具苯環、胺基及磷酸官能基之中孔洞材料的合成與鑑定

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高佳駿(Chia-Chun Kao) 查詢紙本館藏

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論文名稱

具苯環、胺基及磷酸官能基之中孔洞材料的合成與鑑定
(Synthesis and Characterization of Mesoporous Silicas With Benzen bridging, amine and phosphonic acid groups)

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摘要(中)

本篇論文分為三個部分，第一部分是利用 tetraethoxysilane (TEOS) 與 1,4-bis(triethoxysilyl)benzene (BTEB) 為共同矽源，以 CTEABr (cetyltriethylammonium bromide) 作為模板試劑，在酸性條件下合成具有苯環官能基化的中孔洞材料 SBA-1，相較於文獻的合成方法，在此合成條件下能合成出具有較高表面積 (最高可達 1210 m2/g) 及孔洞體積 (最高可達 0.64 cm3/g) 的 SBA-1 中孔洞材料。再藉由二維 29Si{1H} HETCOR 實驗研究發現材料中 T (來自於BTEB) 與 Q (來自於 TEOS) 是均勻分散在結構之中，此方面的訊息是其他技術較無法得知的。
第二部份則是利用 (3-aminopropyl)trimethoxysilane (APTMS) 與 tetraethoxysilane (TEOS) 作為共同矽源，以 CTEABr (cetyltriethylammonium bromide) 作為模板試劑，再利用氯磺酸此強酸條件下，以共聚法合成出具有胺基官能基化之中孔洞材料 SBA-1 。利用 X-ray 繞射 (XRD)、固態核磁共振光譜、熱重分析儀 (TGA)及等溫氮氣吸脫附 (nitrogen sorption) 鑑定材料的特性。最後也利用二維 29Si{1H} HETCOR 實驗指出材料中胺基官能基會有靠近 Q3 SiOH 的特性。
最後一部份是使用 diethylphosphatoethyltriethoxysilane (PETES) 與 tetraethoxysilane (TEOS) 作為共同矽源，以 Pluronic 123 作為模板試劑，在酸性條件下合成出具有六方結構之中孔洞材料 SBA-15 。藉由 29Si{31P} REDOR 實驗推論出此具磷酸官能基化之中孔洞材料內分子的排列情形。

摘要(英)

The thesis is divided into three parts. Studies on functionalization of mesoporous materials. In part one, the mesoporous silica SBA-1 (cubic Pm3n symmetry) functionalized with phenyl groups were synthesized via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and tetraethoxysilane (TEOS) under acidic conditions using cetyltriethylammonium bromide (CTEABr) as a structure-directing agent. By optimizing the synthesis composition, the resulting materials exhibited much higher surface areas (up to 1210 m2/g) and larger pore volumes (up to 0.64 cm3/g) as compared to the previous analogue, which only exhibited a surface area of 381 cm2/g and a pore volume of 0.11 cm3/g. Two dimensional (2D) 29Si{1H} heteronuclear correlation (HETCOR) NMR spectra, acquired as a function of contact time, provided direct spectroscopic evidence that a single mesophase with various Q (from TEOS) and T silicon species (from BTEB) located randomly within the pore walls via co-condensation of BTEB and TEOS at a molecular level. Such information is often not achievable by other characterization techniques
In part two, well-ordered cubic mesoporous silica SBA-1 functionalized with amino functional groups have been synthesized via co-condensation of tetraethoxysilane (TEOS), (3-aminopropyl)trimethoxysilane (APTMS) templated by cetyltriethylammonium bromide (CTEABr), under strongly acidic condition by using chlorosulfonic acid as an acidic medium. The materials thus obtained were characterized by a variety of techniques including X-ray diffraction (XRD), solid state 13C and 29Si NMR spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption measurements. Direct NMR evidence for the amine functional groups in close proximity to the Q3 SiOH species in amino-functionalized mesoporous silica SBA-1 is provided by two-dimensional 29Si{1H} HETCOR-based NMR.
In the third part, highly ordered SBA-15 mesoporous silica contains phosphonic acid groups are synthesized via co-condensation of tetraethylorthosilicate (TEOS) and diethylphosphatoethyltriethoxysilane (PETES) using Pluronic 123 (P123) as a structure-directing agent under acidic conditions. The presence of functional group in th resultant material are confirmed by 29Si{31P} REDOR NMR study.

