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研究生: 林興安
論文名稱: 功能性複合中孔洞材料的製備與應用
Preparation and Applications of Functional Nanocomposite Mesoporous Materials
指導教授: 楊家銘
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2007
畢業學年度: 95
語文別: 中文
論文頁數: 101
中文關鍵詞: 中孔洞二氧化矽微孔洞金奈米粒子一氧化碳氧化
外文關鍵詞: mesoporous silica materials, SBA-15, CO oxidation, cytochrome c
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  • 本篇論文主要是在製備新穎的多功能化中孔洞二氧化矽。我們應用硫酸處理法將中孔洞SBA-15的二氧化矽中孔洞開啟,進行中孔表面疏水化改質後,再以低溫鍛燒的方式將微孔開啟,形成中孔表面與微孔洞表面分別具有親水與疏水兩種不同性質的功能化SBA-15。論文第一部分中,我們將微孔表面修飾上雙鍵官能基,並使之進一步與鈀金屬鹽類形成錯合物,在經過高溫還原後,便在微孔中形成鈀金屬奈米粒子,我們並發現此奈米複合鈀催化劑可在不具有其它配位基的條件下催化Heck反應的進行。第二部分中,我們在不堵塞SBA-15的中孔洞的情形下,於微孔中嵌入氧化鈦、氧化鋅及氧化鐵三種不同金屬氧化物,再將金奈米粒子沉積在金屬氧化物上,而形成新穎的奈米金催化劑。我們發現無論是在含水氣或不含水氣的情況下進行一氧化碳氧化反應,這些樣品都具有極佳的催化活性。最後在第三部分中,我們在不堵塞中孔洞的情形下於微孔中嵌入氧化鐵,利用樣品中孔洞表面原本的疏水性質加上氧化鐵暴露於中孔洞表面所表現的表面性質等雙重作用,進行cytochrome c的吸附。我們發現此樣品表面的雙重作用能夠在接近中性pH (pH 6.5)的條件下增強對cytochrome c的吸附能力並達到最大吸附量。


    In this thesis, we report the preparations of novel multifunctional mesoporous silica materials. We apply the treatment of sulfuric acid to vacate the mesopores of mesoporous SBA-15 silica, followed by the surface functionalization of the mesopores to become hydrophobic. After low-temperature calcination to vacate the micropores, the resulting bifunctional SBA-15 silica has hydrophilic micropores as well as hydrophobic mesopores. In the first part of the thesis, we further graft the micropores with vinyl functional groups, which can then react with palladium salts and trap them in the micropores. After further reduction reaction, metallic palladium nanoparticles in the micropores of SBA-15 are formed. The palladium-containing nanocomposite catalyst show catalytic activity for the Heck reaction without any ligand present in the reaction mixture. In the second part, we selectively incorporate metal oxides, including titanium oxide, zinc oxide and iron oxide, into the micropores of SBA-15 without blocking the mesoporous channels, followed by the deposition of gold nanoparticles on the top of the metal oxides. The resulting novel gold nanocomposite catalysts are active for CO oxidation with or without the presence of moisture. Finally, the SBA-15-based nanocomposite with iron oxide in the micropores and hydrophobic mesopores is applied for cytochrome c adsorption. We find that the novel adsorbent with double surface interactions can achieve the highest adsorption amount near neutral pH condition (pH 6.5).

