2,4-D濃度表示之。在熱處理85oC製備的Hydrolysis-TiO2樣品比其他方法製備的樣品有著更高的光催化活性。其原因可歸因於在銳鈦礦/板鈦礦之異相加成效應，能有效的抑制電子與電洞之間的再結合進而提升光催化降解作用。
相較於單獨光催化的實驗結果，超音波光催化降解系統展現出更好的降解2,4-二氯苯氧乙酸效果。結合探針型超音波產生器和光催化降解顯示出有加成的效果。在本研究中利用不同的操作條件如超音波探針大小、超音波功率、光觸媒的附載量、起始酸鹼值、鹽類添加劑、過氧化氫的添加、添加不同氣體、超音波脈衝模式以及使用不同種類的光觸媒對於2,4-二氯苯氧乙酸的超音波光催化降解速率之影響。在連續式條件下改變不同流速對2,4-二氯苯氧乙酸的超音波光催化降解的影響也被探討。

The sonophotocatalytic degradation of 2,4- dichlorophenoxyacetic acid (2,4-D) under ultraviolet irradiation combined with probe-type ultrasound was carried out in a jacketed glass reactor.
Four synthetic methods were used to prepare titanium oxide powder. The chemical and physical properties of the photocatalyst samples were determined by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectra (UV-vis), also the specific surface area of all samples was measured by BET method.
The sonophotocatalytic activity performance of photocatalyst was evaluated by UV-vis spectrophotometer to detect the concentration of 2,4-dichlorophenoxyacetic acid (2,4-D). Hydrolysis-TiO2 prepared at heat treatment temperature of 85oC has higher photocatalytic than the other synthetic methods prepared at low temperature heat treatment. It can be attributed to that the synergistic effect of heterojunction in anatase/brookite composite can inhibit recombination rate of electrons and holes pairs to improve sonophotodegradation performance.
The operating conditions such as probe size, power intensity, photocatalyst loading, initial pH value of solution, effect of additions, pulse time mode, gas supplying and different kinds of photocatalysts were investigated in batch sonophotocatalytic system, the effect of flow velocity in continuous sonophotocatalytic system was also studied.

ACKNOWLEDGEMENTS I
ABSTRACT (ENGLISH) II
ABSTRACT (CHINESE) IV
TABLE OF CONTENTS V
LIST OF TABLES X
LIST OF FIGURES XI
SYMBOLS XVIII
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 LITERATURE REVIEW 6
2.1 Introduction of advanced oxidation processes (AOPs) 6
2.2 Ultraviolet 7
2.3 Properties and structure of TiO2 8
2.3.1 Semiconductor basic property 12
2.3.2 The photochemical reaction of TiO2 18
2.4 Preparation of titanium dioxide powder 22
2.4.1 Sol-gel method 22
2.4.2 Hydrolysis method 23
2.4.3 Chemical vapor deposition (CVD) 24
2.4.4 Hydrothermal method 24
2.5 Degradation ways 25
2.6 Ultrasound 26
2.6.1 Cavitation 27
2.6.2 The mechanism of ultrasound in aqueous solution 31
2.6.3 Oxygen vacancies (Vo) 32
2.7 Effect of the photocatalytic reaction parameters 34
2.7.1 Effect of initial pH value 34
2.7.2 Effect of ultrasound probe size 35
2.7.3 Effect of photocatalyst loading 35
2.7.4 Effect of ultrasound power intensity 36
2.7.5 Effect of salts and peroxide 36
2.7.6 Effect of flow rates 37
2.7.7 Effect of dissolved gas 38
2.8 2,4-dichlorophenoxyacetic acid (2,4-D) 39
CHAPTER 3 EXPERIMENTAL 42
3.1 Materials 42
3.2 Apparatus and instruments 45
3.3 Preparation of Hydrolysis-TiO2 photocatalyst 53
3.3.1 Hydrolysis-TiO2 53
3.3.2 CH3COOH-TiO2 55
3.3.3 H2O2-TiO2 57
3.3.4 UV-TiO2 59
3.4 Instrumental apparatus for characteristic analysis of photocatalyst 61
3.4.1 Diffuse reflectance spectra analysis 61
3.4.2 X-Ray diffraction analysis 61
3.4.3 Scanning electron microscopy analysis 62
3.4.4 Brunauer-Emmett-Teller sorptometer 62
3.5 Experimental procedure 64
3.5.1 Blank experiment 64
3.5.2 Sonolytic degradation of 2,4-D 65
3.5.3 Photolytic degradation of 2,4-D 66
3.5.4 Photocatalytic degradation of 2,4-D 66
3.5.5 Photocatalytic degradation of 2,4-D in continuous system 67
3.5.6 Sonophotocatalytic degradation of 2,4-D 67
3.5.7 Sonophotocatalytic degradation of 2,4-D in series in continuous system 69
3.5.8 Sonophotocatalytic degradation of 2,4-D in parallel in continuous system 70
CHAPTER 4 RESULTS AND DISCUSSION 75
4.1 Properties of the TiO2 photocatalyst 75
4.1.1 Hydrolysis-TiO2 75
4.1.2 CH3COOH-TiO2 75
4.1.3 H2O2-TiO2 76
4.1.4 UV-TiO2 76
4.1.5 XRD properties of the prepared TiO2 photocatalyst 81
4.1.6 UV-Visible absorption spectra of the TiO2 photocatalyst 89
4.1.7 BET properties of photocatalyst 94
4.1.8 SEM properties of the TiO2 photocatalyst 96
4.2 Blank experiment 101
4.3 Sonophotocatalytic degradation of 2,4-D 104
4.3.1 Comparison of degradation efficiency with four synthetic methods to prepare titanium oxide powder photocatalyst 106
4.3.2 Effect of ultrasound pulse time mode 110
4.3.3 Effect of additive 112
4.3.3.1 Addition of sodium chloride 112
4.3.3.2 Addition of hydrogen peroxide 115
4.3.4 Effect of photocatalyst loading 117
4.3.5 Effect of initial pH value 119
4.3.6 Effect of ultrasound power intensity 122
4.3.7 Effect of different probe sizes 124
4.3.8 Effect of gas supplying 126
4.3.9 Effect of flow velocity in the continuous sonophotocatalytic
system( in series ) 128
4.3.10 Degradation flow velocity in the continuous sonophoto -catalytic system( in parallel ) 132
4.4 Sonophotodegradation kinetics 134
CHAPTER 5 CONCLUSIONS 143
REFERENCES 145
APPENDEX (P25-TiO2 data) 155

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