多層次孔洞MFI含鈦沸石在丙烯選擇性氧化反應之研究

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研究生：	羅景仁 Luo, Jing Ren
論文名稱：	多層次孔洞MFI含鈦沸石在丙烯選擇性氧化反應之研究 Hierarchical titanium-containing MFI zeolite for the selective oxidation of propylene
指導教授：	楊家銘 Yang, Chia-Min
口試委員:	黃暄益 Huang, Hsuan-Yi 林昇佃 Lin, Shawn D.
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	86
中文關鍵詞：	沸石、丙烯選擇性氧化
外文關鍵詞：	zeolite
相關次數：	點閱：2 下載：0
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本論文利用以中央疏水段串連兩端四級銨之新型態的tri-block結構導向試劑N3-(PO)5-N3Br6，成功合成出具多層次孔洞的沸石TS-1與silicalite-1，更利用後修飾法將Ti原子修飾於silicalite-1表面以應用於丙烯選擇性氧化反應。與傳統沸石相比，以tri-block SDA合成的沸石具有高表面積及多層次孔洞特性。在合成TS-1部分，我們以經過陰離子交換為氫氧基的結構導向試劑N3-(PO)5-N3(OH)6來合成沸石，所得樣品以四配位鈦為主，但其形貌為許多顆粒聚集成長呈不規則狀。另外，我們將合成態的silicalite-1透過酸洗步驟，選擇性移除結構導向試劑疏水段部分以曝露出沸石奈米層表面，接著再進一步以titanocene dichloride進行修飾而使silicalite-1表面帶有接近全為四配位鈦的物種，能製備出含幾乎純四配位鈦的沸石材料。我們把這些含鈦的多層次孔洞沸石附載金奈米粒子，應用來催化丙烯選擇性氧化反應。結果發現不論是直接合成的多層次孔洞TS-1或者表面修飾Ti的silicalite-1，其轉化率雖然並沒有大幅改善，但比較傳統TPAOH合成的TS-1在500分鐘以內有較佳催化穩定性。

In the research, triblock structure directing agent (SDA) N3-(PO)5-N3Br6 with hydrophobic middle part and hydrophilic ends was applied to the synthesis of hierarchical silicalite-1 and TS-1. In addition, Ti species were grafted on the surface of silicalite-1 for propylene epoxidation. Compared with conventional MFI zeolites, materials obtained by using tri-block as SDA featured high BET surface area and hierarchical structure. In the synthesis of hierarchical TS-1 prepared by using the SDA N3-(PO)5-N3OH6, the resulted material showed considerable amount of tetrahedral Ti species, but the morphology was irregular. After selectively removing the hydrophobic part of SDA by acid treatment the hierarchical silicalite-1 could exposed the external surface of nanosheets, which was grafted with titanocene dichloride to form tetrahedrally coordinated species . We deposited gold nanoparticles onto the two hierarchical titanium-containing zeolites and used them as catalysts for propylene epoxidation. Although both samples prepared by post-grafting and direct hydrothermal synthesis did not improve the conversion of propylene compared to conventional zeolite, they exhibited greater catalytic stability in 500 minutes.

1.    緒論    1
1-1沸石    1
1-1-1 沸石簡介    1
1-1-2 沸石結構    2
1-1-3 MFI沸石    4
1-2多層次孔洞的沸石材料合成法    6
1-2-1 前驅物組裝法    8
1-2-2後合成法    8
1-2-3模板合成法    12
1-3丙烯選擇性氧化反應    19
1-3-1丙烯選擇性氧化反應之重要性    19
1-3-2丙烯環氧化反應催化劑種類    20
1-3-3 Au-Ti催化劑    21
1-4研究動機    24
2.    實驗部分    26
2-1實驗藥品    26
2-2結構導向試劑的合成與離子交換    27
2-2-1具四級銨分子合成    29
2-2-2兩性高分子的合成    30
2-2-3結構導向試劑的離子交換    31
2-3沸石材料合成    31
2-3-1水熱法合成titanium silicalite-1 (TS-1)    31
2-3-2後修飾法合成TS-1    32
2-3-3製備負載金奈米粒子的沸石材料    34
2-3-4 Silicalite-1表面TMS有機官能基修飾測試    34
2-4材料鑑定與分析方法    34
2-4-1 X光粉末繞射分析 (Powder X-Ray Diffraction )    34
2-4-2熱重分析（Thermo Gravimetric Analysis, TGA）    36
2-4-3氮氣物理吸脫附（N2 physisorption）    37
2-4-4掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)    41
2-4-5固態核磁共振光譜 (Solid state NMR spectroscopy)    42
2-4-6傅立葉紅外線轉換光譜 (FT-IR spectroscopy)    43
2-4-7紫外光-可見光光譜 (UV-Vis spectroscopy)    44
2-4-8 氣相層析 (Gas chromatography, GC)    45
2-4-9感應耦合電漿質譜（Inductively Coupled Plasma-Mass Spectroscopy, ICP-MS）    46
2-4-11 X光吸收光譜術(X-ray absorption spectroscopy, XAS)    46
2-5丙烯選擇性氧化反應    51
2-6樣品命名    52
3.    結果與討論    53
3-1結構導向試劑的鑑定    53
3-2 結構導向試劑之陰離子對合成TS-1沸石材料的研究    56
3-2-1對形貌與結構上之探討    57
3-2-2 Ti配位情形之探討    60
3-3 silicalite-1表面修飾之研究    61
3-3-1 Silicalite-1疏水端的移除    62
3-3-2表面TMS有機官能基修飾測試    66
3-3-3 Silicalite-1表面鈦修飾    69
3-5 Au/TS-1於氣相丙烯選擇性氧化反應的研究    74
3-5-1 Au/TS-1的鑑定    75
3-5-2 Au/TS-1於丙烯選擇性氧化反應的活性測試    77
4. 結論    80
5. 參考文獻    82

                                

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