請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/69213
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬(Soofin Cheng) | |
dc.contributor.author | Yu-Cheng Lin | en |
dc.contributor.author | 林禹丞 | zh_TW |
dc.date.accessioned | 2021-06-17T03:10:42Z | - |
dc.date.available | 2021-07-19 | |
dc.date.copyright | 2018-07-19 | |
dc.date.issued | 2018 | |
dc.date.submitted | 2018-07-18 | |
dc.identifier.citation | 1. Davis, M. E., Nature 2002, 417 (6891), 813-821.
2. Tatsumi, T.; Nakamura, M.; Negishi, S.; Tominaga, H.-o., Journal of the Chemical Society, Chemical Communications 1990, (6), 476-477. 3. Wu, P.; Liu, Y.; He, M.; Tatsumi, T., Journal of Catalysis 2004, 228 (1), 183-191. 4. 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., Journal of the American Chemical Society 1992, 114 (27), 10834-10843. 5. Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S., Nature 1992, 359 (6397), 710-712. 6. Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D., Science 1998, 279 (5350), 548-552. 7. Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D., Journal of the American Chemical Society 1998, 120 (24), 6024-6036. 8. Zhang, F.; Yan, Y.; Yang, H.; Meng, Y.; Yu, C.; Tu, B.; Zhao, D., The Journal of Physical Chemistry B 2005, 109 (18), 8723-8732. 9. Sun, J.; Zhang, H.; Tian, R.; Ma, D.; Bao, X.; Su, D. S.; Zou, H., Chemical Communications 2006, (12), 1322-1324. 10. Chen, S.-Y.; Lee, J.-F.; Cheng, S., Journal of Catalysis 2010, 270 (1), 196-205. 11. Chen, S.-Y.; Tang, C.-Y.; Lee, J.-F.; Jang, L.-Y.; Tatsumi, T.; Cheng, S., Journal of Materials Chemistry 2011, 21 (7), 2255-2265. 12. Hiyoshi, N.; Yogo, K.; Yashima, T., Microporous and Mesoporous Materials 2005, 84 (1–3), 357-365. 13. Das, D.; Lee, J.-F.; Cheng, S., Journal of Catalysis 2004, 223 (1), 152-160. 14. Melero, J. A.; van Grieken, R.; Morales, G., Chemical Reviews 2006, 106 (9), 3790-3812. 15. Chen, C.-C.; Cheng, S.; Jang, L.-Y., Microporous and Mesoporous Materials 2008, 109 (1–3), 258-270. 16. Dufaud, V.; Davis, M. E., Journal of the American Chemical Society 2003, 125 (31), 9403-9413. 17. Davis, M. E.; Lobo, R. F., Chemistry of Materials 1992, 4 (4), 756-768. 18. Kleitz, F., Dissertation for the Doctoral Degree. Germany: der Ruhr-Universität Bochum 2002. 19. Lehn, J.-M., Science 1985, 227 (4689), 849-856. 20. Lindén, M.; Schacht, S.; Schüth, F.; Steel, A.; Unger, K. K., Journal of Porous Materials 1998, 5 (3), 177-193. 21. Raman, N. K.; Anderson, M. T.; Brinker, C. J., Chemistry of Materials 1996, 8 (8), 1682-1701. 22. Huo, Q.; Margolese, D. I.; Ciesla, U.; Feng, P.; Gier, T. E.; Sieger, P.; Leon, R.; Petroff, P. M.; Schuth, F.; Stucky, G. D., Nature 1994, 368 (6469), 317-321. 23. Huo, Q.; Margolese, D. I.; Ciesla, U.; Demuth, D. G.; Feng, P.; Gier, T. E.; Sieger, P.; Firouzi, A.; Chmelka, B. F., Chemistry of Materials 1994, 6 (8), 1176-1191. 24. Huo, Q.; Margolese, D. I.; Stucky, G. D., Chemistry of Materials 1996, 8 (5), 1147-1160. 