    中文摘要 Ⅰ 英文摘要 Ⅱ 目錄 Ⅲ 圖目錄 Ⅶ 表目錄 ⅩⅠ 第一章 緒論 1-1 中孔洞二氧化矽簡介紹 1 1-2 界面活性劑簡介 2 1-3 中孔洞二氧化矽MCM-41合成機制 5 1-4 合成機制比較 7 1-5 中孔洞二氧化矽SBA-15合成機制 9 1-6 中孔洞二氧化矽SBA-15有機模板移除 10 1-7 表面修飾與嵌入化學 1-7-1 表面修飾 11 1-7-2 嵌入化學 14 1-8 奈米金觸媒(nanogold catalysts)簡介 16 1-9 研究動機 19 第二章 實驗部分 2-1 實驗藥品 22 2-2 合成步驟 24 2-2-1-1 合成態SBA-15 24 2-2-1-2 合成態SBA-15硫酸處理 24 2-2-1-3 SBA-15中孔的表面功能化反應 25 2-2-1-4 SBA-15微孔洞表面功能化反應 25 2-2-1-5 SBA-15微孔洞嵌入金屬反應 25 2-2-1-6 Heck reaction 26 2-2-2-1 合成態SBA-15 28 2-2-2-2 合成態SBA-15硫酸處理 28 2-2-2-3 SBA-15中孔的表面功能化反應 28 2-2-2-4 SBA-15移除聚乙烯氧反應 29 2-2-2-5 SBA-15微孔洞嵌入金屬反應 29 2-2-2-6 沉積沉澱法製備金奈米粒子 30 2-2-2-7 一氧化碳氧化反應 32 2-2-3-1 合成態SBA-15 33 2-2-3-2 合成態SBA-15硫酸處理 33 2-2-3-3 SBA-15中孔的表面功能化反應 33 2-2-3-4 SBA-15移除聚乙烯氧反應 34 2-2-2-5 SBA-15微孔洞嵌入氧化鐵金屬反應 34 2-2-2-6 Cytochrome c 吸附測試 34 2-3 實驗鑑定儀器 2-3-1 X光粉末繞射儀 36 2-3-2 氮氣等溫吸脫附分析儀 39 2-3-3 液態核磁共振光譜儀 44 2-3-4 固態核磁共振光譜儀 45 2-3-5 分析式穿透式電子顯微鏡 47 2-3-6 掃描穿透式電子顯微鏡 48 2-3-7 感應耦合電漿質譜分析儀 49 2-3-8 紫外光/可見光分光光譜儀 50 第三章 結果與討論 3-1 在功能化SBA-15的微孔洞嵌入鈀金屬簡介 51 3-1-1 粉末繞射與氮氣物理吸附鑑定 52 3-1-2 13C與29Si固態核磁共振光譜鑑定 57 3-1-3 掃描穿透式電子顯微鏡與感應耦合電漿質譜鑑定 61 3-1-4 一氧化碳化學吸附鑑定 62 3-1-5 Heck reaction反應測試 64 3-2 以功能化SBA-15製備新穎奈米金催化劑簡介 65 3-2-1 粉末繞射與氮氣物理吸附鑑定 67 3-2-2 13C與29Si固態核磁共振光譜鑑定 76 3-2-3 穿透式與掃描穿透式電子顯微鏡 與感應耦合電漿質譜鑑定 78 3-2-4 一氧化碳氧化反應 82 3-3 官能化的中孔洞SBA-15在微孔洞嵌入氧化鐵金屬簡介 88 3-3-1 以樣品E-Fe吸附Cytochrome c測試 89 第四章 結論 93 參考文獻 96

    1. Schüth, F.; Ciesla, U. Microporous. Mesoporous. Mater. 1999, 27, 131.
    2. Hayward, R. C.; Henning, P. A.; Chmelka B. F.; Stucky, G. D. Microporous. Mesoporous. Mater. 2001, 44, 619.
    3. Marlow, F.; McGehee, M. D.; Zhao, D.; Chmelka, B. F.; Stucky, G. D. Adv. Mater 1999, 11, 632.
    4. Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature 1992, 359, 710.
    5. Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt, K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834.
    6. Stockholm and Lund, 1997 , Surfactant and Poltmers in Aqueous
    solution
    7. Evans, D. Fennell. The colloidal domain. VCH: Wiley,New York, 1999.
    8. Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024.
