臺灣博碩士論文加值系統

本研究主要將二氧化鈦披覆於鈦網製成氧化陽極，進行染料溶液(甲基藍,
Methylene Blue 及若丹明B, Rhodamine B)的去色降解，反應程序中以不鏽鋼網製成相
對電極，並添加一偏電壓，以期達到降低電子-電洞對再結合速率，進而提升反應效
率；本研究中且以Nafion 117 質子交換膜代替液態電解質，進行相關探討。研究中
進行探討的動力因子包括溶液pH、紫外光光強度、染料初始濃度、曝氣種類、偏電
壓強度以及電解質濃度。
由實驗結果發現，透過添加偏電壓的方式並無法有效地提升甲基藍的降解速率；
在同時添加偏電壓與Nafion 時，達到最佳的甲基藍去除效果。而若丹明B 方面，相
對於單純光觸媒實驗，以添加偏電壓的方式可以增加15%的去除效果。由於不同的溶
液pH 會造成溶液中不同物種的表面帶電性改變，在靜電力的交互作用下，不僅影響
二氧化鈦對染料分子的吸附能力，也造成不同的反應效率；然而，甲基藍與若丹明B
的最適溶液pH 皆出現在pH 7.0。無論在單純光觸媒或是添加偏電壓的實驗中，較高
的紫外線光強度、溶氧量及電解質濃度都有促進染料降解的效果，而初始濃度效應大
致符合Langmuir-Hinshelwood 模式。
在添加偏電壓的實驗中發現，在不同的溶液pH 下，甲基藍有不同的最適電壓強
度；在pH 5.3 時最適電壓為0.5 V，而在pH 7.0 為0.6 V，更高偏電壓的提升效果有
限。在若丹明B 方面，pH 3.0 及7.0 的最適偏電壓皆為0.4 V，更高的偏電壓反而有
抑制的效果發生。

In this research, Methylene Blue (MB) and Rhodamine B (Rh B) were taken as model pollutants in photocatalytic aqueous reaction. The photocatalytic process with bias potential applied was conducted in aqueous supporting electrolyte and proton exchange membrane (Nafion 117 membrane). The dyestuffs degradation by UV/TiO2 and UV/TiO2/bias processes was experimentally studied by varying the solution pH, UV light intensity, initial dye concentration, gas introduction, supporting electrolyte concentration, and bias potential. Degradation of dye MB was promoted in UV/TiO2/bias process compared with that carried out in UV/TiO2 process, especially as the Nafion membrane was applied. In Rh B experiments, the removal efficiency of experiment conducted in UV/TiO2/bias process was 15% higher than that conducted in UV/TiO2 process. The photocatalytic reaction was controlled strongly by solution pH because of the electrostatic force between TiO2 particles and dye molecules. Under the electrostatic interactions, the best removal efficiencies occurred at pH 7.0 both for MB and Rh B. The photodegradation rates could be assisted by increasing concentration of supporting electrolyte, concentration of dissolving oxygen, or UV light intensity. In UV/TiO2/bias process, the rate constants of MB degradation increased with an increase in bias potential to a certain level, then leveled off. The suitable bias potentials for experiments conducted at pH 5.3 and 7.0 were found to be 0.5 and 0.6 V, respectively. In Rh B treatment, however, the optimum bias potential was found to be 0.4 V at both the pH values, 3.0 and 7.0.

Table of Contents
Acknowledgment……………………………………………………………………………………I
English Abstract………………………………………………………………………………II
Chinese Abstract………………………………………………………………………………III
Table of Contents………………………………………………………………………………IV
List of Figures……………………………………………………………………………….VII
List of Tables…………………………………………………………………………………XII
List of symbols………………………………………………………………………………XIV
Chapter
1 Introduction……………………………………………………………………………………1
1.1 Background……………………………………………………………………………………1
1.2 Objectives and scope………………………………………………………………………2
2 Literature Review……………………………………………………………………………4
2.1 Photocatalyst………………………………………………………………………………4
2.1.1 Basic properties of TiO2………………………………………………………………4
2.1.2 Reactors for UV/TiO2 process…………………………………………………………8
2.1.3 The applications of photocatalyst…………………………………………………11
2.2 Operation factors for UV/TiO2 process………………………………………………12
2.2.1 Effect of light intensity……………………………………………………………20
2.2.2 Effect of gas introduction…………………………………………………………22
2.2.3 Effect of initial concentration……………………………………………………24
2.2.4 Effect of solution pH…………………………………………………………………26
2.3 Operation factors for UV/TiO2/bias process………………………………………33
2.3.1 Effect of bias potential……………………………………………………………37
2.3.2 Effect of supporting electrolyte…………………………………………………38
2.3.3 UV/TiO2/bias Process with applying Nafion………………………………………44
3 Experimental…………………………………………………………………………………50
3.1 Materials……………………………………………………………………………………50
3.2 Apparatus and reactor design…………………………………………………………52
3.3 Procedures…………………………………………………………………………………62
3.3.1 Preparation of TiO2/Ti mesh electrode and counter electrode………………62
3.3.2 Pretreatment of Nafion membrane……………………………………………………63
3.3.3 Background experiments………………………………………………………………63
3.3.4 UV/TiO2 process…………………………………………………………………………65
3.3.5 UV/TiO2/bias process…………………………………………………………………65
3.4 Experimental conditions…………………………………………………………………66
4 Results and Discussion……………………………………………………………………70
4.1 Background experiments…………………………………………………………………70
4.1.1 Zeta potential of TiO2………………………………………………………………70
4.1.2 Photolysis………………………………………………………………………………71
4.1.3 Adsorption test…………………………………………………………………………75
4.1.4 Dyestuff stability……………………………………………………………………78
4.1.5 TiO2 deactivation test………………………………………………………………81
4.2 Degradation of dye aqueous solution in UV/TiO2 process……………………83
4.2.1 Effect of solution pH…………………………………………………………………83
4.2.2 Effect of light intensity……………………………………………………………91
4.2.3 Effect of initial concentration……………………………………………………97
4.2.4 Effect of gas introduction…………………………………………………………101
4.3 Degradation of dye aqueous solution in UV/TiO2/bias process………………107
4.3.1 Effect of solution pH………………………………………………………………107
4.3.2 Effect of light intensity…………………………………………………………114
4.3.3 Effect of initial concentration…………………………………………………121
4.3.4 Effect of gas introduction…………………………………………………………124
4.3.5 Effect of bias potential……………………………………………………………129
4.3.6 Effect of supporting electrolyte…………………………………………………141
4.4 Integrated discussion…………………………………………………………………146
5 Conclusions and Recommendations………………………………………………………154
Reference………………………………………………………………………………………157
Appendix…………………………………………………………………………………………164

157
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