25. Khushalani, D.; Kuperman, A.; Ozin, G. A.; Tanaka, K.; Coombs, N.; Olken, M. M.; Garcés, J., Advanced Materials 1995, 7 (10), 842-846. 26. Firouzi, A.; Kumar, D.; Bull, L.; Besier, T.; Sieger, P.; Huo, Q.; Walker, S.; Zasadzinski, J.; Glinka, C.; Nicol, J.; et, a., Science 1995, 267 (5201), 1138-1143. 27. Huo, Q.; Leon, R.; Petroff, P. M.; Stucky, G. D., Science 1995, 268 (5215), 1324-1327. 28. Chen, C.-Y.; Burkett, S. L.; Li, H.-X.; Davis, M. E., Microporous Materials 1993, 2 (1), 27-34. 29. Ruthstein, S.; Schmidt, J.; Kesselman, E.; Talmon, Y.; Goldfarb, D., Journal of the American Chemical Society 2006, 128 (10), 3366-3374. 30. Chiker, F.; Nogier, J. P.; Launay, F.; Bonardet, J. L., Applied Catalysis A: General 2003, 243 (2), 309-321. 31. Hoffmann, F.; Cornelius, M.; Morell, J.; Fröba, M., Angewandte Chemie International Edition 2006, 45 (20), 3216-3251. 32. Loy, D. A.; Shea, K. J., Chemical Reviews 1995, 95 (5), 1431-1442. 33. Shea, K. J.; Loy, D. A., Chemistry of Materials 2001, 13 (10), 3306-3319. 34. Melde, B. J.; Holland, B. T.; Blanford, C. F.; Stein, A., Chemistry of Materials 1999, 11 (11), 3302-3308. 35. Inagaki, S.; Guan, S.; Fukushima, Y.; Ohsuna, T.; Terasaki, O., Journal of the American Chemical Society 1999, 121 (41), 9611-9614. 36. Asefa, T.; MacLachlan, M. J.; Coombs, N.; Ozin, G. A., Nature 1999, 402 (6764), 867-871. 37. Hönicke, D.; Födisch, R.; Claus, P.; Olson, M. In Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA: 2000. 38. Moffett, R. B. In Organic Syntheses, John Wiley & Sons, Inc.: 2003. 39. Bruson, H. A.; Riener, T. W., Journal of the American Chemical Society 1945, 67 (5), 723-728. 40. Talwalkar, S.; Kumbhar, P.; Mahajani, S., Industrial & Engineering Chemistry Research 2006, 45 (24), 8024-8028. 41. Okazaki, S.; Harada, H., Chemistry Letters 1988, 17 (8), 1313-1316. 42. Maw-Ling Wang, Y. U. M.; Tsuan-Hsuan Huang, Y. U. M.; Wen-Teng, W., Chemical Engineering Communications 2004, 191 (1), 27-46. 43. Gao, R.; Zhu, Q.; Dai, W.-L.; Fan, K., RSC Advances 2012, 2 (14), 6087-6093. 44. Lin, S.-K.; March, J., Molecules 2001, 6 (12), 1064. 45. Vogt, E. T. C.; Whiting, G. T.; Dutta Chowdhury, A.; Weckhuysen, B. M. In Advances in Catalysis, Friederike, C. J., Ed. Academic Press: 2015; Vol. Volume 58, pp 143-314. 46. Nemeth, L.; Bare, S. R. In Advances in Catalysis, Friederike, C. J., Ed. Academic Press: 2014; Vol. Volume 57, pp 1-97. 47. Gallo, E.; Lamberti, C.; Glatzel, P., Physical Chemistry Chemical Physics 2011, 13 (43), 19409-19419. 48. Huybrechts, D. R. C.; Vaesen, I.; Li, H. X.; Jacobs, P. A., Catalysis Letters 1991, 8 (2), 237-244. 49. Clerici, M. G.; Ingallina, P., Journal of Catalysis 1993, 140 (1), 71-83. 50. Liu, Z.; Crumbaugh, G. M.; Davis, R. J., Journal of Catalysis 1996, 159 (1), 83-89. 51. Wu, P.; Tatsumi, T.; Komatsu, T.; Yashima, T., Journal of Catalysis 2001, 202 (2), 245-255. 52. Corma, A.; Navarro, M. T.; Pariente, J. P., Journal of the Chemical Society, Chemical Communications 1994, (2), 147-148. 53. Chen, L. Y.; Chuah, G. K.; Jaenicke, S., Catalysis Letters 1998, 50 (1), 107-114. 