本研究製備不同粒徑之奈米二氧化鈦觸媒極板，並透過各式貴重儀器了解極板之基本特性；同時進行光催化甲基橙染料降解試驗，以探究不同表面顆粒尺寸的觸媒極板基本性質及光催化的差異。

本研究運用Degussa P-25、P-90奈米TiO2粉末製備不同奈米粒徑TiO2觸媒極板，試驗過程中以不同分散劑量、不同極板基材、披覆次數以尋求製備較佳TiO2極板成品，結果顯示分散劑重量使用低劑量時，即可減少表面顆粒堆積；氧化銦錫玻璃(Indium-Tin Oxide, ITO)是較適用的極板基材，表面粒子尺寸不會隨著披覆次數增加而增大，披覆一次時，表面粒子尺寸分別約30及20 nm。由XRD得知，鍛燒溫度為500oC時，奈米觸媒極板表面仍以銳鈦礦結晶體為主要晶形。不同奈米粒徑之觸媒極板於披覆一次時，Degussa P-25及P-90觸媒極板比表面積最佳為21與33 m2 g-1。FTIR分析得知，不同奈米粒徑極板，證實含有氫氧基存在，且兩者皆有相當的活性。

不同奈米粒徑之TiO2極板運用於光觸媒技術處理甲基橙染料廢水，試驗結果顯示，暗吸附試驗無明顯去除效果；在披覆一次的情況下，不同奈米粒徑極板皆有最佳之去除效果，在處理8小時後，甲基橙廢水色度去除率Degussa P-25及P-90極板分別可達約96%與97%，總有機碳去除率可達約62%與67%。由本試驗結果得知，不同奈米粒徑TiO2極板對甲基橙染料廢水之光催化反應，呈現假一階反應特性。

This study focuses on the manufacturing technique to obtain the TiO2 plate with different and via the characterization of this plate under different operational conditions was analyzed. At the same time, it was employed as the photocatalytic electrode to test the color removal efficiency of methyl orange dye wastewater, between different particle of sizes TiO2 surface property and photocatalytic difference.

The nano-scale TiO2 plate was fabricated by dip-coating methods involved commercial Degussa, p-25 and p-90 TiO2 nano-scale powders. During the experiment, different weight surface dispersant, different kinds of the substrate, numbers of the coating to find out manufacture of TiO2 plate. According to the results, the surface features and element composition of all electrodes were observed, low-dose of weight dispersant can be decrease the surface particle accumulation phenomena. It can be shown that nano-scale size of TiO2 particles effectively pile on the ITO substrate was more applicable plate substrate, surface isn’t the number of particle size increases with the coated, when coating once, the surface of the nano particle size was 30 and 20 nm. By XRD, TiO2 plate can be formed at calcination temperature of 500oC, plate principal crystal was the anatase on the surface. The best specific surface area of the P-25 and P-90 nano TiO2 plate is 33 and 21 m2 g-1. Different nano-scale TiO2 plate were analyzed through FTIR, surface catalytic confirmed the existence hydroxyl and both of them have considerable activity.

Different nano-particle TiO2 plate for treating methyl orange dye wastewater by photocatalytic technique. According to experimental results, absorption has no significant removal, the color removal efficiency of methyl orange wastewater Degussa P-25 and P-90 can achieve about 96% and 97%, TOC removal efficiency of wastewater can achieve about 62% and 67%. Different nano particle size TiO2 plate on photocatalytic reaction of waste methyl orange were showing characteristics of pseudo first-order reaction.

