具乙基、苯環及羧酸官能基之中孔洞材料的合成與鑑定

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姓名

鍾智萱(Chih-Hsuan Chung) 查詢紙本館藏

畢業系所

化學學系

論文名稱

具乙基、苯環及羧酸官能基之中孔洞材料的合成與鑑定
(Synthesis and Characterization ofMesoporous Silicas with Ethane, Benzene and Carboxylic Functionality)

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摘要(中)

本篇論文主要是合成具有雙官能基的中孔洞材料，共分為兩個部分，第一部分是利用 P123 (Pluronic 123) 作為模板試劑，
1,2-bis-(trimethoxylsilyl)ethane (BTME) 與 Carboxyethylsilanetriol sodium salt (CES) 為共同矽源，在酸性條件下合成具有乙基與羧酸官能基之中孔洞材料 SBA-15，之後再利用 48 % H2SO4 在高溫下裂解模板 P123，得到雙官能基化的中孔洞材料 SBA-15，而 CES 含量可達60 %，仍具有良好的結構規則度。
第二部份也是利用 P123 (Pluronic 123) 作為模板試劑，
1,4-bis(triethoxysilyl)benzene (BTEB) 與 Carboxyethylsilanetriol sodium salt (CES) 為共同矽源，在酸性條件下合成具有苯環與羧酸官能基之中孔洞材料 SBA-15，之後再利用 48 % H2SO4 在高溫下裂解模板 P123，得到雙官能基化的中孔洞材料 SBA-15，而 CES 含量可達 50 %，仍具有良好的結構規則度。
以上兩部份實驗都會利用 X-ray 粉末繞射、固態核磁共振光
譜、熱重分析儀及等溫氮氣吸脫附等儀器鑑定材料的特性，了解在不同 CES 含量比例之孔洞性質變化趨勢，且對於植入的羧酸官能基定量。

摘要(英)

The thesis is divided to two parts, both studied on
bifunctionalization of mesoporous materials. In part one, carboxylic acid functionalized mesoporous ethane-silicas have been synthesized with P123 as the structure-directing agent under acidic conditions via co-condensation of 1,2-bis-(trimethoxylsilyl)ethane (BTME) and carboxyethylsilanetriol sodium salt (CES). A high degree of structural ordering is still retained up to 60 mol% CES loading (based on silicon) in the synthesis mixture, and we also have acid capacity by acid-base titration, which was 4.53 mmol/g.
In part two, well-ordered hexagonal mesoporous silica SBA-15 functionalized with carboxylic acid functional groups have been synthesized via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and Carboxyethylsilanetriol sodium salt (CES) templated by P123 under acidic condition. A high degree of structural ordering is still retained up to 50 mol% CES loading (based on silicon) in the synthesis mixture.
In the thesis, 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.

關鍵字(中)

★ 中孔洞
★ 羧酸
★ 乙基
★ 苯環

關鍵字(英)

★ mesoporous
★ ethane
★ benzene
★ carboxylic

論文目次

中文摘要.............................................. I
英文摘要.............................................. II
謝誌.................................................. III
目錄.................................................. IV
圖目錄................................................ VI
表目錄................................................ VIII
第一章緒論........................................... 1
1.1 中孔洞分子篩材料的簡介............................ 1
1.1.1 中孔洞材料的發展................................ 1
1.2 界面活性劑簡介.................................... 4
1.2.1 界面活性劑的種類及性質介紹...................... 4
1.2.2 微胞的形成與結構................................ 6
1.2.3 界面活性劑與矽氧化物的交互作用.................. 9
1.3 中孔洞材料形成機制................................ 11
1.3.1 液晶模板機制.................................... 11
1.3.2 協同作用機制.................................... 12
1.3.3 真實液晶模板機制................................ 13
1.4 SBA-15 之形成機制............................. ... 14
1.5 製備中孔洞分子篩.................................. 16
1.6 文獻回顧.......................................... 19
1.6.1 含羧酸官能基之中孔洞材料的發展與應用............ 19
1.7 研究動機與目的.................................... 24
第二章實驗部分....................................... 25
2.1 藥品.............................................. 25
2.2 實驗步驟.......................................... 26
2.2.1 合成含乙基與羧酸官能基的 E-COOH-SBA-15.......... 26
2.2.2 合成含苯環與羧酸官能基的 B-COOH-SBA-15.......... 26
2.2.3 以硫酸溶液裂解 SBA-15 孔洞中的模板.............. 27
2.2.4 以鹽酸溶液脫去酯類上的烷基...................... 27
2.2.5 以酸鹼滴定鑑定COOH-SBA-15 孔洞中的酸當量........ 28
2.3 實驗設備.......................................... 29
2.4 鑑定儀器之原理.................................... 30
2.4.1 同步輻射光束線.................................. 30
2.4.2 X 射線粉末繞射 (Powder X-Ray Diffractometer).... 31
2.4.3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定........ 32
2.4.4
傅立葉紅外線吸收光譜儀 (Fourier Transform Infrared Spectrometer; FTIR) .................................. 35
2.4.5 熱重分析儀(Thermo Gravimetric Analyzer; TGA).... 36
2.4.6 穿透式電子顯微鏡 (Transmission Electron Microscope; TEM) ................................................. 37
2.4.7 固態核磁共振 (Solid State NMR) ................. 39
2.5 固態核磁共振光譜技術介紹.......................... 45
2.5.1 去耦合 (decoupling) 作用........................ 45
2.5.2 魔角旋轉 (Magic Angle Spinning; MAS) ........... 46
2.5.3 29Si MAS NMR 光譜............................... 47
2.5.4 交叉極化 (Cross Polarization; CP) .............. 48
第三章結果與討論..................................... 49
3.1 不同矽源比例合成的 E-COOH-SBA-15.................. 49
3.1.1 E-COOH-SBA-15 系列 XRD.......................... 49
3.1.2 TEM 鑑定........................................ 52
3.1.3 氮氣等溫吸脫附鑑定.............................. 57
3.1.4 FT-IR 紅外線光譜................................ 61
3.1.5 熱重分析........................................ 63
3.1.6 13C DEPTH NMR 鑑定.............................. 68
3.1.7 13C 1-pda NMR 鑑定.............................. 72
3.1.8 29Si MAS NMR 鑑定............................... 75
3.1.9 酸鹼滴定........................................ 77
3.2 不同矽源比例合成的 E-COOH--SBA-15................. 81
3.2.1 B-COOH-SBA-15 系列 XRD.......................... 81
3.2.2 TEM 鑑定........................................ 83
3.2.3 氮氣等溫吸脫附鑑定.............................. 85
3.2.4 FT-IR 紅外線光譜................................ 89
3.2.5 熱重分析........................................ 91
3.2.6 13C 1-pda NMR 鑑定.............................. 97
3.2.7 29Si MAS NMR 鑑定............................... 100
3.2.8 酸鹼滴定........................................ 102
第四章結論........................................... 106
參考文獻.............................................. 107

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指導教授

李光華、高憲明
(Kwang-Hwa Lii、Hsien-Ming Kao)

審核日期

2010-7-27

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