系統識別號 | U0002-1706201012430900 |
---|---|
DOI | 10.6846/TKU.2010.00439 |
論文名稱(中文) | 凝膠衍生P/Si-TiO2薄膜之相穩定性與光催化性質 |
論文名稱(英文) | Phase stabilities and photocatalytic activities of gel-derived P/Si-TiO2 thin films |
第三語言論文名稱 | |
校院名稱 | 淡江大學 |
系所名稱(中文) | 化學工程與材料工程學系碩士班 |
系所名稱(英文) | Department of Chemical and Materials Engineering |
外國學位學校名稱 | |
外國學位學院名稱 | |
外國學位研究所名稱 | |
學年度 | 98 |
學期 | 2 |
出版年 | 99 |
研究生(中文) | 陳立訓 |
研究生(英文) | Li-Hsun Chen |
學號 | 696401479 |
學位類別 | 碩士 |
語言別 | 繁體中文 |
第二語言別 | |
口試日期 | 2010-06-15 |
論文頁數 | 94頁 |
口試委員 |
指導教授
-
余宣賦
委員 - 張裕祺 委員 - 尹庚鳴 |
關鍵字(中) |
二氧化鈦 光觸媒 光催化活性 薄膜 溶膠-凝膠法 |
關鍵字(英) |
titanium dioxide photocatalyst photocatalytic activity thin film Sol-gel process |
第三語言關鍵字 | |
學科別分類 | |
中文摘要 |
本實驗利用溶膠-凝膠法和旋轉塗佈技術來合成TiO2和P/Si-TiO2光觸媒薄膜。實驗程序中,固定摻雜物(磷、矽)的總莫爾添加量以探討磷、矽的莫爾比的改變(R = [P] / ([P]+[Si]))和煆燒溫度對P/Si-TiO2薄膜結晶相態、晶粒尺寸、薄膜厚度、薄膜表面形態、光穿透率、能隙以及光降解特性的影響,並與未摻雜的TiO2薄膜作性質的比較。實驗的結果顯示:同時摻入磷、矽元素於TiO2結構中的P/Si-TiO2(0.33≦R≦0.67)薄膜可與基材有緊密的結合性並且所製得的銳鈦礦TiO2具有優越的熱穩定性,銳鈦礦結構可維持至900℃。製得薄膜的光催化能力以其對亞甲基藍光降解反應所對應的特性時間常數(τ)予以量化,τ值愈小表示二氧化鈦薄膜具愈高的光催化能力。整體而言,經過800℃煆燒處理後的P/Si-TiO2(R=0.5)薄膜利用365-nm紫外光照射12小時後具有最佳的光催化能力,其可分解90%的亞甲基藍並且特性時間常數為5.7小時。 |
英文摘要 |
The P/Si-TiO2 thin films, with a molar ratio [P+Si]/[P/Si-TiO2]=0.03, were synthesized by the sol–gel method and spin-coating technique. Effects of relative ratios of dopants (i.e., R≡[P]/([ P+Si]) and calcination temperatures on phase transformation, grain growth, film thickness, surface morphology, light transmittance, energy gap and photocatalytic activity of the gel-derived P/Si-TiO2 thin films were examined and their results were compared with those of the undoped TiO2 thin films. By simultaneously doping Si and P elements into the Ti-O framework, the P/Si-TiO2 (i.e., 0.33≤ R ≤0.67) thin films calcined at ≦900℃ adhered strongly to the surface of fused-silica substrate and were composed of anatase-TiO2 only. The photocatalytic activities of the thin films were measured and represented using a characteristic time constant (τ) for the MB degradation. The small τ stands for high photocatalytic ability. The P/Si-TiO2 thin film prepared at R = 0.5 and 800℃ gave the best photocatalytic activity; this thin film decomposed about 90 mole% of MB in the water (the corresponding τ = 5.7 h), after 365-nm UV light irradiation for 12 h. |
第三語言摘要 | |
論文目次 |
