摘 要
近年來，半導體觸媒的異相光催化反應在環境污染防治的研究上相當廣泛，其中奈米TiO2因具有高活性、化學穩定性、無毒性及容易取得之優點，故應用性極具潛力。因此，本研究之主要目的為奈米銳鈦礦TiO2合成及其在醋酸廢水處理之應用。實驗是以溶膠凝膠法合成的奈米TiO2微粒，經場發掃描式電子顯微鏡(FE-SEM)、X光粉末繞射儀(XRPD)、界面電位(zeta potential)及穿透式電子顯微鏡(TEM)測試結果直徑為5~20 nm銳鈦礦TiO2之結晶結構，經過30天之靜置測試亦不易沉降。在合成實驗中，其影響因子包括pH值、操作溫度、攪拌子以及轉速，其中以pH值為1.5、溫度358 K、2.5 cm攪拌子及轉速1000 rpm的實驗條件為最佳，可得較佳之分散性，晶體顆粒均較小且分佈均勻。
為了探討添加金屬觸媒對奈米anatase-TiO2之催化提升效果，另製作奈米anatase-TiO2、Cu/TiO2、Fe/TiO2及Zn/TiO2薄膜及自行研製的光催化處理批式系統來處理1000 mg/L的醋酸溶液，並以氣相層析儀(GC)、X光光電子光譜儀(XPS)、電子順磁共振光譜儀(EPR)、延伸細微結構X光吸收光譜(EXAFS)及X光吸收邊緣結構光譜(XANES)來觀察其處理醋酸前後之觸媒結構、化合物種類及其光催化之效果比較。由GC之實驗結果得知處理效果依序為2.25 > 4.5 > 9 > 18 g/L TiO2，在添加不同金屬之效果為Cu/TiO2 >Fe/TiO2 >Zn/TiO2 >TiO2 >P-25，奈米anatase-TiO2懸浮微粒之處理效果為1 >2 >3 g/L TiO2。在XPS分析結果顯示，Cu/TiO2為還原觸媒，Cu在催化反應過程中會抓取醋酸中的氧而造成醋酸崩解成CO2和H2O，而Fe/TiO2及Zn/TiO2為氧化觸媒，提供O源去破壞接觸在觸媒表面之有機物。另外，以EXAFS及XANES，來鑑定處理醋酸溶液前後奈米anatase-TiO2、Cu/TiO2、Fe/TiO2及Zn/TiO2薄膜及懸浮微粒之精細結構，由XANES實驗數據分析結果可知奈米anatase-TiO2、Cu/TiO2、Fe/TiO2及Zn/TiO2薄膜經處理醋酸溶液後，並不會改變其價數(Ti4+)及晶型(anatase)；由EXAFS之數據中顯示，未經處理醋酸溶液之TiO2懸浮微粒，其O的配位數為3.96 ± 0.05，Ti-O鍵長為1.96 ± 0.01 Å，而Cu/TiO2、Fe/TiO2及Zn/TiO2懸浮微粒，由結構參數顯示添加金屬會造成Ti配位數及鍵長的改變，可證明所添加之金屬可能已嵌入奈米銳鈦礦TiO2的晶體結構。
關鍵詞：銳鈦礦二氧化鈦、奈米微粒、凝膠溶膠法、光觸媒、醋酸、金屬觸媒、延伸細微結構X光吸收光譜、X光吸收邊緣結構光譜。

ABSTRACT
Titanium dioxide has been recognized as an excellent photocatalyst material applied in many fields in the past two decades. Recently, nanopahse TiO2 particles have been also studied due to its high surface area and excellent catalytic activities. Therefore, the optimal sol-gel synthesis, film coating techniques, photocatalytic of acetic acid solution, and identification of the fine structures, morphology or oxidation state for the catalytic anatase-typed TiO2 nanoparticles were investigated in the present work. The optimal synthesis conditions of nanopahse anatase-typed TiO2 photocatalysts included pH = 1.5, T = 358 K, stirrer size of 2.5 cm, and mixing rate of 1000 rpm. The anatase-typed TiO2 nanoparticles ranged of 5-20 nm with well dispersion and narrow particle distribution were measured by field-emission scanning microscopy (Fe-SEM), X-ray powder diffractometer (XRPD), transmission electron microscopy (TEM) or zeta-potential meter.
In order to more thoroughly examine the efficiencies of photocatalysis and the nature of the active species involved in photocatalysis of 1000 mg/L acetic acid solution, the analyses of gas chromatograph (GC), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), X-ray absorption near edge structure (XANES) or extended X-ray absorption fine structure (EXAFS) spectroscopy were performed. The efficiencies of CH3COOH photodegradation for anatase-typed TiO2 nanofilms of different concentrations were 2.25 >4.5 >9.0 >18.0 g/L TiO2(anatase) and for suspended anatase-typed TiO2 nanoparticles were 1 >2 >3 g/L TiO2(anatase). Moreover, the efficiencies of P-25, anatase-typed TiO2, and M-doped TiO2 photocatalysts were Cu >Fe >Zn-doped >anatase >P-25 typed-TiO2 nanoparticles. Thus, one may postulate the possibility that Cu was involved in the abstraction of O atoms in acetic acid molecules in the photodegradation process. In addition, the O sources from Fe2O3 species might enhance the abilities of destroying and removing the organics onto the surface of anatase-typed TiO2 photocatalysts. Comparatively, Cu(0)/TiO2 were reductive nanocatalysts and FeO/- or ZnO/TiO2 nanocatalysts were oxidative ones. By using XANES spectra, the photocatalysts were all Ti (IV). The EXAFS data revealed that the nanophase TiO2 photocatalyst had a central Ti atom of coordination number of 3.96 ± 0.05 primarily Ti-O with bond distances of 1.96 ± 0.01 Å. The insertion of Cu, Fe or Zn ions into TiO2 framework was also observed by the EXAFS data of Cu, Fe, or Zn-doped anatase-typed TiO2 photocatalysts.
Keywords: Anatase TiO2, Nanoparticle, Sol-gel method, Photocatalyst, Acetic acid, Metal-doped catalyst, EXAFS, XANES.

