臺灣博碩士論文加值系統

本研究之目的乃利用紫外線(UV/TiO2)程序光催化分解液相中環境荷爾蒙之丙二酚-A，探討分解丙二酚-A的較佳條件及反應機制。另外自製複合光觸媒，探討不同的光觸媒對光催化分解丙二酚-A的相互關係。研究結果顯示分解丙二酚-A的較佳條件是在pH 7、溫度25℃、TiO2劑量100mg、光照時間60min下，幾乎能完全分解濃度20mg/L的丙二酚-A。比較不同的光觸媒光催化分解丙二酚-A，結果含浸純矽藻土的光觸媒光催化分解丙二酚-A效果較好。
以Langmuir-Hinshelwood反應動力模式中之擬一階反應動力式，在改變不同溫度、TiO2劑量、丙二酚-A起始濃度、pH及光觸媒種類(含複合光觸媒)下，探討不同條件下的反應速率常數(K)。結果發現在各種條件中較高的反應速率常數(K)與上述分解丙二酚-A的較佳條件大致相同，因此光催化分解丙二酚-A效率會受溫度、pH、丙二酚-A起始濃度、TiO2劑量及光觸媒種類(含複合光觸媒)的影響。另外光催化分解丙二酚-A過程會產生中間產物，這些中間產物經由GC/MS與HPLC分析，推測這些主要的中間產物應為Acetic Acid、HQ(hydroquinone)及p-HAP(4-hydroxyacetophenoe)。

The objectives of this study were to destruct photocatalytically Bisphenol-A ( one of endocrine disrupting chemicals ) in the aqueous solution using UV/TiO2 process, and further investigate its optimal conditions, reaction mechanism and interactions with various photocatalysts including pure TiO2 and diatomite-impregnated TiO2. The experimental results showed that Bisphenol-A was exactly photodestructed under the process conditions of initial concentration 20mg/L、pH 7、temperature 25℃、 TiO2 dosage 100mg and irradiation time 60min. The destructive performance of diatomite-impregnated TiO2 and showed to be better in comparison with that of pure (non-impregnated) TiO2.
With respect to the reaction kinetics, the pseudo-first order rate derived from Largmuir-Hinshelwood model was successfully used to describe the photodecomposition of Bisphenol-A in the aqueous solution under various conditions (including temperature、TiO2 dosage、Bisphenol-A initial concentration、pH and pure/impregnatated TiO2. On the other hand, the main intermediate products (i.e. acetic acid、hydroquinone and 4-hydroxyacetophenoe) of Bisphenol-A photodegradation were identified based on the analytical results of GC/MS and HPLC. The photocatalytic reaction mechanism was thus addressed to elucidate the experimental results on the basis of intermediate products in this study.

摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 IX
第一章前言 1
1-1研究緣起 1
1-2研究目的 3
第二章 文獻回顧 4
2-1光觸媒 4
2-2二氧化鈦 5
2-2-1二氧化鈦的構造及特性 5
2-2-2二氧化鈦之應用 8
2-2-3二氧化鈦光催化反應 12
2-2-4奈米光觸媒的效應 15
2-3複合光觸媒 16
2-4 UV/TiO2 系統的光催化反應機制 19
2-5 UV/TiO2 系統反應動力 22
2-6丙二酚-A 25
2-7 UV/TiO2 系統去除丙二酚-A之文獻回顧 27
2-8 UV/TiO2降解丙二酚-A之反應途徑 32
第三章 研究方法及實驗設備 36
3-1實驗材料與試藥 36
3-2實驗設備 39
3-2-1液相光催化反應系統 39
3-2-2二氧化鈦含浸矽藻土實驗系統 40
3-3分析儀器 42
3-3-1二氧化鈦物理性質分析 42
3-3-2二氧化鈦理化學性質分析 47
3-3-3丙二酚-A及其光催化反應後產物分析 48
3-3-4中間產物分析 49
3-4實驗步驟 50
3-4-1丙二酚-A藥品製備及儲存 50
3-4-2純矽藻土活化實驗步驟 50
3-4-3複合光觸媒實驗步驟 51
3-4-4光催化實驗步驟 51
3-4-5丙二酚-A 空白試驗 52
3-4-5-1 TiO2 (P25)吸附丙二酚-A 52
3-4-5-2 UV光直接光照丙二酚-A 52
3-4-6 HPLC之檢量線制作 53
第四章 結果與討論 54
4-1二氧化鈦物化特性分析 54
4-1-1物性分析 55
4-1-2化性分析 57
4-1-3 X光繞射儀分析 58
4-2丙二酚-A 空白試驗 61
4-3 UV/TiO2去除丙二酚-A的最佳條件 63
4-3-1 pH效應 63
4-3-2丙二酚-起始濃度效應 67
4-3-3二氧化鈦劑量效應 68
4-3-4溫度效應 69
4-3-5光觸媒種類(含複合光觸媒) 70
4-4化學動力學 72
4-4-1溫度效應 72
4-4-2二氧化鈦劑量效應 73
4-4-3丙二酚-A起始濃度效應 74
4-4-4 pH效應 75
4-4-5光觸媒種類(含複合光觸媒) 76
4-5中間產物 78
4-6反應機制的推導 79
第五章 結論與建議 81
5-1 結論 81
5-2 建議 83
參考文獻 84
附 錄 89
A-1 丙二酚- A 安全與健康資訊 89
A-2 HPLC檢量線 97
A-3 丙二酚-A空白試驗原始數據 99
A-4 UV/TiO2去除丙二酚-A的最佳條件實驗原始數據 101
A-5化學動力學實驗原始數據 107