54. Bérubé, F.; Kleitz, F.; Kaliaguine, S., The Journal of Physical Chemistry C 2008, 112 (37), 14403-14411. 55. Wu, S.; Han, Y.; Zou, Y.-C.; Song, J.-W.; Zhao, L.; Di, Y.; Liu, S.-Z.; Xiao, F.-S., Chemistry of Materials 2004, 16 (3), 486-492. 56. Zhang, W.-H.; Lu, J.; Han, B.; Li, M.; Xiu, J.; Ying, P.; Li, C., Chemistry of Materials 2002, 14 (8), 3413-3421. 57. Chen, Y.; Huang, Y.; Xiu, J.; Han, X.; Bao, X., Applied Catalysis A: General 2004, 273 (1–2), 185-191. 58. Kuo, F.-T.; Chen, S.-Y.; Lin, T.-H.; Lee, J.-F.; Cheng, S., RSC Advances 2013, 3 (31), 12604-12610. 59. Bérubé, F.; Nohair, B.; Kleitz, F.; Kaliaguine, S., Chemistry of Materials 2010, 22 (6), 1988-2000. 60. Hua, Z.; Bu, W.; Lian, Y.; Chen, H.; Li, L.; Zhang, L.; Li, C.; Shi, J., Journal of Materials Chemistry 2005, 15 (6), 661-665. 61. Morey, M. S.; O'Brien, S.; Schwarz, S.; Stucky, G. D., Chemistry of Materials 2000, 12 (4), 898-911. 62. Pérez, Y.; Quintanilla, D. P.; Fajardo, M.; Sierra, I.; del Hierro, I., Journal of Molecular Catalysis A: Chemical 2007, 271 (1–2), 227-237. 63. Aronson, B. J.; Blanford, C. F.; Stein, A., Chemistry of Materials 1997, 9 (12), 2842-2851. 64. Capel-Sanchez, M. C.; Blanco-Brieva, G.; Campos-Martin, J. M.; de Frutos, M. P.; Wen, W.; Rodriguez, J. A.; Fierro, J. L. G., Langmuir 2009, 25 (12), 7148-7155. 65. Bruson, H. A.; Riener, T. W., Journal of the American Chemical Society 1945, 67 (5), 723-728. 66. Kasei, H., Jpn. Patent Kokai 55-19205, 56-59723. 67. Talwalkar, S.; Kumbhar, P.; Mahajani, S., Catalysis Communications 2006, 7 (9), 717-720. 68. Corma, A., Chemical Reviews 1997, 97 (6), 2373-2420. 69. Wróblewska, A.; Makuch, E.; Sokalska, E.; Malko, M., Reaction Kinetics, Mechanisms and Catalysis 2014, 113 (2), 519-542. 70. Wróblewska, A., Molecules 2014, 19 (12), 19907. 71. Wróblewska, A.; Makuch, E., Regeneration of the Ti-SBA-15 Catalyst Used in the Process of Allyl Alcohol Epoxidation with Hydrogen Peroxide. In Journal of Advanced Oxidation Technologies, 2014; Vol. 17, p 44. 72. Walcarius, A.; Delacôte, C., Chemistry of Materials 2003, 15 (22), 4181-4192. 73. J. Macquarrie, D.; B. Jackson, D., Chemical Communications 1997, (18), 1781-1782. 74. Chen, S.-Y.; Yokoi, T.; Tang, C.-Y.; Jang, L.-Y.; Tatsumi, T.; Chan, J. C. C.; Cheng, S., Green Chemistry 2011, 13 (10), 2920-2930. 75. Yap, N.; Andres, R. P.; Delgass, W. N., Journal of Catalysis 2004, 226 (1), 156-170. 76. Blasco, T.; Corma, A.; Navarro, M. T.; Pariente, J. P., Journal of Catalysis 1995, 156 (1), 65-74. 77. Chen, S.-Y.; Tang, C.-Y.; Chuang, W.-T.; Lee, J.-J.; Tsai, Y.-L.; Chan, J. C. C.; Lin, C.-Y.; Liu, Y.-C.; Cheng, S., Chemistry of Materials 2008, 20 (12), 3906-3916. 78. Geobaldo, F.; Bordiga, S.; Zecchina, A.; Giamello, E.; Leofanti, G.; Petrini, G., Catalysis Letters 1992, 16 (1), 109-115. 79. Lin, Y.-C.; Huang, Y.-W.; Sung, K.-H.; Lin, T.-H.; Cheng, S., Journal of Industrial and Engineering Chemistry 2016, 44, 60-66. 80. Taramasso, M.; Perego, G.; Notari, B., 1983. 