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研究生： 鍾智萱
Chih-Hsuan Chung
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
指導教授： 李光華
Kwang-Hwa Lii
高憲明
Hsien-Ming Kao
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
畢業學年度： 98
語文別： 中文
論文頁數： 123
中文關鍵詞： 中孔洞 、羧酸 、乙基 、苯環
外文關鍵詞： mesoporous, ethane, benzene, carboxylic
相關次數： 點閱：12  下載：0 
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    • 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。

    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.

    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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