    9. Hoffmann, F.; Cornelius, M.; Morell, J.; Fröba, M. Angew. Chem. Int. Ed. 2006, 45, 3216.
    10. Attard, G. S.; Glyde, J. C.; Göltner, C. G. Nature 1995, 378, 366.
    11. Monnier, A.; SchEth, F.; Huo, Q.; Kumar, D.; Margolese, D.;
    Maxwell, R. S.; Stucky, G.; Krishnamurty, M.; Petroff, P.; Firouzi, A.; Janicke, M.; Chmelka, B. Science 1993, 261, 1299.
    12. Inagaki, S.; Fukushima, Y.; Kuroda, K. Chem. Commum. 1993, 680.
    13. Huo, Q.; Margolese, D. I.; Ciesla, U.; Feng, P.; Gier, T. E.; Sieger, P.;
    Leon, R.; Petroff, P. M.; SchEth, F.; Stucky, G. D. Nature 1994, 368, 317.
    14. Huo, Q.; Margolese, D. I.; Ciesla, U.; Demuth, D. G.; Feng, P.;
    Gier, T. E.; Sieger, P.; Firouzi, A.; Chmelka, B. F.; Scheth, F.; Stucky, G. D. Chem. Mater. 1994, 6, 1176.
    15. (a) Pileni, M. P. Pure Appl. Chem. 2000, 72, 53. (b) Toshima, N.
    Pure Appl. Chem. 2000, 72, 317. (c) Selvan, S. T.; Spatz, J. P.; Klok,
    H.; Möller, M. Adv. Mater. 1998, 10, 132. (d) Bronstein, L.; Kramer,
    E.; Berton, B.; Burger, C.; Forster S.; Antonietti, M. Chem. Mater. 1999, 11, 1402.
    16. Nagy, J. B.; Hannus, I.; Kiricsi, I. In Nanoparticles and Nanostructured Films; Fendler, J. H., Ed.; Wiley-VCH: Weinheim, 1998; p 389.
    17. Dresco, P. A.; Zaitsev, V. S.; Gambino, R. J.; Chu, B. Langmuir 1999, 15, 1945.
    18. Alivisastos, A. P. Science 1996, 271, 933.
    19. (a) Schmidt-Winkel, P.; Lukens, W. W., Jr.; Zhao, D.; Yang, P.;
    Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1999, 121, 254.
    (b) Lettow, J. S.; Han, Y. J.; Schmidt-Winkel, P.; Yang, P.; Zhao,
    D.; Stucky, G. D.; Ying, J. Y. Langmuir 2002, 16, 8291.
    20. (a) Kim, S. S.; Pauly, T. R.; Pinnavaia, T. J. Chem. Commun.
    2000, 1661. (b) Kim, S. S.; Karkambar, A.; Pinnavaia, T. J.; Kruk,
    M.; Jaroniec, M. J. Phys. Chem. B, 2001, 105, 7663.
    21. (a) Flodstrom, K.; Teixeira, C. V.; Amenitsch, H.; Alfredsson, V.;
    Linden, M. Langmuir 2004, 20, 4885. (b) Flodstrom, K.;
    Wennerstrom, H.; Alfredsson, V. Langmuir 2004, 20, 680. (c)
    Flodstrom, K.; Wennerstrom, H.; Teixeira, C. V.; Amenitsch, H.;
    Linden, M.; Alfredsson, V. Langmuir 2004, 20, 10311.
    22. (a) Ruthstein, S.; Frydman, V.; Kababya, S.; Goldfarb, D. J. Phys.
    Chem. B 2003, 107, 1739. (b) Ruthstein, S.; Frydman, V.;
    Goldfarb, D. J. Phys. Chem. B 2004, 108, 9016.
    23. (a) Kleitz, F.; Schmidt, W.; Schüth, F. Microporous. Mesoporous.
    Mater. 2003, 65, 1.(b) Tian, B.; Liu, X.; Yu, C.; Gao, F.; Luo, Q.; Xie, S.; Tu, B.; Zhao,D. Chem. Commun. 2002, 1186.(c) Yang, C-M.; Zibrowius, B.; Schmidt, W.; Schüth, F. Chem. Mater. 2003, 15, 3739.
