本研究以化學浴沉降技術(chemical bath deposition；CBD)將高光催化效能之ZnO膜均勻且穩固的被覆在經過錳酸鉀活化後的玻璃管上。製得之ZnO膜會進行X-光繞射儀、掃描式電子顯微鏡和紫外光-可見光光譜儀等測試來了解其特性。研究中探討活化過程及煆燒程序的必要性，並調整CBD溶液中乙醇胺及氨水體積比，來瞭解其對所製得ZnO膜微結構的影響。結果顯示，玻璃管經過活化後CBD衍生之ZnO膜被覆均勻，500 oC煆燒的過程也有效的增加ZnO膜與玻璃管之間的結合性。CBD溶液中，乙醇胺及氨水體積比會影響所形成ZnO膜的結晶程度、ZnO柱的尺寸及光催化能力。在適當乙醇胺及氨水體積比下可得到均勻且穩固的ZnO膜。ZnO膜的光催化能力以其光降解水中亞甲基藍所對應的特徵時間常數(τ)來表示，其中τ值越小代表光催化效能越好。光催化分析中，以乙醇胺及氨水體積比為12:2所製得的ZnO膜光催化效果最佳，光催化反應2小時可分解99%的亞甲基藍，其τ值為0.61 h。製得之ZnO膜經過連續10次的光催化測試發現ZnO膜仍具有相同的光催化效能，且比較光催化前後ZnO膜表面微結構並無偵測到明顯差異。光觸媒面積(NS；N:管數，S:單一管之ZnO膜面積)及光照強度(I)會影響光催化效能，經實驗分析得知光觸媒面積與光催化效果成正比關係，而光照強度與光催化效果成指數關係。將不同實驗條件下量測所得特徵時間常數值進行實驗數據的曲線擬合分析，得到其關係式為：τ=[(2.88×〖10〗^(-2) N+8.92×〖10〗^(-2))I^0.23 ]^(-1)。此關係式可充分地描述玻璃管上ZnO膜降解不同濃度的亞甲基藍之行為模式。

ZnO films with high photocatalytic activity were uniformly and firmly deposited on the KMnO4(aq) activated glass tubes by chemical bath deposition method (CBD). The obtained ZnO films were characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), and ultraviolet-visible spectrophotometer (UV-Vis). Photoacatalytic activity of the obtained ZnO film was measured by photocatalytically degrading methylene blue (MB) in water, under illumination of 365-nm UV light. Effects of the glass activation process, heating process and volume ratios of ethanolamine to ammonia in CBD solution on ZnO film microstructure were investigated and discussed. By using proper volume ratios of ethanolamine/ammonia, the CBD-derived ZnO films calcined at 500 oC had strong adhesion to the surface of glass tubes. The photocatalytic ability of ZnO films were represented using a characteristic time constant (τ) for the photocatalytic degradation of methylene blue in water. The smaller τ stands for higher photocatalytic ability of the film. The ZnO film, prepared using volume ratio ethanolamine：ammonia = 12：2 had superior photocatalytic ability; after 2 hour, almost 99% degradation of methylene blue were achieved, and its τ value was 0.61 h. After repeating 10 times of the photocatalytic test, the ZnO film still possessed the same photocatalytic activity and the microstructure of the film didn’t showed any significant differences. Kinetic analysis indicated that the value of τ was affected by the photocatalyst areas (NS; N: tube number, S: single tube ZnO film area) and light intensity (I). The equation, τ=[(2.88×〖10〗^(-2) N+8.92×〖10〗^(-2))I^0.23 ]^(-1), can well describe the photocatalytic performance of the prepared ZnO film at different concentrations of methylene blue and operation conditions.

主目錄
論文提要內容：	I
Abstract：	II
主目錄	IV
圖目錄	VI
表目錄	VIII
第一章	緒論	1
1.1	光觸媒材料之興起	1
1.2	研究目的	3
第二章	文獻回顧	5
2.1	光觸媒與光催化原理	5
2.2	氧化鋅(ZnO)基本性質	7
2.3	ZnO粉體和膜的製備方法	8
2.3.1	水熱法/溶劑熱法(hydrothermal/solvothermal reaction)	8
2.3.2	溶膠-凝膠法(sol-gel method)	10
2.3.3	化學氣相沉積法(chemical vapor deposition；CVD)	13
2.3.4	化學浴沉積法(chemical bath deposition；CBD)	15
2.4	ZnO膜表面微結構	18
第三章	實驗步驟	21
3.1	實驗藥品	21
3.2	玻璃管被覆ZnO光觸媒膜	22
3.2.1	玻璃管表面活化	22
3.2.2	ZnO膜製備	22
3.3	特性分析	25
3.3.1	X-光繞射分析儀(X-ray diffractormeter；XRD)	25
3.3.2	掃描式電子顯微鏡(scanning electron microscope；SEM)	26
3.3.3	紫外光-可見光光譜儀(ultraviolet-visible spectrophotometer；UV-Vis)	28
3.4	光觸媒活性實驗	30
第四章	結果與討論	31
4.1	ZnO膜特性分析	31
4.1.1	玻璃管表面活化的必要性	31
4.1.2	CBD溶液中乙醇胺及氨水比例對ZnO膜特性的影響	36
4.2	ZnO膜光催化能力分析	42
4.2.1	CBD溶液中乙醇胺及氨水體積比的影響	42
4.2.2	光觸媒反應面積的影響	47
4.2.3	光照強度的影響	49
4.2.4	動力學分析	51
4.3	ZnO對不同染料的影響	55
4.4	煆燒程序對光觸媒氧化鋅膜的影響	58
第五章	結論	65
第六章	參考文獻	67

