臺灣博碩士論文加值系統

　在本研究太陽光能分解水產氫的裝置中，主要的材料為二氧化鈦奈米管。利用電化學陽極氧化法將純鈦金屬板氧化成高規則方向一致結構之二氧化鈦奈米管。現今的二氧化鈦對光催化的效果侷限在紫外光的範圍，然而紫外光佔太陽光的比例太低。本實驗主要的目的是藉由摻雜的過程，降低二氧化鈦的能階間隙，使光催化的波長移到可見光區，並藉由管狀的結構，使材料的表面積增加，以提升光的繞射與吸收量。在上述的二氧化鈦奈米管陣列上添加Pt、B、N 等元素，改變二氧化鈦奈米管陣列原有之吸收能階。期中摻雜氮的二氧化鈦奈米管陣列能階間隙將低到2.91eV，照AM1.5標準光源後光電流值最大為: 0.303mA/cm2，最高光電轉換效率為1.07%。實際產氫效果在甲醇加水溶液中用紫外光照射試片最佳可達0.75 ml/h．cm2，在純水中則為0.422 ml/h．cm2 ，利用波長為300~500nm汞燈照射則為0.826 ml/h．cm2。利用微波的方法將白金奈米粒子添加在二氧化鈦奈米管陣列中，在700W及120秒微波條件下，所製備的白金奈米粒子為2~5nm，結果測得白金奈米粒子的添加使二氧化鈦奈米管陣列光催化效能增加，照光水解產氫速率為0.579 ml/h．cm2，汞燈則為1.091 ml/h．cm2。

Highly-ordered TiO2 nanotube arrays (TNA) by anodizing Ti foil were carried out using a slightly modified electrochemical process. The parameters such as anodization potentials and duration have been varied in order to fabricate the specific length and diameter of TNA. The performance of hydrogen production from photoelectrocatalytic effect of larger diameter TNA is found to be higher than the smaller diameter TNA.
One-Dimensional B-doped, N-doped nanotubes arrays were synthesized via an anodization process. The prepared materials were characterized with field emission scanning electron microscope, and their structures were analyzed by using x-ray diffraction (XRD). A shift of the absorption edge toward the visible region of the UV-vis absorption was be observed. Under ultraviolet (UV) or visible light irradiation, the photocurrent conversion efficiency were enhanced in the TiO2 nanotubes which doped N and B.
Under AM1.5 Standard light, the best photocurrent is N-doped TNA (0.303mA/cm2) , N-doped conversion efficiency is 1.07%, under the UV light the best of hydrogen production rate of these doped TiO2 nanotubes was 0.579 ml/h．cm2 , and under Mercury lamp was 0.826 ml/h．cm2.The Pt nanoparticles were synthesized on the TNA by microwave process at 700W for 120s. The particle size of Pt 2 nm to 5 nm. The experimental results show that the photocatalysis potency of Pt nanoparticles added TNA was batter than TNA blank.

目錄
中文摘要 I
Abstract II
謝誌 III
表目錄 VIII
圖目錄 IX
第一章 緒論 1
1.1 前言 1
1.2 二氧化鈦簡介 4
1.2.1二氧化鈦的晶體結構與性質 5
1.3 光觸媒簡介 11
1.4光催化反應 14
1.5研究目的與動機 15
第二章 理論基礎與文獻回顧 17
2.1二氧化鈦奈米管製備與形成機制 18
2.1.1 陽極氧化法(Anodization) 18
2.1.2二氧化鈦奈米管的形成機制 23
2.2二氧化鈦奈米管的應用 28
2.2.1氫感測器 28
2.2.2太陽能電池 29
2.2.3光解水製氫 29
2.3改變二氧化鈦能階間隙的方法 32
2.3.1與其他能隙較小的半導體共同使用 32
2.3.2添加過渡金屬離子到二氧化鈦的結構中 32
2.3.3二氧化鈦結晶中形成氧空缺 34
第三章 實驗方法及設備 37
3.1 實驗藥品 37
3.2 實驗儀器 39
3.2.1 一般儀器 39
3.2.2粉末X-Ray繞射儀 (Powder XRD) 41
3.2.3掃描式電子顯微鏡 ( Scanning Electron Microscopy，SEM ) 42
3.2.4穿透式電子顯微鏡 ( Transmission Electron Microscopy，TEM ) 43
3.2.5電化學分析儀(Electochemical Analyzer) 44
3.2.6紫外可見光光譜儀 45
3.2.7 太陽光模擬器 46
3.3 實驗部分 48
3.3.1二氧化鈦奈米管陣列製備 48
3.3.1.5 二氧化鈦奈米管陣列添加白金粒子 52
3.3.2 摻雜硼與氮元素之二氧化鈦奈米管陣列檢測 54
3.3.3 二氧化鈦奈米管陣列產氫效能量測 55
第四章 結果與討論 58
4.1 二氧化鈦奈米管陣列製備 58
4.1.1 含氟非水溶液電解液製備二氧化鈦奈米管陣列 59
4.1.2摻雜硼之二氧化鈦奈米管陣列製備 61
4.1.3摻雜氮之二氧化鈦奈米管陣列製備 69
4.1.4硼氮共添加二氧化鈦奈米管陣列製備 71
4.1.5二氧化鈦奈米管陣列添加白金奈米粒子EDS分析 73
4.1.6二氧化鈦奈米管陣列結晶性的量測 78
4.2 探討二氧化鈦奈米管陣列的吸收光譜與照光光電流變化 87
4.2.1 UV-VIS量測吸收光譜 89
4.2.2 二氧化鈦奈米管照光光電流與轉換效率 93
4.3 二氧化鈦奈米管陣列光催化效能及產氫效能量測 101
4.3.1 UV-VIS量測光催化裂解亞甲基藍的效能 101
4.3.2 利用UV燈照光水解產氫 103
4.3.3 利用汞燈照光水解產氫 106
4.3.4甲醇系統與純水系統產氫結果比較 108
第五章 結論 109
5.1二氧化鈦奈米管陣列製備 109
5.2 二氧化鈦奈米管陣列能階間隙與照光光電流及轉換效率變化 110
5.3 二氧化鈦奈米管陣列光催化效能與產氫效能量測 112
第六章 參考資料 114