目 錄
摘 要 I
ABSTRACT III
誌 謝 V
目 錄圖 目 錄 VI
圖 目 錄 IX
表 目 錄 XVI
第一章 前言 1
第二章 文獻回顧 4
2.1 光化學觸媒簡介 4
2.1.1 二氧化鈦(TiO2)光催化觸媒之物化特性 4
2.2 奈米光觸媒粒子之特性 9
2.2.1 奈米微粒之特性 9
2.2.2 奈米微粒之應用與製備方法 13
2.2.3 奈米二氧化鈦之特性 16
2.3 二氧化鈦光化學種類及其催化原理 18
'2.3.1 二氧化鈦光化學種類 18
2.3.2 光化學催化反應之原理 19
2.4 影響二氧化鈦光催化反應之因素 22
2.5 二氧化鈦之應用 25
2.5.1 二氧化鈦之環保觸媒應用 25
2.5.2 二氧化鈦薄膜之環保觸媒應用 28
2.5.3 二氧化鈦微結晶粒子的製備及其應用 29
第三章 實驗設備及方法 33
3.1 實驗藥品 33
3.2 實驗儀器 34
3.3 奈米級二氧化鈦懸浮液之製備 35
3.4 奈米級二氧化鈦覆膜之製備 36
3.4.1 奈米二氧化鈦薄膜基材之清洗 37
3.4.2 二氧化鈦薄膜覆膜液之製備 38
3.4.2.1改質的TiO2覆膜液 39
3.4.3 二氧化鈦薄膜之製作 40
3.4.4 光催化反應測試 42
3.5 分析方法 45
3.5.1 X-ray粉末繞射儀及樣品準備 45
3.5.2 場發射掃描式電子顯微鏡 47
3.5.3 穿透式電子顯微鏡與樣品配製 49
3.5.4 氣相層析 52
3.5.5 化學分析電子光譜儀 54
3.5.6 界面電位 56
3.5.6.1 界面電位之測量原理 56
3.5.6.2 粒徑測量原理 58
3.5.7 比表面積 59
3.5.8 紫外-可見光譜 61
3.5.9 電子順磁共振儀(EPR) 62
3.5.10 同步輻射吸收光譜 64
3.5.10.1 同步輻射光吸收實驗 64
3.5.10.2 實驗方法與步驟 66
3.5.10.3 實驗數據分析 67
第四章 結果與討論 69
4.1 奈米二氧化鈦合成之條件 69
4.1.1 反應溫度 69
4.1.1.1 TEM觀察粒子大小 72
4.1.2 pH值 76
4.1.3 轉速影響 81
4.1.4 攪拌子影響 83
4.1.5 煅燒溫度 86
4.1.5.1 比表面積之影響 88
4.2 奈米二氧化鈦薄膜之特性分析 89
4.2.1 奈米二氧化鈦薄膜之FE-SEM分析 89
4.2.2 奈米二氧化鈦改質後薄膜之XPS分析 92
4.3 同步輻射之X光吸收光譜分析 108
4.3.1 X光吸收邊緣結構光譜 108
4.3.2 延伸細微結構X光吸收光譜 124
4.4 EPR分析結果 131
4.5 紫外-可見光譜 132
4.6 奈米二氧化鈦薄膜光催化實驗 135
4.6.1 奈米二氧化鈦薄膜光催化效果之比較 135
4.6.2 奈米二氧化鈦光催化之一階反應速率常數 149
第五章 結論及未來研究方向 156
5.1 結論 156
5.2 未來研究方向 159
參考文獻 160
附錄A XPS之全譜圖 174
附錄B 同步輻射光譜 178

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