本研究採用陽極氧化法，雙電極連接直流電源供應器，在含氟化物溶液中，鈦板為陽極，鉑片為陰極，使鈦金屬氧化成氧化鈦層並受氟離子腐蝕成為奈米管陣列膜。接著以電化學蝕刻技術，形成自身支持(free-standing)的高縱橫比TiO2奈米管陣列貫通(both-ends opened)膜，再利用此透過膜進行甲基橙染料的光(電)催化反應。
本研究分別採用一步陽極氧化與酸蝕法(草酸及氫氟酸)、二步升壓陽極氧化法、二步降壓陽極氧化法、三步陽極氧化法，嘗試製備二氧化鈦奈米管陣列貫通膜。結果顯示，一步法的酸蝕操作條件嚴苛；二步法製備的薄膜不易從基板剝離且易脆；三步陽極氧化法則製備出可資後續光催化應用的奈米管陣列貫通膜。接著進行染料光催化反應，探討溶液pH(2~10)及UV光強度(5~20mW/cm2)對奈米管陣列貫通膜光催化反應速率常數之影響。結果顯示，染料溶液pH 2時有最佳的反應效應，且反應速率常數隨光強度增加而增高。光電催化的反應速率常數，為光催化的2.25倍。

In this study, anodic oxidation method was used to prepare titanium dioxide nanotube. A power supply was connected with two electrodes that immerged in fluoride solution. A titanium plate acts as anode and a platinum plate as cathode. The titanium dioxide layer grows on the titanium plate and sequentially corroded by fluoride to form nanotubes. Anodic growth of self-organized, high-aspect-ratio and highly ordered TiO2 nanotubes arrays membrane was prepared and nanotubes on the membrane were penetrated sequentially by electrochemical etching technique to remove the titanium barrier layer. The titanium plate finally forms a both-ends opened membrane. The membrane was then used as a photocatalyst for the degradation of methylene orange by photocatalytic and photoelectrocatalytic reaction.
We used three methods to prepare the membranes including one-step with acid etching method, two-step with increasing voltage method, two-step with decreasing voltage method and three-step anodic oxidation method. The acid etching parameters are too critical to from a penetrated membrane. The membrane prepared by two-step methods was very brittle and can not peel off from titanium plate. The successfully penetrated membrane was prepared by three-step anodic oxidation method.
The temporal varieties of degradation ratio were studied throughout two parameters including solution pH and UV light intensities. The results showed degradation ratios decrease as solution pH increase within the range from 2 to 10. The degradation ratios increase as UV light intensities increase within the range from 5 to 20mW/cm2. Furthermore, the reaction rate constant of photoelectrocatalysis is 2.25 times that of photocatalysis.

總目錄
摘要 I
Abstract II
誌謝 V
總目錄 Ⅴ
表目錄 IX
圖目錄 Ⅸ
第一章 前言 1
第二章 文獻回顧 3
2.1二氧化鈦晶體結構與特性 3
2.2二氧化鈦奈米管的製備方法 6
2.3陽極氧化法 7
2.4二氧化鈦奈米管陣列膜製備 9
2.5奈米管的生長機制 11
2.6光催化反應與光電效應 18
2.7擴散系數 24
第三章 材料與方法 26
3.1實驗流程 26
3.2實驗儀器設備 29
3.3實驗材料 30
3.4實驗步驟 32
3.4.1二氧化鈦奈米管膜之製備 32
3.4.2一步法製備二氧化鈦陣列貫通膜 32
3.4.3二步法製備二氧化鈦陣列貫通膜 33
3.4.4三步法製備二氧化鈦陣列貫通膜 34
3.5光觸媒電極之特性分析 36
3.5.1 FESEM場發掃描式電子顯微鏡 36
3.5.2 X光繞射儀(X-RAY DIFFACTOMER) 36
3.5.3紫外光/可見光光譜儀 (UV/VIS) 吸收光譜儀量測 37
3.5.4界達電位 38
3.5.5電化學量測 39
第四章 結果與討論 41
4.1陽極氧化過程 41
4.2 陽極氧化製備二氧化鈦陣列貫通膜 44
4.2.1一步陽極氧化及酸蝕刻法 44
(1)草酸浸蝕 46
(2)氫氟酸蒸氣蝕刻 48
4.2.2二步升壓陽極氧化法 49
4.2.3二步降壓陽極氧化法 52
4.2.4三步陽極氧化法 54
小結 56
4.3貫通膜之晶相分析 57
4.4貫通膜之紫外/可見光漫反射光譜(UV/Vis DRS) 58
4.5光催化反應 59
4.5.1溶液pH對貫通膜光催化之效應 59
4.5.2光強度對貫通膜光催化之效應 63
4.6光催化與光電催化 66
4.7擴散係數 68
第五章 結論 71
第六章 建議 72
參考文獻 73








表目錄
表2.1不同二氧化鈦晶型的物化特性比較表 6
表3.1實驗儀器設備 29
表3.2實驗材料 30
表3.3實驗藥劑 31
表4.1不同陽極氧化法製備參數及TiO2 奈米管陣列尺寸 56


圖目錄
圖2.1二氧化鈦三種主要的晶相結構 5
圖2.2陽極氧化製備奈米管的結構成長示意圖 10
圖2.3鈦陽極氧化(a)無氟離子(b)有氟離子 17
圖2.4 (a)電流暫態(b)對應的TiO2形態(c)TiO2溶解與氧化平衡 17
圖2.5(a)管成長的擴散控制(b)電流密度模式(c)管常擴張模式 17
圖2.6 二氧化鈦反應機制圖 18
圖2.7在受光及外加偏壓下電子-電洞在TiO2/電極行徑圖 20
圖2.8 n型半導體與溶液物種接觸前後能帶分佈的情形 22
圖3.1實驗流程 26
圖3.2 TiO2奈米管陣列膜製備流程 27
圖3.3光催化反應裝置圖 28
圖3.4陽極氧化裝置 35
圖3.5光電催化反應裝置 40
圖4.1陽極氧化電流趨勢 42
圖4.2陽極氧化TiO2 奈米管陣列膜之FESEM圖 43
圖4.3陽極氧化二氧化鈦奈米管陣列膜之FESEM圖 45
圖4.4草酸浸蝕之FESEM圖 47
圖4.5氫氟酸蒸氣蝕刻之FESEM圖 49
圖4.6不同厚度鈦板之二步升壓陽極氧化結果 51
圖4.7不同厚度鈦板之二步法降壓陽極氧化結果 53
圖4.8三步陽極氧化法製備之TiO2奈米管陣列貫通膜 55
圖4.9三步陽極氧化法製備之二氧化鈦奈米管陣列貫通膜之XRD圖 57
圖4.10三步陽極氧化法製備二氧化鈦奈米管陣列貫通膜 58
圖4.11 TiO2奈米管貫通膜光催化不同pH染料溶液之降解率 60
圖4.12 TiO2奈米管貫通膜光催化不同pH染料溶液之反應速率常數 61
圖4.13 TiO2貫通膜奈米管之界達電位(Zeta potential) 62
圖4.14光強度對TiO2奈米管陣列貫通膜光催化甲基橙之效應 64
圖4.15光強度對TiO2奈米管陣列貫通膜光催化甲基橙之反應速率常數變化 65
圖4.16光催化與光電催化甲基橙溶液降解率之比較 67
圖4.17貫通膜擴散試驗 69
圖4.18貫通膜擴散試驗之擴散係數 70

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