臺灣博碩士論文加值系統

二氧化鈦是光觸媒中最主要的研究項目。其具有高光催化活性，價格低廉與製備容易，但對於可見光範圍的光降解效果顯示較差。本研究致力於研發具高光催化活性之二氧化鈦光觸媒。利用溶膠凝膠製備具介孔的二氧化鈦，並在製備過程中摻雜氧化鎢，與熔融包覆對光觸媒進行不同形式改質。並採用X-ray繞射儀(XRD)、傅立葉轉換紅外線光譜儀(FTIR)、拉曼光譜儀(Raman)、熱重分析儀(TGA)、比表面積量測儀(BET)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)等儀器對材料做特性分析；且採用所改質的光觸媒對亞甲基藍、甲基橙以及若丹明染料進行光降解反應，來探討其光催化活性。並與市售P-25及ST-01做比較。
實驗結果顯示，第一部份，改質後的二氧化鈦能有效地降解亞甲基藍，且摻雜鎢之光觸媒的催化速率比起純二氧化鈦高出許多。第二部份，採用聚乙烯醇與鎢同時對二氧化鈦做改質，成功地以碳對二氧化鈦進行包覆，且大幅增加其吸附能力，並且對亞甲基藍具有良好的吸附和光降解能力。

TiO2 is the most studied photocatalyst. High photocatalytic activity, low cost and easily prepared, but it shows negligible visible-light activity.
This researchs mainly enhance the effect of TiO2 photocatalytic activities. Mesoporous titanium dioxide were prepared via sol-gel method, and in the prepared process doped tungsten atoms and carbon coating of photocatalyst was successful to prepared.
The synthesized sample was characterized by X-ray Diffraction (XRD), Raman scattering spectroscopy (Raman), Fourier Transform Infrared Spectrometer (FTIR), Brunauer–Emmett–Teller (BET), Thermo Gravimetric analysis (TGA), Field Emission Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM).
The photocatalyic activity of the synthesized composite particles was tested by photodegradation of Methylene Bule (MB) and Methyl Orange (MO) and Rhodamine B under UV illumination (365 nm) and compared with that of commerce photocatalyst P-25, ST-01.
The result shows, the first part, doped titanium dioxide has photocatalytic activity such as photodegradations of Methylene Bule, which are much higher than those with pure titanium dioxide.
The second part, PVA and tungsten on the same time to improve titanium dioxide, carbon coating of photocatalyst was successfully carried out by heating a powder mixture of poly(vinyl alcohol) and TiO2/WOx under N2 gas flow at temperature above 700 oC. Carbonization method was possessing high adsorbability, and have good adsorption and photodegradation ability to the Methylene Bule.

總目錄

中文摘要 III
英文摘要 IV
致謝 VI
表目錄 IX
圖目錄 X

第一章 緒論 1
第二章 基本原理與文獻回顧 2
2-1 光觸媒簡介 2
2-1-1 二氧化鈦 3
2-1-2 二氧化鈦光催化反應原理 6
2-1-3 二氧化鈦之製備 8
2-1-4 影響二氧化鈦光催化反應的因素 12
2-1-5 二氧化鈦光觸媒的改質方式 14
2-1-6 二氧化鈦的應用 15
2-2 活性碳特性 18
2-2-1 活性碳纖維與傳統活性碳之比較 21
2-2-2 活性碳之吸附機制 22
2-2-3 吸附擴散動力分析 24
2-2-4 影響吸附之因素 24
2-2-5 恆溫吸附模式 25
2-2-6 二氧化鈦及碳之協同作用 27
2-3 二氧化鈦光觸媒之發展 28
2-4 二氧化鈦光觸媒以WOx改質之發展 34
2-5 研究動機 40
第三章 實驗部份 41
3-1 實驗材料 41
3-2 實驗儀器 42
3-3 光觸媒之製備與改質步驟 45
3-3-1 純TiO2之製備 45
3-3-2 WOx-TiO2之製備 45
3-3-3 WOx-TiO2/C之製備 45
3-4 光催化活性實驗 51
3-4-1 甲基橙性質 51
3-4-2 亞甲基藍性質 51
3-4-3 若丹明性質 52
第四章 結果與討論 57
4-1 WOx-TiO2光觸媒之特性分析與光催化測試 57
4-1-1 材料組成及特性鑑定 57
4-1-2 光催化活性測試 60
4-1-3 結論 83
4-2 WxT/Cy光觸媒之特性分析與光催化測試 84
4-2-1 材料組成及特性鑑定 84
4-2-2 光催化活性測試 87
4-2-3 結論 111
4-3 本研究所製備的各種光觸媒其光催化效果之探討 112
第五章 總結 115
未來展望 117
參考文獻 118

表目錄
表2-1 為銳鈦礦與金紅石物理性質之比較 6
表2-2 製備TiO2粉體主要方法 9
表2-3 為活性碳孔隙大小分布之情形 18
表2-4 物理吸附與化學吸附之差異 23
表3-1 以溶膠-凝膠法製備出WOx -TiO2之材料和PVA混合經碳化後所得之WOx-TiO2/C樣品代碼 49
表3-2 甲基橙、亞甲基藍、若丹明污染物的基本特性 54
表4-1 為添加不同 Na2WO4．2H2O量改質TiO2之晶粒大小 63
表4-2 為添加不同 Na2WO4．2H2O量改質TiO2之比表面積 71
表4-3 4 mole % Na2WO4．2H2O與不同PVA量對TiO2進行改質之晶粒大小 90
表4-4 4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2改質之比表面積 95