圖目錄
圖2-1二氧化鈦結晶構造 7
圖2-2 pH =1時，各種半導體之能隙 7
圖2-3超親水性防霧 11
圖2-4二氧化鈦光催化反應示意圖 14
圖2-5光引導礦化反應在純TiO2上 18
圖2-6光引導礦化反應在TiO2負載於吸附劑中 18
圖2-7光催化反應機構 21
圖2-8文獻(15)之光催化反應途徑 33
圖2-9文獻(17) 之光催化反應途徑 34
圖2-10文獻(21) 之光催化反應途徑 35
圖3-1實驗設計流程 38
圖3-2液相光催化反應系統 41
圖3-3 Micromeritics Instrument Corporation ASAP 2020型微孔分析儀 45
圖4-1未改質、含浸DE及ADE的光觸媒(P25) XRD分析圖 59
圖4-2未改質、含浸DE及ADE的光觸媒(Kanto) XRD分析圖 59
圖4-3未改質、含浸DE及ADE的光觸媒(Aldrich) XRD分析圖 60
圖4-4未改質、含浸DE及ADE的光觸媒(Alfa) XRD分析圖 60
圖4-5添加光觸媒(P25)之空白試驗 62
圖4-6直接光照之空白試驗 62
圖4-7 BPA 10mg/L之不同pH下DRE％的變化 65
圖4-8 BPA 20mg/L之不同pH下DRE％的變化 65
圖4-9不同pH下TiO2的表面特性 66
圖4-10在不同pH下BPA以不同型態存在 66
圖4-11不同起始濃度下DRE％的變化 67
圖4-12不同劑量下DRE％的變化 68
圖4-13不同溫度下DRE％的變化 69
圖4-14比較四種未改質、含浸DE及ADE的TiO2光觸媒之丙二酚-A破壞去除效率DRE％ 71
圖4-15 BPA光催化，反應30min後之HPLC分析圖 78
圖4-16 推測的BPA降解反應途徑 80


表目錄
表2-1丙二酚-A物理特性 26
表2-2 UV/TiO2之國外研究文獻一覽 27
表2-2 UV/TiO2之國外研究文獻一覽 (續-1) 28
表2-2 UV/TiO2之國外研究文獻一覽 (續-2) 29
表2-2 UV/TiO2之國外研究文獻一覽 (續-3) 30
表2-3 UV/TiO2光催化水中有機物之國內研究文獻一覽 31
表2-4 丙二酚-A液相光催化主要中間產物比較 32
表3-1吸附氣體特性比較 44
表3-2 粉粒體物理特性量測方法比較 45
表4-1未改質、含浸DE及ADE的光觸媒物理分析 56
表4-2含浸DE及ADE的光觸媒元素分析 57
表4-3不同溫度下擬一階反應速率常數K值的比較 72
表4-4不同劑量下擬一階反應速率常數K值的比較 73
表4-5不同起始濃度下擬一階反應速率常數K值的比較 74
表4-6不同pH下擬一階反應速率常數K值的比較 75
表4-7四種未改質、含浸DE及ADE的光觸媒之擬一階反應速率常數K值的比較 77
表4-8文獻(21)與本研究實驗條件之比較 79

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