    24. (a) Zhao, D.; Yang, P.; Melosh, N.; Feng, J.; Chmelka, B. F.; Stucky, G. D. Adv. Mater. 1998, 10, 1380. (b) Yang, P.; Zhao, D.; Chmelka, B. F.; Stucky, G. D. Chem. Mater. 1998, 10, 2033. (c)Zhao, D.; Sun, J. Y.; Li, Q. Z.; Stucky, G. D. Chem. Mater. 2000, 12, 275. (d) Feng, P. Y.; Bu, X. H.; Stucky, G. D.; Pine, D. J. J. Am. Chem. Soc. 2000, 122, 994.
    25. Hayward, R. C.; Henning, P. A.; Chmelka B. F.; Stucky, G. D. Microporous. Mesoporous. Mater. 2001, 44, 619.
    26. Yang, C. M.; Zibrowius, B.; Schmidt, W.; Schüth, F. Chem. Mater. 2004, 16, 2918.
    27. Hayward, R. C.; Henning, P. A.; Chmelka B. F.; Stucky, G. D. Microporous. Mesoporous. Mater. 2001, 44, 619.
    28. Yuranov, I.; Moeckli, P.; Suvorova, E.; Buffat, P.; Kiwi-Minsker, L.; Renken, A. J. Mol.Catal, 2003, 239-251.
    29. Fryxell, G. E. Inorg. Chem. Commun. 2006, 9, 1141.
    30. (a)Long, R.; Yang, R.T. Catal. Lett. 1998, 52, 91.(b) Xia, Q.-H.; Hidajat, K.; Kawi, S. Catal. Today, 2001, 68, 255.
    31. (a) Magnoux, P.; Lavaud, N.; Guisnet, M. Top. Catal. 2000, 13,
    291. (b) Shirai, M.; Suzuki, N.; Nishiyama, Y.; Torii, K.; Arai, M. Appl. Catal. A 1999, 177, 219.
    32. (a) Fukuoka, A.; Higashimoto, N.; Sakamoto, Y.; Sasaki, M.;
    Sugimoto, N.; Inagaki, S.; Fukushima, Y.; Ichikawa, M. Catal. Today 2001, 66, 23.(b) Paetzold, E.; Oehme, G.; Fuhrmann, H.; Richter, M.; Eckelt, R.; Pohl, M.M.; Kosslick, H. Microporous. Mesoporous. Mater. 2001, 517.
    33. (a) Lee, K.B.; Lee, S.M.; Cheon, J. Adv. Mater. 2001, 13, 517.(b) Mehnert, C.P.; Ying, J.Y. Chem. Commun. 1998, 20, 2215.
    34. Bond, G. C.; Sermon, P. A. Gold Bull. 1973, 6, 102.
    35. Bond, G. C.; Sermon, P. A. J. C. S. Chem. Comm. 1973, 444.
    36. Cha, D.Y.; Parravano, G. J. Catal. 1970, 18, 200.
    37. Galvano, S.; Parravano, G. J. Catal, 1978, 55, 178.
    38. Haruta, H. Catech. 2002, 6, 102.
    39. Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115, 301.
    40. Haruta, M.; Tsubota, S.; Kobayashi, T.; Kageyama, H.; Genet, M. J.; Delmon, B. J. Catal. 1993, 144, 175.
    41. Cant, N. W.; Hull, W. K. J. Phys. Chem. B 1971, 75, 2914.
    42. Mingos, D. M. P. J. Chem. Soc. Dalton Trans 1996, 561.
    43. Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. J. Catal. 1989, 115, 301.
    44. Kobayashi, T.; Haruta, M.; Tsubota, S.; Sano, H. Sensors and Actuators, B1 1990, 222.
    45. Tsubota, S.; Haruta, M.; Kobayashi, T.; Ueda, A.; Nakahara, Y.
    Stud. Surf.Sci.Catal., 1991, 63, 695.