圖目錄
圖2-1 為常見半導體之能隙圖 3
圖2-2 二氧化鈦相圖 4
圖2-3 銳鈦礦與金紅石之TiO2晶體結構 5
圖2-4 二氧化鈦分子的鍵結方式 5
圖2-5 二氧化鈦光催化反應機制 8
圖2-6 二氧化鈦之應用範圍 17
圖2-7 活性碳表面可能之含氧酸性官能基 20
圖2-8 活性碳表面可能之含氧鹼性官能基 20
圖2-9 IUPAC分類歸納出來的六類恆溫吸附線示意圖 26
圖2-10 有機污染物在碳塗覆TiO2表面上的吸附和降解過程 27
圖3-1 純TiO2之製備流程圖 46
圖3-2 WOx-TiO2之製備流程圖 47
圖3-3 WOx-TiO2/C之製備流程圖 48
圖3-4 碳化高溫爐裝置圖 50
圖3-5 紫外光燈源的光學發射光譜(短波長254 nm) 53
圖3-6 紫外光燈源的光學發射光譜(長波長365 nm) 53
圖3-7 甲基橙之UV-Visible吸收光譜圖 55
圖3-8 亞甲基藍之UV-Visible吸收光譜圖 55
圖3-8 若丹明之UV-Visible吸收光譜圖 56
圖4-1 添加不同Na2WO4．2H2O莫耳百分比所製備之WxT與TiO2經700 oC氮氣環境下恆溫鍛燒1 hr之X-ray繞射圖 62
圖4-2 添加不同Na2WO4．2H2O莫耳百分比所製備之WxT與TiO2經700 oC氮氣環境下恆溫鍛燒1 hr之Raman光譜儀 64
圖4-3 添加不同Na2WO4．2H2O莫耳百分比所製備之WxT與TiO2經700 oC氮氣環境下恆溫鍛燒1 hr之SEM圖 65
圖4-4 TiO2之SEM-EDS圖 67
圖4-5 W4T之SEM-EDS圖 68
圖4-6 添加不同Na2WO4．2H2O莫耳百分比所製備之WxT與TiO2經700 oC 氮氣環境下恆溫鍛燒1 hr之熱重損失分析圖 69
圖4-7 添加不同Na2WO4．2H2O莫耳百分比所製備之WxT與TiO2經700 oC 氮氣環境下恆溫鍛燒1 hr之氮氣吸附-脫附恆溫曲線圖 70
圖4-8 為添加不同Na2WO4．2H2O量所製備改質之TiO2，經700 oC氮氣環境下恆溫鍛燒1 hr後之孔徑分布圖 72
圖4-9 Na2WO4．2H2O添加量對材料比表面積與孔容之影響 73
圖4-10 TiO2之TEM 圖 74
圖4-11 W4T之TEM 圖 75
圖4-12 為添加不同Na2WO4．2H2O量所製備改質之TiO2光降解亞甲基藍之效率圖 76
圖4-13 為市售光觸媒與改質之觸媒以亞甲基藍為污染物進行光降解效率評估 77
圖4-14 為市售光觸媒與改質之觸媒以甲基橙為污染物進行光降解效率評估 78
圖4-15 為市售光觸媒與改質之觸媒以若丹明為污染物進行光降解效率評估 79
圖4-16 W4T光降解亞甲基藍之效率圖 80
圖4-17 W4T光降解甲基橙之效率圖 81
圖4-18 W4T光降解若丹明之效率圖 82
圖4-19 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以700 oC恆溫鍛燒 1 hr之XRD圖 89
圖4-20 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以700 oC恆溫鍛燒 1 hr之FT-IR圖譜 91
圖4-21 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以 700 oC 恆溫鍛燒1 hr之Raman光譜儀 92
圖4-22 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質之熱重分析圖 93
圖4-23 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以700 oC恆溫鍛燒1 hr之氮氣吸附-脫附恆溫曲線圖 94
圖4-24 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以700 oC恆溫鍛燒1 hr之孔徑分布圖 96
圖4-25 PVA 添加量對材料比表面積與孔容之影響 97
圖4-26 為4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2進行改質，於氮氣環境下以700 oC恆溫鍛燒1 hr之SEM圖 98
圖4-27 W4T/C5之SEM-EDS圖 99
圖4-28 W4T/C5之SEM-Mapping圖 100
圖4-29 W4T/C5之TEM圖 101
圖4-30 4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2改質其光降解亞甲基藍之效率圖 102
圖4-31 W4T/C7.5光降解亞甲基藍之效率圖 103
圖4-32 W4T/C10光降解亞甲基藍之效率圖 104
圖4-33 4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2改質其光降解甲基橙之效率圖 105
圖4-34 W4T/C7.5光降解甲基橙之效率圖 106
圖4-35 W4T/C10光降解甲基橙之效率圖 107
圖4-36 4 mole % Na2WO4．2H2O與不同PVA量同時對TiO2改質其光降解若丹明之效率圖 108
圖4-37 W4T/C7.5光降解若丹明之效率圖 109
圖4-38 W4T/C10光降解若丹明之效率圖 110
圖4-39 各種改質光觸媒與市售光觸媒光降解亞甲基藍之效率圖 112
圖4-40 各種改質光觸媒與市售光觸媒光降解甲基橙之效率圖 113
圖4-41 各種改質光觸媒與市售光觸媒光降解若丹明之效率圖 114

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