81. Wróblewska, A.; Wajzberg, J.; Milchert, E., Epoxidation of 1-butene-3-ol with Hydrogen Peroxide under Autogenic and Atmospheric Pressure. In Journal of Advanced Oxidation Technologies, 2007; Vol. 10, p 316. 82. Sheldon, R. A.; Wallau, M.; Arends, I. W. C. E.; Schuchardt, U., Accounts of Chemical Research 1998, 31 (8), 485-493. 83. Huybrechts, D. R. C.; Bruycker, L. D.; Jacobs, P. A., Nature 1990, 345 (6272), 240-242. 84. Notari, B., Catalysis Today 1993, 18 (2), 163-172. 85. Wu, P.; Tatsumi, T.; Komatsu, T.; Yashima, T., Chemistry Letters 2000, (7), 774-775. 86. Fan, W.; Wu, P.; Namba, S.; Tatsumi, T., Angewandte Chemie International Edition 2004, 43 (2), 236-240. 87. Newalkar, B. L.; Olanrewaju, J.; Komarneni, S., Chemistry of Materials 2001, 13 (2), 552-557. 88. Lin, K.; Pescarmona, P. P.; Houthoofd, K.; Liang, D.; Van Tendeloo, G.; Jacobs, P. A., Journal of Catalysis 2009, 263 (1), 75-82. 89. Yokoi, T.; Karouji, T.; Ohta, S.; Kondo, J. N.; Tatsumi, T., Chemistry of Materials 2010, 22 (13), 3900-3908. 90. Davies, L. J.; McMorn, P.; Bethell, D.; Page, P. C. B.; King, F.; Hancock, F. E.; Hutchings, G. J., Journal of Catalysis 2001, 198 (2), 319-327. 91. Wróblewska, A.; Makuch, E., Reaction Kinetics, Mechanisms and Catalysis 2012, 105 (2), 451-468. 92. Cozzolino, M.; Di Serio, M.; Tesser, R.; Santacesaria, E., Applied Catalysis A: General 2007, 325 (2), 256-262. 93. Guidotti, M.; Gavrilova, E.; Galarneau, A.; Coq, B.; Psaro, R.; Ravasio, N., Green Chemistry 2011, 13 (7), 1806-1811. 94. Maschmeyer, T.; Rey, F.; Sankar, G.; Thomas, J. M., Nature 1995, 378, 159. 95. Chang, C.-C.; Jin, F.; Jang, L.-Y.; Lee, J.-F.; Cheng, S., Catalysis Science & Technology 2016, 6 (20), 7631-7642. 96. Chang, C.-C.; Lee, J.-F.; Cheng, S., Journal of Materials Chemistry A 2017, 5 (30), 15676-15687. 97. Bhattacharjee, S.; Anderson, J. A., Journal of Molecular Catalysis a-Chemical 2006, 249 (1-2), 103-110. 98. Gao, R. H.; Zhu, Q. J.; Dai, W. L.; Fan, K. N., Rsc Advances 2012, 2 (14), 6087-6093. 99. Tschan, M. J. L.; Thomas, C. M.; Strub, H.; Carpentier, J. F., Advanced Synthesis & Catalysis 2009, 351 (14-15), 2496-2504. 100. Behr, A.; Levikov, D.; Vogelsang, D., Journal of Molecular Catalysis A: Chemical 2015, 406, 114-117. 101. Lin, Y. C.; Huang, Y. W.; Sung, K. H.; Lin, T. H.; Cheng, S., Journal of Industrial and Engineering Chemistry 2016, 44, 60-66. 102. Asouti, A.; Hadjiarapoglou, L. P., Tetrahedron Letters 2000, 41 (4), 539-542. 103. Blasco, T.; Camblor, M. A.; Corma, A.; Perez-Pariente, J., Journal of the American Chemical Society 1993, 115 (25), 11806-11813. 104. Zuo, Y.; Liu, M.; Zhang, T.; Hong, L.; Guo, X.; Song, C.; Chen, Y.; Zhu, P.; Jaye, C.; Fischer, D., RSC Advances 2015, 5 (23), 17897-17904. 105. Reichardt, C.; Welton, T. In Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA: 2010; pp 425-508. 106. Cabaret, D.; Joly, Y.; Renevier, H.; Natoli, C. R., Journal of Synchrotron Radiation 1999, 6 (3), 258-260. 107. Huang, C.-H.; Gu, D.; Zhao, D.; Doong, R.