臺灣博碩士論文加值系統

　　本研究以開發新式可見光光觸媒為目標，希望藉由摻入雜質來提升光觸媒於可見光下的使用效益。在室內一般日光燈下紫外光能量僅有0.1～1μW，對於一般光觸媒，都不足以使其產生分解污染物的作用。因此如何改善上述問題是當前最重要的突破，藉由光觸媒原理來改善一般光觸媒的電子電洞快速重組問題與吸附效能以及增加在可見光區吸收效率。
　　在本研究中以溶膠凝膠法搭配靜電紡絲技術製備GO/TiO2複合型超細纖維光觸媒與GO/Ag/TiO2複合型超細纖維光觸媒，其具有在可見光下降解亞甲基藍以及甲基橙的功能，並探討不同比例的GO/TiO2複合型超細纖維與GO/Ag/TiO2複合型超細纖維的性質。利用SEM、EDS、TEM、XRD、Raman、FT-IR、TGA、BET、UV-Visible DRS來檢測超細纖維的型態與分佈情形、晶相、元素組成、比表面積、可見光吸收與能隙值。最後以固-液相之亞甲基藍染料與甲基橙染料光降解，評估在可見光下降解效果。
　　由SEM表面型態來觀察得知GO/TiO2與GO/Ag/TiO2都為纖維型態，而添加GO使纖維型態有類似蜘蛛網結構產生增加比表面積。TEM觀察到GO/Ag/TiO2纖維表面有Ag奈米粒子分佈。EDS顯示不同GO/Ag/TiO2纖維的Ag重量百分比例其元素比例符合預期結果。由BET可得知，添加入GO是可提高比表面積，而GO-Ag也因奈米銀粒子的導入有助於粒徑降低因而更提高纖維的比表面積。由XRD顯示所製備的TiO2複合型光觸媒主要為銳鈦型晶礦，而添加入GO時會有明顯較寬的繞射峰產生。由Raman圖譜我們可以明顯觀察到TiO2複合型光觸媒會有明顯的D band與G band產生。UV-Visible分析結果顯示GO/TiO2與GO/Ag/TiO2纖維在可見光區有大幅的吸收度以及能隙值降低的現象。
　　最後本研究進行一系列亞甲基藍與甲基橙水溶液可見光降解的實驗，結果顯示在GO/TiO2超細纖維中添加20mgGO具有最佳的可見光降解效率；在GO/Ag/TiO2超細纖維中添加0.5mgGO-2wt%Ag具有最佳的可見光降解效率，這表明三效協同異質結構GO/Ag/TiO2超細纖維具有良好的可見光催化的效果。

　　In this study, the development of new visible light photocatalyst target, hoping to enhance the incorporation of impurities in the photocatalyst efficiency in the use of visible light. Indoors general fluorescent lamp of UV energy is only 0.1 ~ 1μW, for the general photocatalyst are not sufficient to produce the decomposition of pollutants effect. Therefore, how to improve the above problem is the most important breakthrough in improving the general principle by the photocatalyst photocatalyst fast electron hole recombination question the effectiveness and increase the absorption and adsorption efficiency in the visible region.
　　In this study, sol-gel method to prepare a spinning technique with electrostatic GO/TiO2 composite photocatalyst and microfiber GO/Ag/TiO2 composite photocatalyst microfiber, which has a visible drop of Methylene Blue and Methyl Orange features and explore the different proportions of GO/TiO2 composite microfiber and GO/Ag/TiO2 composite superfine fiber properties. The use of SEM, EDS, TEM, XRD, Raman, FT-IR, TGA, BET, UV-Visible DRS to detect patterns and distribution microfiber case, crystal, elemental composition, specific surface area, visible light absorption and energy gap . Finally, solid - liquid phase of methylene blue dye and degradation of methyl orange light, visible light degrades assessment results.