關鍵字(中)

★ 胺基
★ 磷酸
★ 中孔洞
★ 苯環

關鍵字(英)

★ Mesoporous
★ Benzen
★ amine
★ phosphonic

論文目次

中文摘要………………………………………………………………………... I
英文摘要………………………………………………………………………... III
目錄……………………………………………………………………………... V
圖目錄…………………………………………………………………………... VIII
表目錄…………………………………………………………………………... XI
第一章序論……………………………………………………………………. 1
1-1 中孔洞分子篩的歷史與發展…………………………………………. 1
1-2 中孔洞分子篩 SBA 系列簡介……………………………………….. 3
1-3 SBA-1 形成機制………………………………………………………. 6
1-4 界面活性劑性質簡介…………………………………………………. 7
1-5 中孔洞分子篩的應用……………………………….………………… 11
1-6 文獻回顧………………………………………………………………. 13
1-6-1 含苯環官能基之 PMO 材料…………………………………... 13
1-6-2 含胺基官能基之孔洞材料……………………………………… 16
1-6-3 含磷酸官能基之孔洞材料……………………………………… 19
1-7 研究動機與目的………………………………………………………. 21
第二章實驗部份………………………………………………………………. 22
2-1 藥品……………………………………………………………………. 22
2-2 實驗步驟………………………………………………………………. 23
2-2-1 合成界面活性劑 CTEABr……………………………………… 23
2-2-2 合成含苯環官能基的 SBA-1 (BTEB-SBA-1) ………………… 24
2-2-3 合成含胺基官能基的 SBA-1 (NH2-SBA-1) ………………....... 24
2-2-4 以溶劑萃取法移除具苯環及具胺基官能基之 SBA-1材料孔洞中的模板……………………………………………………………...
25
2-2-5 中孔洞材料 NH2-SBA-1 酸鹼滴定實驗……………………… 25
2-2-6 中孔洞材料 NH2-SBA-1 酸化實驗………………………….... 25
2-2-7 合成含磷酸官能基的SBA-15 (PO3H2-SBA-15) ……………… 25
2-2-8 以濃硫酸移除 SBA-15 孔洞中的模板……………………....... 26
2-2-9 濃鹽酸水解 PO3H2-SBA-15 實驗……………………............... 26
2-3 實驗設備………………………………………………………………. 27
2-4 鑑定儀器………………………………………………………. 28
2-4-1 同步輻射光束線………………………………………………… 28
2-4-2 X 射線粉末繞射 (Powder X-Ray Diffractometer) …………... 29
2-4-3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定……………… 30
2-4-4 熱重分析(Thermo Gravimetric Analyzer；TGA) …………… 32
2-4-5 元素分析(Elemental Analyzer；EA) ……………………….. 33
2-4-6 固態核磁共振 (Solid State NMR) ……………………………... 34
2-5固態核磁共振光譜技術介紹……………………………………........... 35
2-5-1 去耦合 (decoupling) 作用…………………………………….... 39
2-5-2 魔角旋轉 (magic angle spinning，MAS) ……………………..... 39
2-5-3 29Si MAS NMR 光譜…………………………………….......... 40
2-5-4 1H MAS NMR 光譜……………………………………............ 41
2-5-5 交叉極化 (Cross Polarization, CP) ……………………............ 41
2-5-6 2D HETCOR (Heteronuclear Correlation) 實驗………............. 42
2-5-7 2D Exchange 實驗…………………………………….............. 44
2-5-8 REDOR (Rotational-Echo Double resonance) 實驗................... 45
第三章結果與討論. ……………….…………………...................................... 48
3-1 BTEB-SBA-1……..……………….………………….......................... 48
3-1-1 界面活性劑比例…………………….…………………............... 48
3-1-2 BTEB-SBA-1 系列 XRD..........….…………………................ 50
3-1-3 氮氣等溫吸脫附……………….…………………....................... 52
3-1-4 13C CP/MAS NMR……..……….………………….................... 55
3-1-5 29Si MAS NMR……..……….…………………......................... 57
3-1-6 熱重分析……….…………………............................................... 60
3-1-7 1H MAS NMR…......……….…………………........................... 62
3-1-8 29Si {1H} HETCOR NMR 實驗結果分析…….......................... 63
3-1-9 2D 1H-1H Homonuclear Correlation MAS NMR (exchange experiment) ……….………………….....................................................
67
3-2 NH2-SBA-1…….…….…………………............................................. 70
3-2-1 XRD……….….…………………............................................... 70
3-2-2 氮氣等溫吸脫附…………………................................................ 72
3-2-3 13C CP/MAS NMR ………………............................................. 75
3-2-4 29Si MAS NMR …….………….................................................. 77
3-2-5 元素分析………………................................................................ 80
3-2-6 酸鹼滴定實驗………………........................................................ 82
3-2-7 熱重分析…………........................................................................ 85
3-2-8 1H MAS NMR ……………….................................................... 87
3-2-9 29Si {1H} HETCOR NMR 實驗結果分析.................................. 88
3-3 PO3H2-SBA-15 ……………................................................................... 91
3-3-1 XRD ……………….................................................................... 91
3-2-2 氮氣等溫吸脫附………................................................................ 93
3-3-3 13C CP/MAS NMR …….............................................................. 95
3-3-4 29Si MAS NMR ……................................................................... 97
3-3-5 31P MAS NMR …….................................................................... 101
3-3-6 29Si {31P} REDOR MAS NMR 實驗結果分析.......................... 103
第四章結論…………………………………………………………………… 123
參考文獻……………………………………………………………………….. 124

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指導教授

高憲明(Hsien-Ming Kao)

審核日期

2009-8-4

推文