-A., Chemistry of Materials 2010, 22 (5), 1760-1767. 108. Jin, F.; Chen, S. Y.; Jang, L. Y.; Lee, J. F.; Cheng, S. F., Journal of Catalysis 2014, 319, 247-257. 109. Chen, S. Y.; Tang, C. Y.; Lee, J. F.; Jang, L. Y.; Tatsumi, T.; Cheng, S., Journal of Materials Chemistry 2011, 21 (7), 2255-2265. 110. Chen, H.-J.; Wang, L.; Chiu, W.-Y., Materials Chemistry and Physics 2007, 101 (1), 12-19. 111. Fraile, J. M.; Garcia, J. I.; Mayoral, J. A.; Vispe, E.; Brown, D. R.; Naderi, M., Chemical Communications 2001, (16), 1510-1511. 112. Wang, S.; Yang, Q.; Wu, Z.; Li, M.; Lu, J.; Tan, Z.; Li, C., Journal of Molecular Catalysis A: Chemical 2001, 172 (1–2), 219-225. 113. Jiménez-Lozano, P.; Skobelev, I. Y.; Kholdeeva, O. A.; Poblet, J. M.; Carbó, J. J., Inorganic Chemistry 2016, 55 (12), 6080-6084. 114. Moliner, M.; Corma, A., Microporous and Mesoporous Materials 2014, 189, 31-40. 115. Khoury, P. R.; Goddard, J. D.; Tam, W., Tetrahedron 2004, 60 (37), 8103-8112. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/69213 | - |
dc.description.abstract | 基於有限的石油蘊藏量及人類大量的取用下,原油供應日益短缺,油價隨政治與社會環境變化而波動,整個石化產業的成本增加。因此,石化產品的高值化是目前石油化學工業非常重要的發展方向。而在石油精煉的過程,會產生大量低沸點的五碳化合物之衍生物,例如:環戊二烯。環戊二烯在常溫會經由 Diels-Alder reaction 自行聚合生成二聚體-雙環戊二烯。
本研究開發官能化二氧化矽材料做為雙環戊二烯衍生物之觸媒,生成具有較高經濟價值的雙環戊二烯醇以及雙環戊二烯環氧化物。第一部分著重在使用具有磺酸官能基之短隧道大孔徑之介孔二氧化矽材料當作固態酸觸媒,催化雙環戊二烯水解反應,生成具有較高經濟價值的雙環戊二烯醇。與傳統的勻相催化相比,發現使用固體酸觸媒催化反應時可獲得較高的雙環戊二烯醇選擇率,並可有效的減少雙環戊二烯在強酸催化條件下自身聚合成無法利用的寡聚物。之後更進一步對反應的幾個變因做最佳化調控,包括:雙環戊二烯/水的比例、反應溫度與觸媒用量,並評估觸媒重複使用性,發現在過量水的條件下,不加入共溶劑可以得到較高的雙環戊二烯轉化率及雙環戊二烯一醇產率,成功開發出有效的觸媒催化雙環戊二烯的水解反應以生成雙環戊二烯一醇。 第二部分則是著重在開發能將雙環戊二烯轉化為雙環戊二烯之環氧基衍生物的固體觸媒,而嵌入二氧化矽骨架結構,呈四配位的鈦離子被發現是催化選擇性氧化反應的活性位置,故含鈦之介孔二氧化矽材料為主要的開發目標。所製備的含鈦介孔材料利用X光繞射圖譜鑑定其結構,利用氮氣吸脫附圖檢測其孔洞性質,利用紫外-可見光光譜鑑定鈦離子的配位數,利用元素分析確認Ti(IV)離子含量。在所有合成之含鈦介孔材料中,發現利用一步合成法合成的Ti-MCM-41能最有效的將雙環戊二烯轉化為雙環戊二烯雙環氧化物,之後探討了不同的反應條件與觸媒用量及試劑比例,發現以第三丁基過氧化氫(TBHP)做為氧化劑在反應溫度95oC下反應5小時之後,產率可高達85%以上,後續並測試了觸媒的重複使用性,並且評估觸媒材料及催化製程之工業化可行性。 含鈦介孔材料中,由於SBA-15介孔二氧化矽必須在酸性的環境下進行合成,使用一步法合成Ti-SBA-15會因為鈦離子在酸性下溶解而只能將少量的鈦離子嵌入在二氧化矽結構內,導致催化反應性不佳。改採用後修飾法,發現利用正丁醇作為嫁接溶劑可將鈦離子分散嫁接在材料SBA-15的表面上,得到高活性的Ti-SBA-15,由紫外-可見光光譜確認鈦離子主要的配位環境為四配位,而使用常見的甲苯作為嫁接溶劑時則會得到六配位為主的配位環境。在發現這一現象之後,我們合成了不同鈦/矽莫耳比例的Ti-SBA-15,以環己烯以及雙環戊二烯的環氧化反應作為觸媒的活性測試比較,探討不同的鈦離子前驅物對觸媒活性的影響,最後發現7%Ti-SBA-15的活性最高,可得到最好的轉化率以及產率,並可有效的回收重覆使用。催化結果與紫外-可見光光譜的鑑定結果一致,確定四配位的Ti(IV)為催化活性位置。 | zh_TW |
dc.description.abstract | Cyclopentadiene (CPD) and dicyclopentadiene (DCPD) are commercially obtained from coal tar and by steam cracking of Naphtha. DCPD is formed by dimerization of CPD via a Diels–Alder reaction, and can be used as a monomer in polymerization reactions, either in olefin polymerization or in ring-opening metathesis polymerization. As the global oil supply and crude oil price are markedly affected by geo-political events and natural disasters, value-added products of raw petrochemical materials are urgently developed worldwide. Among them, the oxygen containing derivatives, like alcohols, epoxides, and ketones of DCPD have attracted the researchers.
