本研究利用具有橢圓截面孔道之中孔洞二氧化矽MMT-1做為載體，在中孔洞表面進行選擇性功能化及附載鈀奈米顆粒，並將之應用於催化苯酚選擇性氫化反應。由於合成MMT-1所使用的陽離子型界面活性劑cetyltrimethylammonium bromide (C16H33N(CH3)3Br, CTAB)與非離子型界面活性劑tetraethylene glycol dodecyl ether (C12H25(OCH2CH2)4OH, C12EO4)在孔洞內的分佈不均，兩者與孔壁的作用力亦不同，因此我們得以氯仿先萃取出作用力較弱的C12EO4，並將暴露出的表面以及材料外表面嫁接trimethylsilyl (-Si(CH3)3, TMS)官能基，再萃取出剩餘的CTAB，並以dimethylsilyl (-SiH(CH3)2, DMS)或trivinylsilyl (-Si(CHCH2)3, TVS)官能基修飾所暴露的表面，達成在MMT-1中進行選擇性功能化的目的。TMS官能基可在孔洞內形成較疏水的環境，有利於疏水分子在孔道中的擴散，而鈀金屬的附載可藉由以下兩種策略達成，第一個策略是使用具有還原力的DMS官能基將Pd(II)直接還原成鈀奈米顆粒，第二種則是利用TVS官能基與Pd(II)形成π鍵結錯合物，再將之還原。在苯酚的選擇性氫化反應中，選擇性嫁接TMS及TVS官能基並附載鈀奈米顆粒的MMT-1在水相、常壓氫氣(1 atm)及室溫(25℃)的反應條件下，可達到極高的苯酚轉化率(99%)與環己酮選擇率(98%)，且在此反應條件下回收觸媒並重複反應十次，其苯酚轉化率(73%)與環己酮選擇率(98%)仍有不錯的表現。相較於商用Pd/C以及附載於隨機嫁接TMS及TVS官能基的MMT-1(或MCM-41)或內表面未功能化的MMT-1的鈀催化劑，使用選擇性嫁接TMS及TVS官能基並附載鈀奈米顆粒的MMT-1有最高的反應催化活性。

摘要 I
目錄 III
圖目錄 VII
表目錄 XII
第一章 緒論 1
1-1 中孔洞二氧化矽材料 1
1-2 孔洞形貌與結構的調控 6
1-3 Mesoporous Material from Tsing-Hua, MMT-1 10
1-4 中孔洞二氧化矽於催化的應用 18
1-4-1 中孔洞二氧化矽表面修飾有機官能基 19
1-4-2 中孔洞二氧化矽附載貴金屬 22
1-4-3 苯酚的選擇性氫化反應 25
1-5 研究動機與目的 30
第二章 實驗部分 32
2-1 實驗藥品 32
2-2 樣品命名 34
2-3 合成MMT-1及MCM-41 36
2-4 萃取界面活性劑 36
2-4-1 氯仿選擇性萃取C12EO4 36
2-4-2 HMDS/氯仿選擇性萃取及嫁接TMS官能基 36
2-4-3 NH4NO3/乙醇萃取 37
2-4-4 HCl/乙醇萃取 37
2-5 嫁接有機官能基 37
2-5-1 嫁接DMS官能基 37
2-5-2 嫁接TVS官能基 38
2-5-3 MMT-1 (或MCM-41)外表面嫁接TMS官能基 38
2-5-4 MMT-1 (或MCM-41)同時嫁接TMS及TVS官能基 39
2-6 附載鈀金屬 39
2-6-1 嫁接DMS官能基的MMT-1附載鈀金屬 39
2-6-2 嫁接TVS官能基的MMT-1 (或MCM-41)附載鈀金屬 40
2-6-3 內表面未功能化的MMT-1附載鈀金屬 40
2-7 苯酚的選擇性氫化反應 41
2-8 儀器鑑定與分析 42
2-8-1 X光粉末繞射光譜(Powder X-Ray Diffraction, PXRD) 42
2-8-2 熱重分析(Thermogravimetry Analysis, TGA) 44
2-8-3 液態核磁共振光譜(Liquid State Nuclear Magnetic Resonance Spectroscopy, Liquid state NMR) 44
2-8-4 固態核磁共振光譜(Solid State Nuclear Magnetic Resonance Spectroscopy, Solid state NMR) 45
2-8-5 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 46
2-8-6 掃描穿透式電子顯微鏡(Field Emission Scanning Transmission Electron Microscope, FE-STEM) 47
2-8-7 氮氣物理吸脫附(N2 Physical Adsorption) 48
2-8-8 感應耦合電漿質譜分析(Inductively Coupled Plasma-Mass Spectroscopy, ICP-MS) 52
2-8-9 氣相層析(Gas Chromatography, GC) 53
2-8-10 X光光電子能譜(X-ray Photoelectron Spectroscopy, XPS) 53
2-8-11 元素分析(Elemental Analysis, EA) 54
第三章 結果與討論 55
3-1 MMT-1界面活性劑的去除 55
3-2 選擇性嫁接TMS及DMS官能基並附載鈀金屬的MMT-1 64
3-2-1 NMR鑑定 65
3-2-2 X光粉末繞射與氮氣物理吸脫附鑑定 67
3-2-3 穿透式電子顯微鏡鑑定 69
3-3 選擇性嫁接TMS及TVS官能基並附載鈀金屬的MMT-1 71
3-3-1 NMR鑑定 72
3-3-2 X光粉末繞射與氮氣物理吸脫附鑑定 74
3-3-3 穿透式電子顯微鏡與感應耦合電漿質譜鑑定 77
3-4 苯酚的選擇性氫化反應 79
3-4-1 對照樣品的製備與鑑定-隨機嫁接TMS及TVS官能基並附載鈀金屬的MMT-1(及MCM-41) 79
3-4-2 對照樣品的製備與鑑定-內表面未功能化的MMT-1附載鈀金屬 84
3-4-3 苯酚的選擇性氫化反應結果 87
第四章 結論 93
第五章 參考文獻 95

