臺灣博碩士論文加值系統

本研究係以水熱法將三種不同金屬(鐵、鈷、鎳)成功的添加市售二氧化鈦光觸媒中，以提升其可見光光解甲基藍之效能。由氮氣吸附曲線可觀察出，添加不同金屬後之二氧化鈦粉體，其比表面積及孔徑分佈與添加前並無改變。在漫反射光譜分析中，添加金屬離子後之二氧化鈦粉体在400〜700 nm奈米波長範圍裡有光線吸收峰值，並向可見光區轉移。根據Kubelka-Munk圖表計算得知，在添加相同濃度金屬溶液之狀況下，光觸媒材料其能隙大小依序為；添加鐵(2.98eV)＞添加鈷(2.88eV)＞添加鎳(2.63eV)。而Langmuir-Hinshelwood模式可求出在液相環境中，光觸媒光解甲基藍的活性大小。根據以上各種分析結果發現，隨著光觸媒能隙值越低，其光分解之活性就越高。此現象歸因於添加金屬的二氧化鈦光觸媒有較狹窄的能階，當受到可見光激發時，其電子電洞對能有較佳之活性來進行氧化還原反應，因而達到最佳的可見光光解效能。
本研究以水熱法合成之可見光光觸媒，能有效的光解有機染料。在實際效能驗證方面，吾人以吐司及瓷磚為載具，進行可見光光解效能測試。實驗結果指出，添加金屬離子後之二氧化鈦光觸媒能有效的抑制大腸桿菌生長，得以延長吐司的防腐期。另一方面，經過添加金屬之二氧化鈦光觸媒塗佈之磁磚，在兩週後表面依舊保持清潔，而以市售商用二氧化鈦光觸媒塗佈之瓷磚，其在可見光下對大腸桿菌並不具殺菌/抑菌之能力，大腸桿菌依舊可以在瓷磚上滋長。正因為這些獨特之效能，本研究之合成技術確能提供具有經濟效益之可見光奈米光觸媒製造方法，可廣泛應用於室內各項營建材料，改善環境品質。

In this dissertation, a hydrothermal treatment was employed to doping three types of metal ions (Fe, Co, and Ni) into commercial TiO2 photocatalysts for improving the photocatalytic reactivity of methylene blue (MB) under visible light irradiation. Nitrogen physisorption measurement indicated that surface areas and porosities of metal-doped titania powders still maintain an identical value, comparing to the starting material. The diffuse reflection spectra of metal-doped titania reflected a light absorption edge, shifting to the visible light range of ca. 400–700 nm. According to Kubelka-Munk plot, the optical band gaps were found to have the following order： Fe-doping (2.98 eV) > Co-doping (2.88 eV) > Ni-doping (2.63 eV), based on the fixed dopant concentration. A Langmuir-Hinshelwood model was used to investigate the photocatalytic activity for removing MB from liquid phase. It was found that the decreasing optical band gap is accompanied by increasing photo degradation activity of MB. This result can be attributed to a fact that metal-doped titania photocatalyst with the narrowest band gap is capable of generating better redox ability of electron–hole pairs under visible light, thus leading to the greatest photocatalytic activity.
According to the results, the visible-light-derived photocatalysts prepared by the above hydrothermal synthesis exhibit an excellent photocatalytic capability in decomposing organic dyes. In practical operation, we employed ceramic tile and toast as substrates for evaluating the photocatalytic ability under visible illumination. Experimental results indicated that the metal-doped titania photocatalysts enable to prevent the growth of E. coli, thus extending the anti-spoiled period of toast. After coating them onto ceramic tile, the prepared tile leads to keep a cleaner surface than the tile coated with commercial photocatalysts after two weeks. This fascinating effect proves that this fabrication technique is an efficient method in preparing visible-light-derived photocatalysts that can be extensively used in a variety of applications such as indoor decoration, ceramic tile, glass, house furnishings, and so on.

第一章　緒　論 1
1.1 研究動機 1
1.2 研究範圍 2
1.3 研究目的 3
1.4 研究方法 4
1.5 研究流程 5
第二章　奈米科技發展回顧 6
2.1 奈米科技的源起與定義 6
2.1.1 奈米的定義 8
2.1.2 奈米科技涵蓋範圍 8
2.1.3 奈米材料科技之發展過程 9
2.2 奈米材料 12
2.2.1 原子團簇 13
2.2.2 奈米微粒 13
2.2.3 奈米微粒的物理性質與化學性質 14
2.3 奈米材料之製備技術 17
2.3.1 製備奈米粒子的物理方法 18
2.3.2 製備奈米粒子的化學方法 21
第三章 奈米光觸媒發展回顧 26
3.1 觸媒與半導體基本原理 26
3.2 光觸媒催化反應基本原理 31
3.3 TiO2奈米光觸媒之物理性質 32
3.4 TiO2奈米光觸媒之光化學催化反應 36
3.5 可見光TiO2奈米光觸媒製作之研究 41
第四章　實驗計畫 43
4.1 實驗藥品 43
4.2 實驗儀器裝置 44
4.3 實驗方法 45
4.4 實驗流程 46
4.5 特性分析與性質測試 47
4.5.1 光觸媒粉體之表面形態檢測 47
4.5.2 光觸媒粉體之晶相關察 49
4.5.3 比表面積及孔隙度分析 51
4.5.4 晶體微結構分析 54
4.5.5 光觸媒之吸收光譜分析 55
第五章　實驗結果討論分析 58
5.1 TiO2之結構與表面特性分析 58
5.1.1 TiO2奈米粉體之表面積與孔洞分佈 58
5.1.2 TiO2奈米粉體之表面形態 60
5.1.3 TiO2奈米粉體之晶體結構 62
5.2 TiO2之紫外-可見光吸收光譜分析 64
5.3 可見光TiO2奈米光觸媒之活性測試 69
5.4 實驗結論 74
第六章 可見光TiO2奈米光觸媒效能驗證 75
6.1 實驗藥品 75
6.2 實驗方法 76
6.3實驗流程 77
6.4 可見光奈米光觸媒效能驗證 78
第七章 結論與建議 93
7.1 結論 93
7.2 建議與後續研究 95
參考文獻 97

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