The purpose of this research is to incorporate functional groups on mesoporous silica materials in order to use as the recyclable catalysts in preparing oxygen-containing derivatives of DCPD. Mesoporous silica materials of ordered pores were chosen because their relatively large pores facilitate the diffusion of bulky molecules. The first part of this research focused on using sulfonic acid-functionalized SBA-15 materials (SA-SBA-15) to catalyze the hydration of DCPD. The target product, cydecanol (DCPD-OH) has been used as a modifier for polyester or alkyd resin. Propylsulfonic acid functionalized SBA-15 with medium acidic strength was found to be more efficient than the silica gel counterpart or arylsulfonic acid functionalized material in catalyzing DCPD hydration to yield DCPD-OH. The second part focused on using titanium incorporated mesoporous silica to catalyze the epoxidation of DCPD. The target product is DCPD diepoxide. Among all the catalysts prepared, Ti-incorporated MCM-41 prepared by one-pot co-condensation show the highest activity in DCPD epoxidation using tert-butyl hydroperoxide (TBHP) as oxidant. In the effort of preparing Ti-incorporated SBA-15 (Ti-SBA-15), one-pot co-condensation can only incorporate very small amount of Ti(IV) due to the dissolution of TiO2 under acidic synthesis environment of SBA-15. The third part of this research focused on the preparation of Ti-SBA-15 by grafting with titanium alkoxides. Using 1-butanol as the solvent was found to give better dispersion of Ti(IV) than using toluene. The DR UV-vis spectra revealed that Ti(IV) species grafted on SBA-15 were mainly in tetrahedral coordination. Epoxidation of cyclohexene using tert-butyl hydroperoxide as oxidant was chosen to test the catalytic activity. Among Ti-SBA-15 catalysts prepared, 7%Ti-SBA-15 gave the highest cyclohexene conversion and epoxide yield, and the catalyst was fully recyclable. The catalytic activity was in consistence with the results of DR UV-vis spectra, inferring that Ti(IV) species in tetrahedral coordination are the active centers for catalytic epoxidation of olefins. | en |
dc.description.provenance | Made available in DSpace on 2021-06-17T03:10:42Z (GMT). No. of bitstreams: 1 ntu-107-R04223161-1.pdf: 3408126 bytes, checksum: 275b207ee355a7f75c39977b67a2a441 (MD5) Previous issue date: 2018 | en |
dc.description.tableofcontents | 謝誌 i
摘要 ii Abstract iv 目錄 vi 圖目錄 ix 表目錄 xiii Chapter 1 Introduction 1 1-1 Background of Microporous and Mesoporous Materials 1 1-2 Formation Mechanism of Mesoporous Silica Materials 2 1-2-1 Template-assisted synthesis 2 1-2-2 Surfactant packing 5 1-2-3 Interactions between Inorganic Components and the Surfactants. 