目錄
中文摘要 I
Abstract II
致謝 IV
表目錄 II
圖目錄 IV
第一章 緒論 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 奈米觸媒材料介紹 4
2-1-1 奈米材料特性 4
2-1-2 觸媒材料簡介 7
2-1-3 二氧化鈦的基本性質 12
2-2 二氧化鈦奈米極板製備方式 17
2-2-1化學氣相沉積法 17
2-2-2溶膠凝膠法 21
2-2-3 真空濺鍍法 25
2-3 TiO2光催化反應及應用 27
2-3-1 光、電催化原理與機制 27
2-3-2 光觸媒技術於環境工程之應用 30
2-3-3 電觸媒技術於環境工程之應用 32
第三章 試驗材料與方法 34
3-1 研究架構 34
3-2 試驗藥品 36
3-3試驗步驟及參數 38
3-3-1 不同奈米尺寸TiO2極板製備 39
3-3-2 甲基橙廢水之光觸媒處理 46
第四章 結果與討論 49
4-1不同奈米TiO2極板的製備及特性 49
4-1-1分散劑濃度對於二氧化鈦的製備之影響 49
4-1-2 基材種類對二氧化鈦極板製備之影響 53
4-1-3 披覆次數對二氧化鈦極板製備之影響 55
4-1-4 不同奈米尺寸TiO2極板的特性比較 66
4-2甲基橙廢水之光觸媒處理 68
4-2-1 TiO2極板對甲基橙直接光解及暗吸附 68
4-2-2 不同奈米尺寸TiO2極板對光觸媒降解之影響 70
4-2-3 不同披覆次數TiO2極板對光觸媒降解之影響 73
4-2-4 不同甲基橙濃度對TiO2極板光觸媒之影響 77
4-2-5 光強度試驗 79
4-2-6 奈米TiO2降解甲基橙之反應動力 81
第五章 結論與建議 83
5-1 結論 83
5-2 建議 85
第六章 參考文獻 86
英文文獻 86
中文文獻 94
表目錄
表 1-1 氫氧自由基生成與有機污染物降解化學方程式.......................... 2
表 2-1 各類半導體的能隙表................................................................... 10
表 2-2 半導體的種類............................................................................... 11
表 2-3 TiO2 不同結晶之物理特性比較表................................................ 16
表 2-4 化學氣相沉積法分類方式.......................................................... 20
表 2-5 兩種前驅物之各項性質比較....................................................... 23
表 2-6 二氧化鈦不同製備方式之優缺點............................................... 26
表 2-7 光觸媒反應方程式...................................................................... 29
表 2-8 氧化劑之標準還原電位表.......................................................... 33
表3-1 奈米二氧化鈦粉末製備試驗藥品項目...........................................36
表3-2 總有機碳分析試驗藥品項目........................................................ 37
表3-3 極板製備操作條件........................................................................ 40
表3-4 奈米二氧化鈦極板特性分析儀器設備製造商及型號................. 42
表3-5 製備奈米二氧化鈦極板設備製造商及型號................................ 43
表3-6 奈米二氧化鈦分析設備及型號.................................................... 44
表3-7 染料廢水降解試驗操作條件........................................................ 47
表4- 1 不同操作條件二氧化鈦極板之比表面積................................... 66
表4- 2 不同奈米粒徑TiO2 觸媒極板之假一階反應動力常數.............. 82
表4- 3 不同光強度之假一階反應動力常數........................................... 82
IV
圖目錄
圖2- 1 表面原子數之比例與粒徑關係圖................................................. 5
圖2- 2 半導體能隙之量子效應圖............................................................ 6
圖2- 3 電子從價電帶躍升至傳導帶之示意圖......................................... 7
圖2- 4 不同導體之能帶結構示意圖......................................................... 8
圖2- 5 不同觸媒材料之能隙圖................................................................ 9
圖3- 1 研究架構圖................................................................................... 35
圖3- 2 奈米二氧化鈦粉末製備流程圖................................................... 41
圖3- 3 光催化處理染料廢水示意圖........................................................ 48
圖4- 1 奈米級TiO2 觸媒極板表面形貌圖-未添加分散劑...................... 51
圖4- 2 奈米級TiO2 觸媒極板表面形貌圖-分散劑添加0.02 g ............... 51
圖4- 3 奈米級TiO2 觸媒極板表面形貌圖-分散劑添加0.002 g ............. 52
圖4- 4 奈米級TiO2 觸媒極板表面形貌圖-ITO 為基材.......................... 53
圖4- 5 奈米級TiO2 觸媒極板表面形貌圖-二氧化矽為基材.................. 54
圖4- 6 奈米級TiO2 觸媒極板表面形貌圖-鈦板基材.............................. 54
圖4- 7 未披覆極板表面形貌圖............................................................... 56
圖4- 8 奈米級TiO2 觸媒極板表面形貌圖-披覆一次.............................. 56
圖4- 9 奈米級TiO2 觸媒極板表面形貌圖-披覆三次.............................. 57
圖4- 10 奈米級TiO2 觸媒極板表面形貌圖-披覆五次............................ 57
圖4- 11 奈米級P-25 TiO2 觸媒極板表面形貌圖-披覆一次.................... 58
圖4- 12 奈米級P-25 TiO2 觸媒極板表面形貌圖-披覆三次.................... 58
圖4- 13 奈米級P-25 TiO2 觸媒極板表面形貌圖-披覆五次.................... 59
圖4- 14 奈米級P-90 TiO2 觸媒極板表面形貌圖-披覆一次.................... 60
V
圖4- 15 奈米級P-90 TiO2 觸媒極板表面形貌圖-披覆三次.................... 61
圖4- 16 奈米級P-90 TiO2 觸媒極板表面形貌圖-披覆五次................... 61
圖4- 17 奈米級TiO2 觸媒極板元素分析圖-披覆一次............................ 62
圖4- 18 奈米級P-25 TiO2 觸媒極板結晶分析圖.................................... 64
圖4- 19 奈米級P-90 TiO2 觸媒極板結晶分析圖.................................... 64
圖4- 20 JCPDS 資料庫銳鈦礦（Anatase）晶相標準圖譜..................... 65
圖4- 21 JCPDS 資料庫金紅石（Rutile）晶相標準圖譜........................ 65
圖4- 22 不同觸媒極板之紅外線光譜..................................................... 67
圖4- 23 TiO2 極板直接光解及暗吸附的色度去除效率圖...................... 69
圖4- 24 TiO2 極板直接光解及暗吸附TOC 之去除效率圖..................... 69
圖4- 25 不同粒徑尺寸觸媒極板的色度去除效率圖.............................. 71
圖4- 26 不同奈米TiO2 粒徑觸媒極板對TOC 之去除效率圖................ 71
圖4- 27 甲基橙染料結構式圖................................................................. 72
圖4- 28 奈米級P-25 TiO2 不同披覆次數對色度去除分析趨勢圖........ 73
圖4- 29 奈米級P-25 TiO2 不同披覆次數對TOC 之去除趨勢圖........... 74
圖4- 30 奈米級P-90 TiO2 不同披覆次數對色度去除趨勢圖............... 75
圖4- 31 奈米級P-90 TiO2 不同披覆次數對TOC 之去除趨勢圖........... 76
圖4- 32 不同初始濃度色度去除趨勢圖.................................................. 77
圖4- 33 不同初始濃度TOC 去除變化趨勢圖........................................ 78
圖4- 34 不同光強度色度去除趨勢圖..................................................... 80
圖4- 35 不同光強度TOC 去除趨勢圖................................................... 80

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