　　Observed by the SEM surface patterns that GO/TiO2 and GO/Ag/TiO2 are fiber patterns, and add fiber patterns GO has a similar structure to produce more than the surface area of the cobwebs. TEM observation GO/Ag/TiO2 fiber surface distribution of Ag nanoparticles. EDS shows the percentage by weight of Ag different GO/Ag/TiO2 fibers in line with the proportion of cases expected results of its elements. BET can be made that, added to the GO is the specific surface area can be increased, but also because the import GO-Ag nano silver particles help to reduce the particle size and thus more surface area to improve the fiber. TiO2 composite photocatalyst prepared by the XRD show mainly anatase crystal mine, and added the GO will significantly wider diffraction peak production. The Raman spectra, we can clearly observe TiO2 composite photocatalyst have significant D band and G band production. UV-Visible analysis showed that the GO/TiO2 and GO/Ag/TiO2 fibers in the visible region of the absorption of a substantial energy gap and reduce the phenomenon.
　　Finally, this study conducted a series of aqueous methylene blue and methyl orange visible degradation experiments showed that adding GO/TiO2 superfine fiber 20mgGO has the best visible degradation efficiency; add in GO/Ag/TiO2 superfine fiber 0.5mgGO -2wt% Ag has the best degradation efficiency of visible light, which indicates that three-way co-heterostructure GO/Ag/TiO2 visible light microfiber with good catalytic effect.

摘 要 I
ABSTRACT III
致 謝 V
目 錄 VI
表目錄 XII
圖目錄 XIV
符號說明 XXII
第一章 緒論 1
1-1 前言 1
1-2 研究背景 2
1-3 研究動機與目的 4
第二章　文獻回顧 7
2-1 半導體介紹 7
2-1.1 半導體定義 7
2-1.2 摻雜型半導體 8
2-1.3 半導體光觸媒 11
2-2 奈米材料 12
2-2.1 奈米材料與複合材料定義 12
2-2.2 奈米材料特殊效應 14
2-2.3 奈米纖維 16
2-3 石墨烯、氧化石墨稀簡介 16
2-3.1石墨烯介紹 16
2-3.2改質材料特性 17
2-3.2.1石墨烯（Graphene）之特性 17
2-3.2.2 氧化石墨稀(Graphene oxide) 19
2-3.3石墨烯與氧化石墨稀製備方法 20
2-3.3.1 石墨稀（Graphene）之製備 20
2-3.3.2 氧化石墨稀（Graphene oxide） 21
2-4 光觸媒與二氧化鈦介紹 22
2-4.1 光觸媒簡述與應用特性【54】 22
2-4.2 二氧化鈦基本性質介紹 23
2-4.2.1 二氧化鈦構造及其特性 23
2-4.2.2 二氧化鈦光催化的機制 26
2-4.2.3 TiO2製備方法 28
2-4.2.4 影響光催化效率之因素 30
2-4.2.5 添加物對二氧化鈦光催化效率的影響 31
2-4.2.5.1 非金屬類原子與二氧化鈦的摻雜 31
2-4.2.5.2金屬類原子與二氧化鈦的摻雜 35
2-5 靜電紡絲技術 37
2-5.1電紡絲原理與介紹 37
2-5.2影響靜電紡絲技術之參數 38
2-5.2.1流速( Flow Rate )參數 39