6 1-2-4 Mechanisms of Mesoporous Silica Materials Formation 8 1-3 Functionalization of Mesoporous Materials 10 1-3-1 Grafting process (Postsynthetic Functionalization) 11 1-3-2 Co-Condensation process (Direct Synthesis) 12 1-3-3 Preparation of Periodic Mesoporous Organosilicas (PMOs) 13 1-4 DCPD and Its Derivatives 13 1-5 Epoxidation of Olefins Catalyzes by Ti-Catalyst 16 1-6 Ti-incorporated Mesoporous Materials 19 1-7 Purpose and Motivation 21 Chapter 2 Reagents and Characterization Methods 23 2-1 Reagents 23 2-2 Characterization of Catalysts 25 2-2-1 Powder X-ray diffraction 25 2-2-2 Nitrogen physisorption 26 2-2-3 Inductively-coupled plasma-mass spectrometry 26 2-2-4 Electron Probe X-Ray Microanalyzer (EPMA) 26 2-2-5 Diffuse-reflectance UV-Vis spectroscopy 27 2-2-6 Thermogravimetric Analysis (TGA) 28 2-2-7 Infrared spectroscopy (IR) 28 2-2-8 Gas chromatography / Gas chromatography–mass spectrometry (GC-MS) 28 Chapter 3 Hydration of DCPD using Sulfonic Acid Functionalized SBA-15 as Catalyst 30 3-1 Backgrounds 30 3-2 Experimental 32 3-2-1 Preparation of Sulfonic Acid Functionalized SBA-15 Materials 32 3-2-2 Characterization 34 3-2-3 Catalytic reaction 35 3-3 Results and Discussion 37 3-3-1 Catalyst Characteriztion 37 3-3-2 Reactant and product analysis 39 3-3-3 Catalytic results without co-solvents 42 3-3-4 Catalytic results with co-solvents 46 3-3-5 Recycling of the SA-SBA-15 catalyst 47 3-4 Summary 49 Chapter 4 Epoxidation of DCPD using Titanium Incorporated Silica as Catalyst 50 4-1 Backgrounds 50 4-2 Experimental 51 4-2-1 Preparation of Titanium Incorporated Slica Materials 51 4-2-2 Characterization 54 4-2-3 Catalytic reaction 55 4-3 Results and Discussion 56 4-3-1 Characterization of Titanium Incorporated Silica Materials 56 4-3-2 Catalyst test 67 4-3-3 Optimization of Reaction Condition 72 4-3-4 Catalyst Reuse 75 4-4 Summary 77 Chapter 5 Importance of Solvents in Preparing Highly Active Ti-SBA-15 for Epoxidation Catalysts by Grafting Method 78 5-1 Backgrounds 78 5-2 Experimental 80 5-2-1 Preparation of Titanium Incorporated SBA-15 Materials 80 5-2-2 Characterization 81 5-2-3 Catalytic reaction 82 5-3 Results and Discussion 83 5-3-1 Influence of Ti/Si atomic ratio on grafting Ti(IV) onto SBA-15 83 5-3-2 Influence of Ti grafting agents on the structure of Ti(IV) in SBA-15 88 5-3-3 Influence of solvent on grafting Ti(IV) onto SBA-15 91 5-3-4 Turbidity studies of TBOT in different solvents 94 5-3-5 Catalytic performance of Ti-SBA-15 materials 98 5-3-6 Recycling of Ti-SBA-15 catalysts 104 5-4 Summary 106 Chapter 6 Conclusions 107 References 109 | |
dc.language.iso | en | |
dc.title | 官能化介孔二氧化矽材料作為雙環戊二烯衍生物合成之觸媒的開發與研究 | zh_TW |
dc.title | Functionalized Mesoporous Silica as Catalysts for the Preparation of DCPD Derivatives | en |
dc.type | Thesis | |
dc.date.schoolyear | 106-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 邱靜雯,蔡蘊明,萬本儒 | |
dc.subject.keyword | 雙環戊二烯,固態酸觸媒,環氧化,含鈦介孔觸媒, | zh_TW |
dc.subject.keyword | DCPD,solid acid catalyst,functionalized SBA-15,Ti-SBA-15,Ti-MCM-41, | en |
dc.relation.page | 113 | |
dc.identifier.doi | 10.6342/NTU201801601 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2018-07-18 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-107-1.pdf 目前未授權公開取用 | 3.33 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。