    46. (a) Okumura, M.; Tanaka, K.; Ueda, A.; Haruta, M. Solid State Ionics 1997, 95, 143.(b) Okumura, M.; Tsubota, S.; Iwamoto, M.; Haruta, M. Chem. Lett. 1998, 315.
    47. Haruta, M.; Daté, M. Applied Catalysis A 2001, 222, 427.
    48. Schubert, M. M.; Hackenberg, D.; Veen, A. C.; Muhler, M.; Plzak, V.; Behm, R. J. J. Catal. 2001, 179, 113.
    49. Yuranov, I.; Kiwi-Minsker, L.; Buffat,P.; Renken, A. Chem. Mater. 2004, 16, 760.
    50. (a) Yang, C. M.; Liu, P. H.; Ho, Y. F.; Chiu, C. Y.; Chao, K. J. Chem.
    Mater. 2003, 15, 275.(b) Niederer, J. P. M.; Arnold, A. B. J.; Holderich, W. F.; Spliethof, B.; Tesche, B.; Reetz, M.; Bonnemann, H. Top. Catal. 2002, 18, 265. (c) Zhang, Z. T.; Dai, S.; Blom, D. A.; Shen, J. Chem. Mater. 2002, 14, 965.(d) Yuranov, I.; Moeckli, P.; Suvorova, E.; Buffat, P.; Kiwi-Minsker, L.; Renken, A. J. Mol. Catal. A Chem. 2003, 192, 239.
    51. Galureau, A.; Cambon, H.; Di Renzo, F.; Ryoo, R.; Choi, M.; Fajula, F. New J. Chem. 2003, 27, 73.
    52. Dat, M.; Okumura, M.; Tsubota, S.; Haruta, S. Angew. Chem. Int. Ed. 2004, 43, 2129.
    53. Klibanov, A. M. Science 1983, 219, 719.
    54. Weetall, H. H. Appl. Biochem. Biotechnol. 1993, 41, 157.
    55. Docoslis, A.; Wu, W.; Giese, R. F., Van Oss, C. J. Colloids Surf. B 1999, 13, 83.
    56. Malmsten, M. J. Colloid Interface Sci. 1994, 166, 333.
    57. Jo¨nsson, U.; Ivarsson, B.; Lundström, I.; Berghem, L. J. Colloid
    Interface Sci. 1982, 90, 148.
    58. (a) Diaz, J. F.; Balkus, K. J. Jr. J. Mol. Catal. B: Enzymatic 1996,
    2, 115.(b) Washmon-Kriel, L.; Jimenez, V. L.; Balkus, K. J. Jr. J. Mol.Catal. B Enzymatic 2000, 10, 453.
    59. (a) Takahashi, H.; Li, B.; Sasaki, T.; Miyazaki, C.; Kajino, T.;
    Inagaki, S. Microporous. Mesoporous. Mater. 2001, 44-45, 755. (b)
    Takahashi, H.; Li, B.; Sasaki, T.; Miyazaki, C.; Kajino, T.; Inagaki, S.
    Chem. Mater. 2000, 12, 3301.
    60. Eggleston, C. M.; Khare, N.; Lovelace, D. M. J. Electron Spectrosc
    -opy and Related Phenomena. 2006, 150, 220.
    61. (a) Sen, A.; Lai, T. W. J. Am. Chem. Soc. 1981, 103, 4627. (b) Sen, A. Acc. Chem. Res. 1988, 21, 421. (c) Hahn, C.; Morvillo, P.; Vitagliano, A. Eur. J. Inorg. Chem. 2001, 419.
    62. (a)Cameron, D.; Holliday, R.; Thompson, D. J. Power Sorrces. 2003, 118, 298.(b)Costello, C. K.; Kung, M. C.; Oh, H.-S.; Wang, Y.; Kung, H. H.; Appl. Catal. A 2002, 232, 159.
    63. Daniells, S. T.; Makkee, M.; Moulijn, J. A. Catal. Lett. 2005, 100, 39.

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