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研究生： 邱柏瑞
Po-Jui Chiu
論文名稱： 具雙硫官能基中孔洞材料 SBA-1 的合成與鑑定
Synthesis and Characterization of Cubic Mesoporous Silicas SBA-1 with Disulfide Functionality
指導教授： 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
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 104
中文關鍵詞： 雙硫官能基 、中孔洞材料
相關次數： 點閱：8  下載：0 
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    • 本篇論文分為三個部分，前兩部分為合成具雙硫官能基中孔洞材料 SBA-1，第一部分是利用 Tetraethyl orthosilicate (TEOS) 與 3-Mercaptopropyltrimethoxysilane (MPTMS) 為共同矽源，以 Cetyltriethylammonium bromide (CTEABr) 作為模板試劑，在直接合成法下利用具有氧化力的硫酸條件試著合成出具有雙硫官能基的中孔洞材料 SBA-1，預期原本的 SH 官能基會自行鍵結成 S-S 鍵。藉由 X-ray 繞射儀 (XRD)、固態核磁共振儀 (Solid-state NMR)、熱重分析儀 (TGA) 及氮氣等溫吸脫附儀等儀器鑑定材料的特性。
    第二部分是在硫酸條件下，利用直接合成法，以 CTEABr 作為模板試劑，使用 TEOS 與 Bis[3-(triethoxysilyl)propyl] disulfide (BTSPDS) 為共同矽源，合成出具有雙硫官能基的中孔洞材料 SBA-1，期望能合成出高比例且含硫量較多的材料，以利使用在往後的應用方面。同樣地，藉由 X-ray 繞射儀 (XRD)、固態核磁共振儀 (Solid-state NMR)、熱重分析儀 (TGA) 及氮氣等溫吸脫附儀等儀器鑑定材料的特性。
    第三部分將前兩部分合成之具雙硫官能基中孔洞材料 SBA-1 拿來應用，測試此材料對重金屬離子 Hg2+ 吸附的能力。

    The thesis is divided into three parts. Studies on synthesizing well-ordered mesoporous silicas SBA-1 (Cubic Pm3n symmetry) functionalized with disulfide groups. In part one, the mesoporous silica SBA-1 functionalized with disulfide groups were synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and 3-Mercaptopropyltrimethoxysilane (MPTMS) under oxidized sulfuric acid condition, and using cetyltriethylammonium bromide (CTEABr) as a structure-directing agent. The materials obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption measurements.
    In part two, well-ordered cubic mesoporous silica SBA-1 functionalized with disulfide functional groups have been synthesized via co-condensation of TEOS and Bis[3-(triethoxysilyl)propyl] disulfide (BTSPDS) templated by CTEABr under sulfuric acid condition. The materials obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption measurements.
    In part three, using the former two part’s samples to do the metal ion adsorption experiment. That can test the ability of adsorption Hg2+ metal ion.

    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 序論……………………………………………………………………. 1 1-1 觸媒簡介………………………………………………………………. 1 1-2 界面活性劑簡介……………...……………………………………….. 2 1-2-1 分子結構………………………………………………………… 2 1-2-2 種類……………………………………………………………… 2 1-2-3 微胞……………………………….……………………………... 3 1-2-4 分子排列………………………………………………………… 4 1-3 中孔洞分子篩的歷史與發展…………………………………............. 6 1-3-1中孔洞的定義……………………………………………………. 6 1-3-2 中孔洞分子篩 M41S 系列…………………………………….. 7 1-3-3 中孔洞分子篩 SBA 系列……………………………………… 8 1-4 矽酸鹽化學概念………………………………………………………. 12 1-5 中孔洞分子篩形成機制………………………………………………. 13 1-6 官能基化中孔洞分子篩簡介…………………………………………. 16 1-6-1 修飾的方法……………………………………………………… 16 1-6-2 PMOs 的發展與簡介……………………………………………. 18 1-7 文獻回顧………………......................................................................... 20 1-7-1 含硫官能基中孔洞材料.………………………........................... 20 1-7-2 磺酸官能基中孔洞材料………………………............................ 23 1-8 研究動機與目的…………………………............................................. 29 第二章 實驗部分………………......................................................................... 30 2-1 藥品……………………......................................................................... 30 2-2 實驗步驟……………………................................................................. 31 2-2-1 合成界面活性劑 CTEABr……………………………………… 31 2-2-2 合成含雙硫官能基的 SBA-1 (S-S-X)…………………………. 31 2-2-3 合成含雙硫官能基的 SBA-1 (DS-Y)………………………….. 32 2-2-4 以溶劑萃取法移除 SBA-1 孔洞中的模板…………................. 32 2-3 實驗鑑定儀器…………………………………………………………. 33 2-4 鑑定儀器之原理………………………………………………………. 34 2-4-1 同步輻射光束線 (NSRRC Beam Line) ………………………... 34 2-4-2 X光粉末繞射 (Powder X-Ray Diffractometer, XRD) ……….. 36 2-4-3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定………………. 37 2-4-4 熱重分析儀 (Thermo Gravimetric Analyzer, TGA)……………. 41 2-4-5 元素分析(Elemental Analyzer, EA) …………………………….. 42 2-4-6 固態核磁共振 (Solid State NMR) ……………………………... 42 第三章 結果與討論. ……………….…………………...................................... 52 3-1 S-S-X 部分……..……………….…………………............................ 52 3-1-1 XRD…………………….…………………................................. 52 3-1-2 氮氣等溫吸脫附..........….…………………............................... 54 3-1-3 13C CP/MAS NMR………….………………….......................... 57 3-1-4 29Si MAS NMR……..……….…………………......................... 59 3-1-5 熱重分析……….………………….............................................. 62 3-1-6 元素分析…......……….………………….................................. 64 3-1-7 SEM……..................................................................................... 66 3-2 DS-Y 部分…….…….…………………............................................. 68 3-2-1 XRD……….….…………………............................................... 68 3-2-2 氮氣等溫吸脫附…………………............................................. 70 3-2-3 13C CP/MAS NMR ………………............................................. 74 3-2-4 29Si MAS NMR …….………….................................................. 76 3-2-5 熱重分析……………................................................................. 79 3-2-6 元素分析………………............................................................. 81 3-2-7 SEM…………............................................................................. 83 3-3 汞吸附實驗部分..................................................................................... 84 3-3-1 實驗步驟........................................................................................ 84 3-3-2 ICP-MS 之原理.......................................................................... 84 3-3-3 汞吸附數據................................................................................... 85 第四章 結論…………………………………………………………………… 89 參考文獻……………………………………………………………………….. 90

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