1. U. Ciesla and F. Schüth, Microporous Mesoporous Mater., 1999, 27, 131-149.
2. T. Yanagisawa, T. Shimizu, K. Kuroda and C. Kato, Bull. Chem. Soc. Jpn., 1990, 63, 988-992.
3. C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature, 1992, 359, 710-712.
4. J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D. Schmitt, C. T. W. Chu, D. H. Olson and E. W. Sheppard, J. Am. Chem. Soc., 1992, 114, 10834-10843.
5. R. Schmidt, E. W. Hansen, M. Stoecker, D. Akporiaye and O. H. Ellestad, J. Am. Chem. Soc., 1995, 117, 4049-4056.
6. N. K. Raman, M. T. Anderson and C. J. Brinker, Chem. Mater., 1996, 8, 1682-1701.
7. Q. Huo, D. I. Margolese, U. Ciesla, P. Feng, T. E. Gier, P. Sieger, R. Leon, P. M. Petroff, F. Schuth and G. D. Stucky, Nature, 1994, 368, 317-321.
8. F. Hoffmann, M. Cornelius, J. Morell and M. Fröba, Angew. Chem. Int. Ed., 2006, 45, 3216-3251.
9. C.-Y. Chen, H.-X. Li and M. E. Davis, Microporous Mater., 1993, 2, 17-26.
10. C.-Y. Chen, S. L. Burkett, H.-X. Li and M. E. Davis, Microporous Mater., 1993, 2, 27-34.
11. A. Firouzi, F. Atef, A. G. Oertli, G. D. Stucky and B. F. Chmelka, J. Am. Chem. Soc., 1997, 119, 3596-3610.
12. Q. Huo, D. I. Margolese, U. Ciesla, D. G. Demuth, P. Feng, T. E. Gier, P. Sieger, A. Firouzi and B. F. Chmelka, Chem. Mater., 1994, 6, 1176-1191.
13. A. Monnier, F. Schüth, Q. Huo, D. Kumar, D. Margolese, R. S. Maxwell, G. D. Stucky, M. Krishnamurty, P. Petroff, A. Firouzi, M. Janicke and B. F. Chmelka, Science, 1993, 261, 1299-1303.
14. B. Lindman and H. Wennerström, in Micelles, Springer Berlin Heidelberg, 1980, vol. 87, pp. 1-83.
15. J. N. Israelachvili, D. J. Mitchell and B. W. Ninham, J. Chem. Soc., Faraday Trans. 2, 1976, 72, 1525-1568.
16. G. J. d. A. A. Soler-Illia, C. Sanchez, B. Lebeau and J. Patarin, Chem. Rev., 2002, 102, 4093-4138.
17. M. D. Ward and M. J. Horner, CrystEngComm, 2004, 6, 401-407.
18. R. Ryoo, S. H. Joo and J. M. Kim, J. Phys. Chem. B, 1999, 103, 7435-7440.
19. S. Gustafsson, P.-O. Quist and B. Halle, Liq. Cryst., 1995, 18, 545-553.
20. H. Hagslätt, O. Söderman and B. Jönsson, Liq. Cryst., 1992, 12, 667-688.
21. C.-M. Yang, C.-Y. Lin, Y. Sakamoto, W.-C. Huang and L.-L. Chang, Chem. Commun., 2008, 5969-5971.
22. H. Qiu, Y. Sakamoto, O. Terasaki and S. Che, Adv. Mater., 2008, 20, 425-429.
23. J. E. Haskouri, S. Cabrera, M. Caldés, C. Guillem, J. Latorre, A. Beltrán, D. Beltrán, M. D. Marcos and P. Amorós, Chem. Mater., 2002, 14, 2637-2643.