圖目錄
圖 1.1.1不同光觸媒半導體能隙分佈圖	2
圖 1.1.2光觸媒研究十大方向	3
圖 2.1.1光催化示意圖	6
圖 2.2.1氧化鋅纖維鋅礦結構	7
圖 3.2.1玻璃管表面活化程序	23
圖 3.2.2化學浴沉積技術在玻璃管上製備ZnO膜的步驟	24
圖 3.3.1 X光對晶格所產生之繞射	26
圖 3.3.2掃描式電子顯微鏡剖面機構示意圖	27
圖 4.1.1玻璃管表面活化與未活化和後續以CBD製得之氧化鋅膜表面巨觀狀態	33
圖 4.1.2玻璃管表面活化與未活化和後續以CBD製得氧化鋅膜之XRD圖	34
圖 4.1.3玻璃管表面(a)、(b)未活化與(c)、(d)活化後以CBD製得氧化鋅膜表面之SEM圖。	35
圖 4.1.4活化後的玻璃管在不同乙醇胺及氨水體積比下所製得ZnO膜之狀態	37
圖 4.1.5活化過玻璃管表面經CBD製程所製得ZnO膜之XRD圖	38
圖 4.1.6乙醇胺及氨水體積比7:7(E7A7)氧化鋅膜表面之SEM圖	39
圖 4.1.7不同乙醇胺及氨水體積比下(a)、(b) E14A0高倍率(c)、(d)E12A2高倍率(e) 、(f)E10A4高倍率氧化鋅膜表面之SEM圖	39
圖 4.1.8不同乙醇胺及氨水體積比下(a)、(b) E14A0高倍率(c)、(d)E12A2高倍率(e)、(f)E10A4高倍率氧化鋅膜截面之SEM圖	40
圖 4.1.9不同乙醇胺及氨水體積比(a) E10A4 (b) E12A2 (c) E14A0 之能隙計算結果	41
圖 4.2.1不同乙醇胺及氨水體積比下氧化鋅膜降解亞甲基藍濃度隨反應時間變化關係圖	44
圖 4.2.2乙醇胺及氨水體積比12:2 (E12A2)氧化鋅膜分解亞甲基藍濃度隨反應時間變化關係圖	44
圖 4.2.3不同乙醇胺及氨水體積比下所製得氧化鋅膜之τ值	45
圖 4.2.4乙醇胺及氨水體積比12:2(E12A2)氧化鋅膜經過10次光催化反應後對應的降解分率及τ值	45
圖 4.2.5乙醇胺及氨水體積比12:2(E12A2)氧化鋅膜(a)光催化前(b)經過10次光催化後表面狀態	46
圖 4.2.6 E12A2氧化鋅膜光觸媒反應面積在紫外光(128W)下亞甲基藍濃度隨反應時間變化關係圖	48
圖 4.2.7 E12A2光觸媒氧化鋅膜反應面積與τ值之關係圖	48
圖 4.2.8 E12A2氧化鋅膜光觸媒(16根)在不同光照強度下亞甲基藍濃度隨反應時間變化關係圖	50
圖 4.2.9光照強度與τ值之關係圖	50
圖 4.2.10 (a)在紫外光80W照射下10根氧化鋅膜光觸媒，(b)在紫外光96W照射下12根氧化鋅膜光觸媒分解亞甲基藍濃度隨反應時間變化關係圖	53
圖 4.2.11在紫外光128W照射下16根氧化鋅膜光觸媒分解不同初始亞甲基藍濃度之莫耳濃度隨反應時間變化關係圖	54
圖 4.2.12在紫外光128W照射下16根氧化鋅膜光觸媒分解不同初始亞甲基藍濃度之莫耳濃度分率隨反應時間變化關係圖	54
圖 4.3.1 E12A2在紫外光下分解(a)MB、(b)MO吸收光譜圖	56
圖 4.3.2 E12A2氧化鋅膜光觸媒在紫外光(365 nm, 128W)下對MB及MO的光降測試結果	57
圖 4.4.1不同熱處理程序下所製得ZnO膜之XRD圖	59
圖 4.4.2不同熱處理程序下氧化鋅(002)晶面之特性峰(2θ=34.42 o)	60
圖 4.4.3 CBD-衍生氧化鋅膜乾燥後(a)、(b)及(c)和進一步煆燒500 oC後(d)、(e)及(f) 表面之SEM圖	61
圖 4.4.4 CBD-衍生氧化鋅膜乾燥後(a)和(b)和進一步煆燒500 oC後(c)和(d)截面之SEM圖	62
圖 4.4.5 CBD-衍生氧化鋅膜(未煆燒)經超音波震盪五次之表面SEM圖	63
圖 4.4.6不同熱處理程序下氧化鋅膜降解亞甲基藍其濃度隨反應時間變化關係圖	64

表目錄
表 2.2.1 ZnO物理特性	7
表 3.1.1實驗藥品	21
表 4.2.1 E12A2氧化鋅樣品在不同玻璃管數(N)與365-nm紫外燈光源強度(I)下光催化降解水中MB所對應的特徵時間常數(τ)	52
表 4.3.1染料基本性質	55

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