表目錄
表1 1二氧化鈦晶格參數與空間群資料[16] 5
表1- 2銳鈦礦(Anatase),金紅石(Rutile)及板鈦礦(Brookite)物理性質 9
表2-1二氧化鈦奈米粒子與奈米管比較 . . . . . . . . . . . . . . . .17
表2- 2光化學產氫的重要文獻數據 31
表4-1不同摻雜後管徑及管壁結果. . . . . . . . . . . . . . 72
表4- 2 EDS分析數據(未摻雜的二氧化鈦奈米管) 74
表4- 3 EDS分析數據(摻雜硼的二氧化鈦奈米管) 75
表4- 4 EDS分析數據(摻雜氮的二氧化鈦奈米管) 76
表4- 5 EDS分析數據(硼氮共摻雜的二氧化鈦奈米管) 77
表5- 1二氧化鈦奈米管陣列摻雜後轉換效率與光電流變化表 111
表5- 2二氧化鈦奈米管陣列在不同條件下照光水解產氫速率表 113






圖目錄
圖1-1二氧化鈦的晶型結構圖[17] 6
圖1-2二氧化鈦之相圖[18] 7
圖1-3日照中各種光線比例關係圖[19] 10
圖1-4常見金屬半導體的能隙[49] 12
圖1-5光觸媒受光激發後由價帶跳至傳導帶之示意圖 13
圖1-6 TiO2 光觸媒之反應機構 13
圖2-1 0.5wt%氫氟酸為電解液作不同電壓極化處理之SEM影. . 19
圖2-2用0.15wt%氫氟酸與1M硫酸電解液，電壓為20V，做陽極化處理之SEM影像圖[27](a.剖面圖、b.俯視圖及c.底試圖) 20
圖2-3用1M的磷酸銨與0.5wt%氟化銨陽極化處理2小時之SEM影像圖[28]( a.俯視圖、b.剖面圖及c.底試圖) 21
圖2-4用DMSO與乙醇及4wt%氫氟酸陽極氧化處理之SEM影像圖[30]( a.b.c.俯視圖、d.剖面圖) 22
圖2-5鈦片在HF水溶液中陽極氧化的電流時間曲線[33] 24
圖2-6定電壓下陽極氧化二氧化鈦奈米管演化示意圖[34] 25
圖2-7孔洞分離機制的示意圖 26
圖2-8調整電化學參數以達到高縱橫比結構，(a)溶解反應與機制之示意圖 (b)孔洞內的pH值分佈圖 (c)管壁內溶解速率分佈圖， 27
圖2-9 Anpo教授產氫裝置圖 30
圖2-10添加導電金屬以增加催化能力 36
圖3-1粉末X-Ray繞射儀(中原大學) . . . . . . . . . . . . . . . .41
圖3-2高解析度場發射掃描式電子顯微鏡(台灣科技大學) 42
圖3-3高解析度場發射掃描式電子顯微鏡(核能研究所) 42
圖3-4化學分析影像能譜儀(台科大) 43
圖3-5 電化學分析儀(核能研究所) 44
圖3-6紫外可見光光譜儀(核能研究所) 45
圖3-7 YSS 80A 儀器圖(核能研究所) 47
圖3-8陽極氧化反應裝置 48
圖3-9陽極氧化製備流程圖 49
圖3-10二氧化鈦奈米管陣列添加白金奈米粒子流程圖 53
圖3-11電化學分析儀量測 54
圖3-12量測氣體生成量之排水集氣裝置 56
圖3-13圓底燒瓶置於UV-box內照光 56
圖3-14樣品置於UV-box內照光利用流量計測量氣體 57
圖4-1 SEM正面影像圖(60V/2hr) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .60
圖4-2 SEM側面影像圖(60V/2hr) 60
圖4-3二氧化鈦試片浸泡硼酸溶液(0.5M/1Hr) 61
圖4-4空氣中鍛燒500℃、3小時後二氧化鈦試片 62
圖4-5電鍍法製備成的二氧化鈦(0.5M/2Hr) 63
圖4-6空氣中鍛燒500℃、3小時後二氧化鈦試片 63
圖4-7 SEM正面影像圖(圖4-3-a) 65
圖4-8 SEM正面影像圖(圖4-3-b) 65