24. D. Zhao, Q. Huo, J. Feng, J. Kim, Y. Han and G. D. Stucky, Chem. Mater., 1999, 11, 2668-2672.
25. P. Kékicheff and B. Cabane, J. Phys. France, 1987, 48, 1571-1583.
26. S. Alpérine, Y. Hendrikx and J. Charvolin, J. Physique Lett., 1985, 46, 27-31.
27. W.-C. Huang, L.-L. Chang, Y. Sakamoto, C.-Y. Lin, N.-C. Lai and C.-M. Yang, RSC Adv., 2011, 1, 229-237.
28. A. Taguchi and F. Schüth, Microporous Mesoporous Mater., 2005, 77, 1-45.
29. R. J. White, R. Luque, V. L. Budarin, J. H. Clark and D. J. Macquarrie, Chem. Soc. Rev., 2009, 38, 481-494.
30. A. Barau, V. Budarin, A. Caragheorgheopol, R. Luque, D. Macquarrie, A. Prelle, V. Teodorescu and M. Zaharescu, Catal. Lett., 2008, 124, 204-214.
31. J. Demel, Sujandi, S.-E. Park, J. Čejka and P. Štěpnička, J. Mol. Catal. A: Chem., 2009, 302, 28-35.
32. W. Long, N. A. Brunelli, S. A. Didas, E. W. Ping and C. W. Jones, ACS Catal., 2013, 3, 1700-1708.
33. C.-M. Yang, H.-A. Lin, B. Zibrowius, B. Spliethoff, F. Schüth, S.-C. Liou, M.-W. Chu and C.-H. Chen, Chem. Mater., 2007, 19, 3205-3211.
34. C. Hahn, P. Morvillo and A. Vitagliano, Eur. J. Inorg. Chem., 2001, 2001, 419-429.
35. A. Sen, Acc. Chem. Res., 1988, 21, 421-428.
36. A. Sen and T.-W. Lai, J. Am. Chem. Soc., 1981, 103, 4627-4629.
37. A. Dedieu, Chem. Rev., 2000, 100, 543-600.
38. U. Schuchardt, D. Cardoso, R. Sercheli, R. Pereira, R. S. da Cruz, M. C. Guerreiro, D. Mandelli, E. V. Spinacé and E. L. Pires, Appl. Catal. A: Gen., 2001, 211, 1-17.
39. H. Li, J. Liu, S. Xie, M. Qiao, W. Dai, Y. Lu and H. Li, Adv. Funct. Mater., 2008, 18, 3235-3241.
40. M. Chatterjee, H. Kawanami, M. Sato, A. Chatterjee, T. Yokoyama and T. Suzuki, Adv. Synth. Catal., 2009, 351, 1912-1924.
41. N. Mahata and V. Vishwanathan, J. Catal., 2000, 196, 262-270.
42. P. Claus, H. Berndt, C. Mohr, J. Radnik, E.-J. Shin and M. A. Keane, J. Catal., 2000, 192, 88-97.
43. N. Mahata, K. V. Raghavan and V. Vishwanathan, Appl. Catal. A: Gen., 1999, 182, 183-187.
44. G. Neri, A. M. Visco, A. Donato, C. Milone, M. Malentacchi and G. Gubitosa, Appl. Catal. A: Gen., 1994, 110, 49-59.
45. S. Velu, M. P. Kapoor, S. Inagaki and K. Suzuki, Appl. Catal. A: Gen., 2003, 245, 317-331.
46. H. Liu, T. Jiang, B. Han, S. Liang and Y. Zhou, Science, 2009, 326, 1250-1252.
47. Y. Pérez, M. Fajardo and A. Corma, Catal. Commun., 2011, 12, 1071-1074.
48. J. Matos and A. Corma, in Appl. Catal. A: Gen., 2011, vol. 404, pp. 103-112.
49. C. M. Cirtiu, A. F. Dunlop-Briere and A. Moores, Green Chem., 2011, 13, 288-291.
50. P. Makowski, R. Demir Cakan, M. Antonietti, F. Goettmann and M.-M. Titirici, Chem. Commun., 2008, 999-1001.
51. Y. Wang, J. Yao, H. Li, D. Su and M. Antonietti, J. Am. Chem. Soc., 2011, 133, 2362-2365.
52. H. Liu, Y. Li, R. Luque and H. Jiang, Adv. Synth. Catal., 2011, 353, 3107-3113.
53. Z. Li, J. Liu, C. Xia and F. Li, ACS Catal., 2013, 3, 2440-2448.
54. J.-F. Zhu, G.-H. Tao, H.-Y. Liu, L. He, Q.-H. Sun and H.-C. Liu, Green Chem., 2014, 16, 2664.
55. V. Z. Fridman and A. A. Davydov, J. Catal., 2000, 195, 20-30.
56. N. Lang and A. Tuel, Chem. Mater., 2004, 16, 1961-1966.
57. R. Boukherroub, C. Chatgilialoglu and G. Manuel, Organometallics, 1996, 15, 1508-1510.
58. J. Trébosc, J. W. Wiench, S. Huh, V. S. Y. Lin and M. Pruski, J. Am. Chem. Soc., 2005, 127, 3057-3068.
59. N. Yilmaz, M. Mizukami and K. Kurihara, Langmuir, 2007, 23, 6070-6075.
60. C. H. Rochester and D.-A. Trebilco, J. Chem. Soc., Faraday Trans. 1, 1978, 74, 1137-1145.