臺灣博碩士論文加值系統

本文之研究目的在探討二氧化鈦光觸媒負載鉑金屬並摻雜石墨烯奈米片之光催化活性，其製備方法為以溶膠凝膠法合成二氧化鈦，並利用光還原法將鉑金屬離子還原沉積在二氧化鈦的表面，再將石墨烯奈米片(graphene nonoplatelet, GNP)摻雜於二氧化鈦中，將其應用於光催化反應。觸媒製備變數包含煅燒溫度、溶劑種類、水量、分散劑種類及比例、GNP比例、鉑比例添加、及不同波長紫外光源製備負載鉑金屬。以石英玻璃反應器在50 ppm甲基橙水溶液250 ml於150分鐘紫外光照射下進行觸媒活性反應測試，光催化反應變因包含不同波長光源、不同初濃度之甲基橙水溶液及光降解亞甲基藍水溶液。
實驗結果顯示，添加1 wt% 石墨烯奈米片於二氧化鈦中並負載1 wt%鉑金屬之觸媒能夠有效提升觸媒的分散情況及反應活性，負載於二氧化鈦上之鉑顆粒尺寸均一且細小，其顆粒尺寸約為2-3 nm。於150 min光催化反應，其甲基橙水溶液之降解率可達88.9 %。
以異丙氧基鈦合成之二氧化鈦為基材所製備的Pt(1)( TiO2(99)GNP(1))(99)觸媒進行光催化反應，當以365 nm波長之光源進行光照反應，經150 min甲基橙轉化率可達91.4 %；而以同觸媒對亞甲基藍水溶液進行光降解反應，於可見光波長420 nm光照下，其反應常數為1.2 min-1，是無添加石墨烯奈米片觸媒Pt(1)TiO2(99)的1.3倍，顯示Pt(1)( TiO2(99)GNP(1))(99)之高催化活性。

In this thesis, the purpose is to study the photocatalytic activity of titania photocatalyst, which is supported by platinum and doped with graphene nonoplatelet (GNP). The preparation of the novel photocatlyst is as follows：sythesis of titania by sol-gel method, deposition of platinum by photoreduction, then doping with GNP. The photocatalytic activity of the catalyst is tested by photodegadation of methyl orange using quartz glass reactor under the UV light illumination. The parameters of catalyst preparation include temperature of calcination, amount of water, kinds and ratios of dispersant, weight of CTMAB addition, weight of GNP doping, loading of platinum, and sources of UV light for photoreduction of platinum. Operating conditions in photocatalytic reaction included initial concentration of methyl orange solution, wavelength of illumination and photodegradation of methylene blue.
The results revealed that the doping of 1 wt% graphene-nanoplatelet and loading of 1wt% platinum in titania effectively improve the dispersion and reaction activity of the catalyst. The particle size of platinum metal is very small to be 2-3 nm and distributed uniformly. Under 150 min of the UV light illumination, the conversion of photodegradation of methyl orange solution is above 88 %.
The photodegradation of the methyl orange solution is also performed by the catalyst Pt(1)( TiO2(99)GNP(1))(99) under irradiation of UV light (365 nm), and the conversion of the degradation is 91.4 % in 150 min. The reaction rate constant for photodegradation of the methylene blue solution under irradiation of visible light (420 nm), is 1.2 min-1 which is 1.3 times of the catalyst Pt(1)TiO2(99) without doping GNP, showing the high catalytic efficiency of Pt(1)( TiO2(99)GNP(1))(99).

