本研究運用層狀沸石結構hierarchical silicalite-1 octahedra作為模板，填入金、二氧化鈦，使金生長於模板狹縫狀孔洞中，成功合成出具有碟狀形貌的金奈米顆粒，並且於金奈米顆粒周圍修飾上二氧化鈦的光催化劑。金碟狀奈米顆粒擁有強的局域表面電漿共振吸收，並且二氧化鈦在金碟狀奈米顆粒的周圍，可以幫助穩定局域表面電漿共振產生的光致電子，幫助電子電洞對分離，提升光催化活性。將此材料作為可見光催化產氫光催化劑，在可見光照射下，以甲醇作為犧牲試劑的條件下，具有高達264 μmolg-1h-1的產氫活性，是Au/P25活性的24倍。此外，由於金奈米顆粒被層狀沸石、二氧化鈦所包覆，所以可以運用層狀沸石的孔道進行犧牲試劑大小的篩選，此光催化劑在分別以甲醇、乙醇做為犧牲試劑的條件下，在可見光照射下，能夠選擇性的只與甲醇進行光催化產氫反應。

In this thesis, photocatalysts which contained Au nanodisks were synthesized by intercalating Au and TiO2 into inter-sheet spacing of hierarchical silicalite-1 octahedra which were self-pillared zeolite nanosheets. Au nanodisks exhibited high light absorption in visible light region by localized surface plasmon resonance and neighboring TiO2 could stabilize LSPR induced electrons. This photocatalyst showed 24 times higher activity( 264 μmolg-1h-1 ) than Au/P25 for photocatalytic hydrogen production in methanol solution by visible light irradiation. Because Au nanodisks and TiO2 were sandwiched between zeolite nanosheets, this photocatalyst could selectively react with sacrificial agents with different sizes by size exclusion effect which provided by zeolite nanosheets. By using methanol and ethanol as sacrificial agent, this photocatalyst showed no activity for photocatalytic hydrogen production in ethanol solution by visible light irradiation.

摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 XI
第一章 緒論 1
1-1 光催化水分解產氫 1
1-1-1 光催化分解水之工作原理 2
1-1-2 犧牲試劑之工作原理 3
1-2 半導體光觸媒 4
1-2-1 金屬氧化物半導體 5
1-2-2 二氧化鈦光觸媒簡介 6
1-3 光催化活性的改善 8
1-3-1 改變結晶性及顆粒大小 8
1-3-2 負載共催化劑 9
1-3-3 局域表面電漿共振效應 10
1-4 多層次( hierarchical )孔洞的沸石材料簡介 13
1-4-1 沸石簡介 13
1-4-2 沸石結構與分類 13
1-4-3 MFI結構沸石 15
1-4-4 軟模板合成法 17
1-5 研究動機 18
第二章 實驗部分 20
2-1 實驗藥品 20
2-2 樣品製備 21
2-2-1 多層次孔洞沸石材料合成 21
2-2-2 多層次孔洞沸石材料中結構導向試劑疏水端的移除 25
2-2-3 後修飾金/二氧化鈦之多層次孔洞沸石材料合成 25
2-2-4 光催化活性對照樣品合成 26
2-3 光催化反應 27
2-4 樣品命名 30
2-5 材料鑑定與分析技術簡介 32
2-5-1 X光粉末繞射( Powder X-Ray Diffraction, PXRD ) 32
2-5-2 氮氣物理吸脫附( N2 Physisorption ) 33
2-5-3 掃描式電子顯微術( Scanning Electron Microscopy, SEM ) 37
2-5-4 穿透式電子顯微術( Transmission Electron Microscopy, TEM ) 37
2-5-5 紫外/可見光吸收光譜( UV-Visible Spectroscopy, UV-Vis ) 38
2-5-6 X光吸收光譜( X-ray Absorption Spectroscopy, XAS ) 38
2-5-7 核磁共振光譜( Nuclear Magnetic Resonance Spectroscopy, NMR ) 40
第三章 結果與討論 41
3-1 結構導向試劑的鑑定 41
3-2 多層次孔洞沸石材料的分析與鑑定 47
3-2-1 多層次孔洞沸石材料中結構導向試劑疏水端的移除 49
3-3 後修飾金/二氧化鈦之多層次孔洞沸石材料 51
3-3-1 含浸液pH值的影響 52
3-3-2 Au/TiO2前驅物含浸量的影響 56
3-3-3 鍛燒對樣品的影響 61
3-4 樣品於光催化產氫活性之研究 64
3-4-1 樣品鍛燒溫度對活性之影響 65
3-4-2 樣品金屬含量對活性之影響 68
3-5 犧牲試劑種類對可見光催化水分解產氫活性影響 71
3-6 樣品可見光產氫反應失活原因探討 75
第四章 結論 76
第五章 參考文獻 78

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