圖4-9 SEM正面影像圖(泡硼酸2小時) 66
圖4-10 SEM正面影像圖(泡硼酸4小時) 66
圖4-11 SEM正面影像圖(電鍍法 0.5M硼酸水溶液) 68
圖4-12 SEM正面影像圖(電鍍法，1M硼酸水溶液) 68
圖4-13 氨氣氛圍中鍛燒500℃、3小時後二氧化鈦試片 69
圖4-14 SEM正面影像圖(在氨氣氛圍下鍛燒) 70
圖4-15 SEM正面影像圖(硼氮共摻雜) 71
圖4-16 EDS分析圖譜(未摻雜的二氧化鈦奈米管) 74
圖4-17 EDS掃描區域(未摻雜二氧化鈦奈米管) 74
圖4-18 EDS掃描區域(摻雜硼的二氧化鈦奈米管) 75
圖4-19 EDS分析圖譜(摻雜硼的二氧化鈦奈米管) 75
圖4-20 EDS掃描區域(摻雜氮的二氧化鈦奈米管) 76
圖4-21 EDS分析圖譜(摻雜氮的二氧化鈦奈米管) 76
圖4-22 EDS掃描區域(硼氮共摻雜的二氧化鈦奈米管) 77
圖4-23 EDS分析圖譜(硼氮共摻雜的二氧化鈦奈米管) 77
圖4-24未摻雜的二氧化鈦奈米管陣列XRD量測 78
圖4-25二氧化鈦(Anatase相)XRD標準圖譜 79
圖4-26鈦金屬XRD標準圖譜 79
圖4-27用浸泡法煅燒後，TiO2主要的特徵峰變成rutile相 80
圖4-28用電鍍法煅燒後，摻雜硼TiO2主要的特徵峰變成Anatase相 81
圖4-29 二氧化鈦奈米管之主峰因添加硼偏移之情形(20°~30°) 82
圖4-30 二氧化鈦奈米管之主峰因添加硼偏移之情形(45°~55°) 82
圖4-31氨氣氛圍煅燒後，摻雜氮TiO2主要的特徵峰為Anatase相 83
圖4-32二氧化鈦奈米管之主峰因添加氮偏移之情形(23°~27°) 84
圖4-33二氧化鈦奈米管之主峰因添加氮偏移之情形(45°~55°) . .84
圖4-34硼氮共摻雜TiO2主要的特徵峰為Anatase相. . . . . . . 85
圖4-35二氧化鈦奈米管添加白金粒子主要的特徵峰為Anatase相 86
圖4-36電化學分析儀量測圖(照光與無照光比較) 88
圖4-37電化學分析儀量測圖(遮光與無遮光比較) 88
圖4-38 UV-vis吸收光譜圖(未摻雜二氧化鈦奈米管) 89
圖4-39 UV-vis吸收光譜圖(摻雜硼二氧化鈦奈米管) 89
圖4-40 UV-vis吸收光譜圖(摻雜氮二氧化鈦奈米管) 91
圖4-41 UV-vis吸收光譜圖(硼氮共摻雜二氧化鈦奈米管) 92
圖4-42 照光光電流圖(未摻雜二氧化鈦奈米管) 93
圖4-43 轉換效率圖(未摻雜二氧化鈦奈米管) 94
圖4-44 照光光電流圖(摻雜硼二氧化鈦奈米管) 95
圖4-45轉換效率圖(摻雜硼二氧化鈦奈米管) 96
圖4-46 照光光電流圖(摻雜氮二氧化鈦奈米管) 97
圖4-47 轉換效率圖(摻雜氮二氧化鈦奈米管) 98
圖4-48 照光光電流圖(硼氮共摻雜二氧化鈦奈米管) 99
圖4-49 轉換效率圖(硼氮共摻雜二氧化鈦奈米管) 100
圖4-50 UV-VIS量測光催化裂解亞甲基藍效能 102
圖4-51 摻雜硼氮後對TiO2奈米管分解亞甲基藍之影響。 102
圖4-52照光產氫試片之剖面圖 103
圖4-53照光產氫流量圖. . . . . . . . . . . . . . . . . . . .104
圖4-54照光產氫流量圖(添加白金奈米粒子) . . . . . . . . . . .105
圖4-55照汞燈產氫流量圖 106
圖4-56照汞燈產氫流量圖(添加白金奈米粒子) . . . . . . . . . .107
圖4-57照ＵＶ燈產氫流量圖(甲醇+水) 108

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