誌謝 i
摘要 ii
Abstract iii
目錄 v
圖目錄 x
表目錄 xviii
符號說明 xxii
第一章 緒論 1
1.1. 前言 1
1.2. 研究目的與方法 2
1.2.1. 研究目的 2
1.2.2. 研究方法 3
第二章 文獻回顧與基本原理 6
2.1.　二氧化鈦基本性質 6
2.1.1.　二氧化鈦的構造及特性 6
2.2.　觸媒之製備方法 9
2.2.1.　溶膠-凝膠法(Sol-Gel method) 9
2.2.2.　水熱法 (Hydrothermal method) 12
2.2.3.　熱水解法 (Thermal hydrolysis method) 12
2.2.4.　含浸法 (Impregnation method) 12
2.2.5. 液相沉積法 (Liquid phase deposition, LPD) 13
2.2.6. 微乳膠法 (Microemulsion method) 13
2.2.7.　化學氣相沉積法 (Chemical vapor deposition, CVD） 13
2.2.8. 光催化還原法(Photocatalytic reduction method) 14
2.2.9. 沉澱固著法(Deposition-precipitation method) 15
2.3.　半導體光催化反應原理 16
2.3.1. 量子尺寸效應(Quantum Size Effects) 16
2.3.2. 光催化原理及機制 17
2.3.3. 二氧化鈦光催化之反應 18
2.4. 二氧化鈦光觸媒之改質 19
2.4.1. 摻入過渡金屬離子 20
2.4.2 金屬原子負載 20
2.4.3. 複合半導體 21
2.5. 石墨烯 23
2.5.1石墨烯之基本特性 23
2.5.2.　石墨烯之製備與合成方法 27
2.5.3　石墨烯之應用 29
2.6. 光觸媒反應文獻回顧 32
第三章 實驗設備與方法 37
3.1. 實驗藥品 37
3.2. 實驗設備 39
3.3. 分析儀器 39
3.3.1. 場發射掃描式電子顯微鏡 (Field Emission Scanning Electron Microscope, FE-SEM) 40
3.3.2. X光能量散佈儀(X-ray Energy Dispersive Spectrometer, EDS) 41
3.3.3. 穿透式電子顯微鏡(Transmitted Electron Microscope, TEM) 41
3.3.4. 傅立葉轉換紅外線光譜儀(FT-IR) 42
3.3.5. 熱重分析儀(Thermogravimetric Analysis, TGA)氣相層析儀 43
3.3.6. X-ray繞射儀(X-ray Diffraction Spectrometer) 44
3.3.7. BET表面積與孔洞分析儀(Brunauer-Emmett-Teller) 46
3.3.8. 紫外-可見光光譜儀(UV-vis Spectrophotometer) 47
3.4. 實驗方法 48
3.5. 觸媒於甲基橙及亞甲基藍光催化反應 51
3.5.1. 觸媒於甲基橙光催化反應之反應機構 51
3.5.2. 觸媒於亞甲基藍光催化反應之反應機構 52
3.5.3. 觸媒於甲基橙及亞甲基藍光催化反應計算 53
3.6. 甲基橙(MO)及亞甲基藍(MB)水溶液檢量線 56
第四章 觸媒活性與特性分析 58
4.1. 前言 58
4.2. 不同煅燒溫度對二氧化鈦光觸媒之影響 62
4.3. 不同溶劑種類製備二氧化鈦對光觸媒之影響 74
4.4. 不同水量添加對二氧化鈦光觸媒之影響 84
4.5. 石墨烯性質探討 94
4.6. 不同分散劑對TiO2(99)GNP(1)光觸媒之影響 97
4.7. 不同分散劑CTMAB比例對TiO2(99)GNP(1)光觸媒之影響 108
4.8. 不同鉑比例添加量對TiO2(99)GNP(1)光觸媒之影響 118
4.9. 添加不同石墨烯奈米片比例對光觸媒之影響 133
4.10. 不同紫外光波長製備添加 0.5 wt%鉑對 TiO2(99)GNP(1)光觸媒之影響 146
4.11. 結論 158
第五章 光催化反應操作條件探討 161
5.1. 前言 161
5.2. 不同初濃度甲基橙水溶液對光催化反應之影響 161
5.3. 不同波長光源對甲基橙光催化反應之影響 166
5.4. 不同混光源對甲基橙光催化反應之影響 171
5.5. 光降解亞甲基藍水溶液 175
5.6. 結論 179
第六章 總結 181
6.1. 觸媒製備與特性分析 181
6.2. 光催化反應 183
參考文獻 186

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