近幾年，複合奈米材料為研究之大宗。二氧化鈦因為有便宜、無毒性、化學穩定性高等優點，常用於各種應用中，但由於其帶隙過寬(3.0-3.2 eV)且電子電洞再結合率過高，故在光催化應用上有所限制；許多研究試著延展二氧化鈦的光吸收範圍，其中一項便是加入奈米金粒子，其優點除了能夠降低電子電洞再結合率以外，亦能降低光催降解之活化能，使其在光催化應用上有更多的發展性，因此貴金屬半導體複合材料在光催化應用上扮演重要角色；此外，加入金屬硫族化物被證實能夠延展材料在可見光範圍的吸收，其中硒化銀為一具有前瞻性之材料。故本論文架構出一個簡易合成二氧化鈦-金-硒化銀三層奈米結構之方法，先使用油相方法於270 oC合成二氧化鈦奈米棒後，添加金銀合金晶種使其與二氧化鈦複合，再藉由加入硒粉將銀自合金中析出，進而形成二氧化鈦-金-硒化銀三層奈米結構。此材料之二氧化鈦奈米棒長度約為32 nm，長寬比約11-11.5，而金-硒化銀微型結構則為dumbbell形貌，大小介在8-15 nm，比表面積藉由UV-Vis儀器鑑定後證實三層結構在可見光吸收波段有強吸收，EPR則顯示其在照光後可產生氫氧自由基。本研究將其應用在太陽光光催化降解雙酚A，最佳條件可在照光1.5 h後降解97 % 雙酚A，反應常數為0.01745 min-1，為二氧化鈦奈米棒、二氧化鈦-金反應性的5倍，證實本實驗所合成出之三層結構複合材料為一具有前瞻性的光催化劑。

Over the past decades, the fabrication and application of hybrid composites that integrate two or more nanoscale components have received much attention. The combination of noble metal and semiconductor such as Au-TiO2 is one of the most popular heterostructures because of the low cost, nontoxicity, suitable optical property and chemical stability, which can be used in a wide variety of applications. More recently, the addition of metal calcogenides, has been shown to effectively enhance the harvest efficiency of visible light of TiO2-Au. Silver selenide (Ag2Se) is a metal calcogenide with narrow bang gap which has special electronic and optical properties to extend the absorption wavelength of Au-TiO2. In this study, we synthesized the ternary TiO2-Au-Ag2Se nanorods using a facile method. The 1-dimentional TiO2 nanorods were first fabricated in nonaqueous solution at 270 ºC , and were then mixed with AuAg alloy seeds to form TiO2-Au-Ag2Se nanorods in the presence of Se powder and 1-dodecanethiol. The morphology as well as microstructures of TiO2-Au-Ag2Se nanorods have been characterized. The TEM images and XRD patterns showed that the as-prepared TiO2 nanorods were mainly in anatase phase and the average dimension was 2.8  32 nm. In addition, the particle size of dumbbell-likeAu-Ag2Se was 8.5 nm, where Au was in fcc structure and Ag2Se was in alpha form. The TiO2-Au-Ag2Se exhibited a wide absorption wavelength range of 300-1500 nm. In addition, bisphenol A was found to be rapidly decomposed by TiO2-Au-Ag2Se under visible light, showing that the ternary TiO2-Au-Ag2Se nanorods are promising materials for potential applications in the fields of optoelectronics, water splitting and photodegradation.

摘要……………………………………………………………………………….......i
Abstract ……………………………………………………………………………….ii
目錄 ………………………………………………………………………………….iii
表目錄 ……………………………………………………………………………….vi
圖目錄 ………………………………………………………………………………vii


第一章 緒 論 1
1-1 前言 1
1-2 研究動機 2
1-3 研究目的 2
第二章 文獻回顧 3
2-1 光催化劑工作原理 3
2-2 二氧化鈦 3
2-2-1 二氧化鈦結構與性質 3
2-2-2 二氧化鈦合成方法 5
2-2-3 二氧化鈦修飾方法 9
2-3 合成不同結構之光催化劑 13
2-4 汙染物介紹─雙酚A 18
第三章 實驗方法與步驟 21
3-1 實驗藥品與器材 21
3-2 實驗架構 22
3-3 一層結構 (TiO2 nanorod) 23
3-4 二層結構 (TiO2-Au) 24
3-5 三層結構 (TiO2-Au-Ag2Se) 25
3-6 熱處理 27
3-7 光催化實驗架構圖 28
3-8 材料特性鑑定及汙染物測定 29
3-8-1 X光粉末繞射儀 (XRD) 29
3-8-2 比表面積分析儀 (BET) 29
3-8-3 穿透式電子顯微鏡 (TEM) 30
3-8-4 電子能譜儀 (XPS) 30
3-8-5 電子順磁共振光譜儀(EPR) 31
3-8-6 紫外光─可見光分光光譜儀(UV-Vis) 31
3-8-7 感應耦合電漿發射光譜儀(ICP-OES) 32
第四章 結果與討論 33
4-1 二氧化鈦合成與鑑定 33
4-1-1 TEM 33
4-1-2 XRD 36
4-1-3 FTIR 38
4-1-4 BET 39
4-1-5 TGA 40
4-2 二層結構複合材料：二氧化鈦-金 42
4-2-1 二層結構複合材料合成與鑑定 42
4-2-2 二層結構光催化反應表現 56
4-3 三層結構複合材料：二氧化鈦-金 61
4-3-1 Ternary(1.5wt%Au)合成與鑑定 61
4-3-2 Ternary(0.5wt%Au)合成與鑑定 74
4-3-3 三層結構複合材料光催化反應表現 89
第五章 結 論 101
 

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