2-5.2.2 電壓（Voltage）參數 39
2-5.2.3 分子量（Molecular Weight）與濃度（Concentration）參數 40
2-5.2.4 濃度（Concentration）與黏度（Viscosity）參數 41
2-5.2.5 溶劑參數 42
2-5.2.6 針頭至收集板距離（Distance）參數 44
2-5.2.7 收集方式（Collector） 44
2-6 固－液光催化反應 45
2-6.1 亞甲基藍光分解反應 45
2-6.2 甲基橙光分解反應 46
第三章 實驗內容及方法 50
3-1 實驗藥品與實驗儀器 50
3-1.1 實驗藥品 50
3-1.2 實驗儀器 53
3-1.2.1 實驗設備 53
3-1.2.2 分析儀器 55
3-2 實驗流程 57
3-3實驗溶液配製流程 58
3-3.1 GO/TiO2 Sol-Gel溶液配製流程 58
3-3.2 GO/Ag/TiO2 Sol-Gel溶液配製流程 59
3-4實驗溶液配製的最佳比例及步驟 60
3-5靜電紡絲及實驗參數 63
3-6纖維鍛燒 64
3-7纖維型光觸媒基本性質檢測 65
3-7.1 X光粉末繞射儀（X-ray Diffractometer） 65
3-7.2顯微拉曼光譜（Microscopes Raman Spectrometer）分析 66
3-7.3傅立葉轉換紅外線光譜儀（FT-IR） 67
3-7.4熱重分析儀（TGA） 67
3-7.5場發射掃描電子顯微鏡（SEM） 68
3-7.6 X光能量散佈光譜儀（EDS） 69
3-7.7穿透式電子顯微鏡（TEM） 69
3-7.8比表面積測定儀（BET） 70
3-7.9紫外光/可見光吸收光譜儀（UV-Visible） 72
3-8光降解示性實驗 73
3-8.1最佳鍛燒溫度實驗 73
3-8.2亞甲基藍染料示性光分解實驗流程 73
3-8.3甲基橙染料pH值示性光分解實驗流程 74
3-9光降解示量效率實驗 75
3-9.1亞甲基藍染料示量光分解實驗流程 75
3-9.2甲基橙染料示量光分解實驗流程 76
3-9.3光降解效率規劃 77
第四章 數據分析與討論 79
4-1 TIO2 /GO/AG複合超細纖維光觸媒基本性質檢測 79
4-1.1 Sol-Gel溶液黏度與靜電紡絲參數分析 79
4-1.2 鍛燒溫度分析 82
4-1.3 SEM檢測分析 85
4-1.3.1 TiO2超細纖維的SEM圖分析 85
4-1.3.2 不同比例的GO超細纖維的SEM圖分析 86
4-1.3.3 不同比例的GO-Ag超細纖維的SEM圖分析 90
4-1.4 EDS檢測分析 94
4-1.5 TEM檢測分析 97
4-1.6 XRD檢測分析 102
4-1.6.1 自製的氧化石墨XRD分析 102
4-1.6.2 TiO2複合型纖維XRD分析 103
4-1.7 Raman檢測分析 107
4-1.7.1 Graphite與GO的Raman分析 107
4-1.7.2 TiO2複合型超細纖維的Raman分析 107
4-1.8 反射式UV-Vis光譜檢測分析 109
4-1.8.1 紫外光與可見光區的吸收強度以及吸收範圍分析 109
4-1.8.2 不同比例的複合型光觸媒能隙值分析 110
4-1.9 TGA檢測分析 113
4-1.9.1 基本材料的TGA分析 113
4-1.9.2 未鍛燒GO超細纖維光觸媒的TGA分析 114
4-1.9.3鍛燒450℃後超細纖維光觸媒的TGA分析 115
4-1.10 FT-IR檢測分析 117
4-1.10.1 基本材料FT-IR檢測分析 117
4-1.10.2 複合材料FT-IR檢測分析 118
4-1.11 BET檢測分析 119
4-2 TIO2/GO/AG複合超細纖維光觸媒光降解定量檢測 120
4-2.1 染料亞甲基藍光降解分析實驗 120
4-2.1.1 純可見光的光降解定性實驗 120
4-2.1.2 亞甲基藍（MB）的光降解與暗吸附定量分析實驗 124
4-2.1.2.1 TiO2超細纖維對亞甲基藍光降解與暗吸附分析 125
4-2.1.2.2 ATZ超細纖維對亞甲基藍光降解與暗吸附分析 127
4-2.1.2.3 不同比例GO超細纖維對亞甲基藍光降解與暗吸附分析 130
4-2.1.2.4 不同GO-Ag超細纖維對亞甲基藍光降解與暗吸附分析 139
4-2.1.2.5 亞甲基藍水溶液光降解統整比較分析 148
4-2.2 染料甲基橙光降解分析實驗 149
4-2.2.1 甲基橙初始降解pH值的影響 150
4-2.2.2 甲基橙（MO）的光降解與暗吸附定量分析實驗 151
4-2.2.2.1 TiO2超細纖維對甲基橙光降解與暗吸附分析 151
4-2.2.2.2 ATZ超細纖維對甲基橙光降解與暗吸附分析 154
4-2.2.2.3 不同比例GO超細纖維對甲基橙光降解與暗吸附分析 156
4-2.2.2.4 不同GO-Ag超細纖維對甲基橙光降解與暗吸附分析 165
4-2.2.2.5 甲基橙水溶液光降解統整比較分析 174
第五章　結論 176
參考文獻 180

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