主目錄 中文摘要I 英文摘要III 主目錄IV 圖目錄VI 表目錄IX 第一章 緒論1 第二章 文獻回顧6 2-1 二氧化鈦應用與基本性質6 2-2 奈米二氧化鈦薄膜的製備方法10 2-3 二氧化鈦光觸媒光催化原理15 2-4 影響光催化活性的因素17 2-4-1 量子尺寸效應17 2-4-2 結晶形態對於光催化活性的影響19 2-5 提升二氧化鈦光催化效率的方法20 第三章 實驗步驟與特性分析23 3-1 實驗藥品23 3-2 實驗儀器24 3-3 實驗步驟26 3-3-1 基材的清洗26 3-3-2 TiO2溶膠的製備27 3-3-3 P/Si-TiO2溶膠的製備28 3-3-4 TiO2和P/Si-TiO2薄膜的製備與煆燒29 3-4 儀器分析與操作狀態31 3-4-1 X光繞射分析31 3-4-2 掃描式電子顯微鏡32 3-4-3 原子力顯微鏡33 3-4-4 紫外光-可見光光譜儀34 3-4-5 多用途光學量測系統35 3-5 光觸媒活性檢測36 第四章 實驗結果38 4-1 TiO2與Si-TiO2薄膜特性差異38 4-2 P/Si-TiO2特性分析47 第五章 結果討論83 第六章 結論86 參考文獻88 圖目錄 圖1-1 常見化合物半導體的能帶示意圖2 圖1-2 二氧化鈦光觸媒材料在人類環境中可應用的領域3 圖2-1 二氧化鈦的相圖7 圖2-2 金紅石與銳鈦礦的晶體結構8 圖2-3(a) 金紅石相態結構組成 (b)銳鈦礦相態結構組成8 圖2-4 二氧化鈦光催化反應示意圖16 圖2-5 量子尺寸效應對於能隙大小的影響18 圖3-1 TiO2溶膠的製備流程圖27 圖3-2 P/Si-TiO2溶膠的製備流程圖28 圖3-3 二氧化鈦薄膜製備實驗流程圖30 圖3-4 X光對晶體所產生之繞射31 圖3-5 掃描式電子顯微鏡剖面機構示意圖33 圖3-6 亞甲基藍化學結構式36 圖4-1(a) 未摻雜之TiO2薄膜於不同煆燒溫度下的XRD圖譜40 圖4-1(b) Si-TiO2 (R=0)薄膜於不同煆燒溫度下樣品的XRD圖譜41 圖4-2(a) 未摻雜之TiO2薄膜的紫外光-可見光穿透光圖譜44 圖4-2(b) Si-TiO2 (R=0)薄膜的紫外光-可見光穿透光圖譜44 圖4-3 不同煆燒處理溫度下TiO2與Si-TiO2 (R=0)薄膜在365nm UV光照射12小時後其亞甲基藍去除能力46 圖4-4(a) P/Si-TiO2 (R=0.33)薄膜的XRD圖譜49 圖4-4(b) P/Si-TiO2 (R=0.5)薄膜的XRD圖譜50 圖4-4(c) P/Si-TiO2 (R=0.67)薄膜的XRD圖譜51 圖4-5 不同煆燒溫度TiO2與P/Si-TiO2薄膜結晶相態與晶粒尺寸的改變53 圖4-6 TiO2及P/Si-TiO2薄膜在(a)600℃ (b)800℃ (c)900℃ (d)1000℃煆燒處理後光降解亞甲基藍濃度的改變曲線圖57 圖4-7 不同煆燒溫度下TiO2及P/Si-TiO2薄膜經過365-nmUV光照射12小時後對於水溶液中亞甲基藍的去除能力59 圖4-8 以AFM 觀察P/Si-TiO2 (R=0.5)薄膜在不同煆燒溫度處理下之表面型態圖(a)600℃ (b)800℃ (c)900℃ (d)1000℃ 64 圖4-9 以SEM觀察不同溫度處理之P/Si-TiO2 (R=0.5)薄膜表面(a)600℃ (b)800℃ (c)900℃ (d)1000℃ 67 圖4-10 以SEM觀察在煆燒溫度為800℃時(a)TiO2薄膜及P/Si-TiO2薄膜 (b)R=0 (c)R=0.33 (d)R=0.67 的表面形態70 圖4-11 煆燒溫度的改變對於P/Si-TiO2薄膜平均膜厚的影響71 圖4-12 TiO2薄膜及P/Si-TiO2薄膜(0≦R≦0.67)於800℃煆燒處理後紫外光-可見光穿透光圖譜76 圖4-13 P/Si-TiO2 (R=0.5)薄膜的紫外光-可見光穿透光圖譜77 圖4-14 煆燒溫度對於TiO2薄膜及P/Si-TiO2薄膜之能隙的影響78 圖4-15(a) TiO2薄膜及P/Si-TiO2薄膜經800℃煆燒溫度的SEM剖面圖(a)TiO2 (b)R=0 (c)R=0.33 (d)R=0.5 (e)R=0.67 82 圖5-1 TiO2、Si-TiO2 (R=0)及P/Si-TiO2 (0.33≦R≦0.67)薄膜在不同煆燒溫度處理後特性時間常數值85 表目錄 表2-1 金紅石與銳鈦礦相態之二氧化鈦的晶體尺寸與物理性質9 表3-1 實驗相關反應物莫耳比例30 表4-1 不同煆燒溫度對於晶粒成長的影響39 表4-2(a) TiO2薄膜在不同煆燒溫度處理下紫外光-可見光穿透率值43 表4-2(b) Si-TiO2 (R=0)薄膜在不同煆燒溫度處理下紫外光-可見光穿透率值43 表4-3 不同煆燒溫度對於未摻雜TiO2、Si-TiO2和P/Si-TiO2薄膜中TiO2晶粒成長的影響52 表4-4 在365nm UV光照射30小時後不同組成比例與煆燒溫度處理後特性時間常數值57 表4-5 在365nm UV光照射12小時後不同組成比例與不同煆燒處理溫度下其亞甲基藍去除能力59 表4-6 P/Si-TiO2 (R=0.5)薄膜在不同煆燒溫度下之表面平均粒子粗糙度64 表4-7 不同煆燒溫度處理下對於TiO2和P/Si-TiO2薄膜厚度的影響72 表4-8 TiO2薄膜及P/Si-TiO2薄膜(0≦R≦0.67)於800℃煆燒處理後紫外光-可見光穿透率值76 表4-9 P/Si-TiO2 (R=0.5)薄膜在不同煆燒溫度處理下紫外光-可見光穿透率值77 |
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