具硫基官能基之中孔洞材料 SBA-1 的合成與鑑定

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沈姿誼(Tzu-Yi Shen) 查詢紙本館藏

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論文名稱

具硫基官能基之中孔洞材料 SBA-1 的合成與鑑定
(Synthesis and Characterization of Cubic Mesoporous Silicas SBA-1 with Thiol Functionality)

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摘要(中)

中文摘要
在本篇研究是以MPTMS ((3-Mercaptopropyl)trimethoxysilane) 與TEOS (Tetraethtyl orthosilicate) 為共同矽源，使用 C16TEABr (cetyltriethylammonium bromide) 作為模板試劑，在反應溫度為273 K下直接合成具有硫基官能基的中孔洞材料SBA-1，之後經由HCl / EtOH溶劑做萃取處理，移除模板後，得到的中孔洞材料仍然具有SBA-1的結構存在。研究發現硫基官能基化的中孔洞材料SBA-1，其MPTMS含量可達20%，對於中孔洞立方結構不會造成相轉變或是結構破壞，而其表面積、孔洞體積以及孔洞直徑均會隨MPTMS含量的增加而有遞減的趨勢。
藉由改變不同的酸量、不同的水熱時間、不同的攪拌時間以及不同矽源，探討對於合成具有硫醇官能基的SBA-1的影響。在改變不同的酸量的方面，可以觀察到不同的結果，在XRD 的結果中，可發現隨著酸量的增加，可加入在SBA-1中的MPTMS 之含量也隨之增加，而在29Si MAS NMR也觀察到隨著酸量的增加，有助於中孔洞材料SBA-1結構的穩定。在水洗測試也可得知，加入官能基可以有效的改善SBA-1結構不能水洗及不能溶劑萃取的缺點。

摘要(英)

Abstract
One-step synthesis of well-ordered cubic mesoporous silicas SBA-1 containing simultaneously tetraethoxysilane (TEOS) and 3-mercapto- propyltrimethoxysilane (MPTMS) and has been synthesized by cetyltriethylammonium bromide (CTEABr) under strongly acidic conditions. In order to get optimized the thiol-functionalized mesoporous silicas SBA-1 which has been studied by in a wide range of synthesis conditions. All kinds of results of formating the parameter, including the relative reagent concentration (TEOS/MPTMS ratio), HCl concentration, synthesis temperature, and hydrothermal time.
The materials obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), nitrogen sorption measurements, 13C and 29Si magic angle spinning (MAS), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA).
The lower TEOS/MPTMS ratios resulted in materials with higher functional group loadings. The direct synthesis of thiol- functionalized SBA-1 materials, the concentration of MPTMS that can co-condense with TEOS will be up to 20% without observing a significant loss in the structure order and uncontrollable phase transformation of the cubic SBA-1 mesostructure. The HCl concentration of change was found that can determine the stability of thiol-functionalized SBA-1 towards the solvent extraction treatment. The difference in the morphology between pure SBA-1 and thiol- functionalized SBA-1 becase of the incorporated MPTMS can slow down the condensation rate of TEOS.

論文目次

中文摘要.................................................... I
英文摘要.................................................... II
目錄........................................................ III
圖目錄...................................................... VI
表目錄...................................................... IX
第一章序論............................................... 1
1-1 中孔洞分子篩材料的歷史............................... 1
1-2 界面活性劑性質簡介................................... 2
1-2.1 分子結構....................................... 2
1-2.2 界面活性劑種類................................. 4
1-2.3 微胞的形成..................................... 5
1-2.4 界面活性劑聚集的結構........................... 6
1-3 中孔洞形成機制....................................... 8
1-4 SBA-1簡介............................................ 10
1-4.1 SBA-1的形成機制................................ 11
1-4.2 SBA-1結構鑑定.................................. 12
1-5 中孔洞分子篩表面修飾................................. 14
1-6 表面修飾中孔洞分子篩之應用........................... 17
1-7 研究動機與目的....................................... 20
第二章實驗部分............................................ 21
2-1 藥品................................................. 21
2-2 實驗步驟............................................. 22
2-2.1 合成界面活性劑 CTEABr.......................... 22
2-2.2 合成含硫基官能基的SBA-1(SH-SBA-1).............. 22
2-2.3 以溶劑萃取法移除含硫基官能基SBA-1孔洞中的模板.. 25
2-2.4 中孔洞分子材料 SH-SBA-1 吸附金屬離子實驗....... 25
2-3 實驗鑑定儀器......................................... 26
2-4 鑑定儀器之原理....................................... 26
2-4.1 X光繞射 (Powdr X-Ray Diffractometer；XRD)...... 26
2-4.2 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定...... 27
2-4.3 固態核磁共振 (Solid State NMR)................. 32
2-4.3-1 去氫偶合 (proton decoupling)............... 33
2-4.3-2 魔角旋轉 (Magic Angle Spinning)............ 33
2-4.3-3 交叉極化 (Cross-Polarization, CP).......... 35
2-4.4 低真空掃描式電子顯微鏡 (LV-SEM)................ 36
2-4.5 熱重分析儀 (Thermo Gravimetric Analyzer；TGA).. 36
2-4.6感應耦合電漿原子發射光譜分析儀ICP-AES........... 37
第三章結果與討論.......................................... 38
3-1 不同酸量下合成的中孔洞材料SH-SBA-1................... 38
3-1.1 XRD 結果...................................... 38
3-1.2 氮氣等溫吸脫附的結果.......................... 43
3-1.3 13C CP/MAS NMR 結果........................... 51
3-1.4 29Si MAS NMR 結果............................. 53
3-1.5 TGA 結果...................................... 59
3-1.6 SEM 結果...................................... 62
3-2 在不同水熱時間下合成的中孔洞材料SH-SBA-1............. 67
3-2.1 XRD 結果...................................... 67
3-2.2 氮氣等溫吸脫附的結果.......................... 66
3-2.3 29Si MAS NMR 結果............................. 68
3-3 不同矽源合成的中孔洞材料SH-SBA-1..................... 70
3-3.1 XRD 結果...................................... 70
3-3.2 氮氣等溫吸脫附的結果.......................... 72
3-3.3 29Si MAS NMR 結果............................. 74
3-4 在不同反應溫度合成的中孔洞材料SH-SBA-1............... 76
3-4.1 XRD 結果...................................... 76
3-4.2 氮氣等溫吸脫附的結果.......................... 79
3-4.3 SEM 結果...................................... 82
3-5 SH-SBA-1之水洗測試................................... 84
3-6 吸附金屬離子測試..................................... 86
第四章結論................................................. 87
參考文獻................................................... 88

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指導教授

高憲明(Hsien-Ming Kao)

審核日期

2006-7-19

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