臺灣博碩士論文加值系統

本篇研究主要是使用 BTME (1,2-Bis(trimethoxysilyl)ethane)、TMOS (Tetramethyl orthosilicate) 與 MPTMS ((3-Mercaptopropyl)trimethoxy-
silane) 為共同矽源，以 C16TEABr (Cetyltriethylammonium bromide) 作為模板試劑，在酸性條件下直接合成含有硫基和乙烷有機官能基的 cubic(Pm3n) 中孔洞材料。經由粉末 X-ray 繞射圖譜和等溫氮氣吸脫附的數據，顯示出中孔洞材料的組成有均一的孔洞性質。其 MPTMS 和 BTME 可植入中孔結構中的最大量分別可達 20 ? 和 16 ?。且能在反應中加入過氧化氫試劑，將原本結構中的硫基官能基 (–CH2CH2CH2–SH) 同時行進一步的氧化反應，將硫基官能基氧化成磺酸官能基 (–CH2CH2CH2–SO3H)。最後使用粉末 X-ray 繞射、等溫氮氣吸脫附 (BET)、元素分析 (EA)、29Si 和 13C MAS-NMR、掃描電子顯微鏡 (SEM)、熱重分析儀 (TGA) 做鑑定。

The synthesis of a new class of sulfuric acid-functionalized ethane-bridged, mesoporous hybrid organosilicas is reported. Materials were synthesized by co-condensation of ethane-bridged organosilane (MeO)3SiCH2CH2Si(OMe)3 with 3-mercaptopropyltrimethoxysilane (MeO)3SiCH2CH2CH2SH in the presence of cetyltrimethylammonium bromide surfactant. Powder X-ray diffraction patterns and nitrogen sorption analysis reveal the formation of mesoporous material with uniform porosity. The maximum content of incorporated mercaptopropylsilane in the mesoporous framework obtained was 20 percentage. The thiol (–SH) moieties of mercaptopropyl groups that protrude into the pore channels are readily accessible for further oxidation. The surface moieties functionalized with propylsulfonic groups (–CH2CH2CH2–SO3H) were generated by the controlled oxidation of propylthiol surface groups using hydrogen peroxide. Further, the materials were characterized using elemental analysis (EA) , 29Si and 13C MAS-NMR, scanning electron microscopy (SEM) and TGA.

中文摘要…………………………………………………………… I

英文摘要…………………………………………………………… II

目錄………………………………………………………………… III

圖目錄……………………………………………………………… VI

表目錄……………………………………………………………… X

第一章 緒論……………………………………………………… 1
1-1 中孔洞分子篩的歷史與發展………………………………1
1-2 觸媒簡介……………………………………………………4
1-3 界面活性劑性質簡介………………………………………5
1-3.1 分子結構……………………………………………5
1-3.2 界面活性劑種類………………………………………7
1-3.3 微胞的簡介……………………………………………8
1-3.4 界面活性劑分子的排列………………………………9
1-4 中孔洞形成機制……………………………………………12
1-5 SBA-1 簡介…………………………………………………14
1-5.1 SBA-1 的形成機制…………………………………16
1-6 中孔洞分子篩表面修飾……………………………………17
第二章 文獻回顧……………………………………………………20
2-1 含有磺酸官能基之孔洞材料………………………………20
2-2 含有磺酸官能基孔洞材料之應用…………………………23
2-3 研究動機與目的……………………………………………26
第三章 實驗部分……………………………………………………27
3-1 藥品…………………………………………………………27
3-2 實驗步驟……………………………………………………28
3-2.1 合成界面活性劑C16TEABr…………………………28
3-2.2 合成含硫基和乙烷官能基的 SBA-1 (SH-PMO-SBA-1)……28
3-2.3 合成含磺酸根和乙烷官能基的SBA-1 (SO3H-PMO-SBA-1)29
3-2.4 以溶劑萃取法移除SH and SO3H-PMO-SBA-1孔洞中的模板 30
3-3 實驗設備……………………………………………………30
3-3.1 實驗合成設備………………………………………30
3-3.2 實驗鑑定儀器………………………………………31
3-4 鑑定儀器之原理……………………………………………31
3-4.1 同步輻射中心光束線 (NSRRC Beam Line)………31
3-4.2 X光粉末繞射 (Powder X-Ray Diffractometer；XRD)………32
3-4.3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定……………33
3-4.4 熱重分析儀 (Thermo Gravimetric Analyzer；TGA)…………38
3-4.5 固態核磁共振 (Solid State NMR)………………39
3-4.5.1 去氫偶合 (proton decoupling)……………39
3-4.5.2 魔角旋轉 (Magic Angle Spinning)………40
3-4.5.3交叉極化 (Cross-Polarization, CP)………41
3-4.6 低真空掃描式電子顯微鏡 (LV-SEM)………………42
3-4.7 元素分析儀 (Elemental Analyzer；EA)…………43
第四章　結果與討論…………………45
4-1 不同酸下合成的中孔洞材料 SH-PMO-SBA-1………………45
4-1.1 XRD 結果…………………………………………45
4-2 不同酸量下合成的中孔洞材料 SH-PMO-SBA-1…………48
4-2.1 XRD 結果……………………………………………48
4-3 BTME的量對合成孔洞材料 SH-PMO-SBA-1 的影響………50
4-3.1 XRD 結果……………………………………………50
4-4不同攪拌時間對合成中孔洞材料 SH-PMO-SBA-1 的影響……52
4-4.1 XRD 結果……………………………………………52
4-5不同水熱時間對合成中孔洞材料 SH-PMO-SBA-1 的影響…54
4-5.1 XRD 結果……………………………………………54
4-6不同反應溫度對合成中孔洞材料 SH-PMO-SBA-1 的影響……… 56
4-6.1 XRD 結果……………………………………56
4-7 在室溫下合成中孔洞材料 SH-PMO-SBA-1………………58
4-7.1 XRD 結果……………………………………58
4-8 在 273 K 下以鹽酸合成 SH-PMO-SBA-1…………………68
4-8.1 XRD 結果……………………………………………68
4-8.2 氮氣等溫吸脫附的結果……………………………71
4-8.3 13C CP/MAS NMR 結果……………………………74
4-8.4 29Si MAS NMR 結果………………………………76
4-8.5 實驗值與元素分析數據之比較……………………80
4-8.6 TGA 結果…………………………………………82
4-8.7 SEM 結果……………………………………………84
4-9 在 273 K 下以硫酸合成 SH-PMO-SBA-1………………86
4-9.1 XRD 結果……………………………………………86
4-9.2 氮氣等溫吸脫附的結果……………………………89
4-9.3 13C CP/MAS NMR 結果………………………92
4-10 在 273 K 下以鹽酸合成 SO3H-PMO-SBA-1……………94
4-10.1 XRD 結果……………………………………………94
4-10.2 氮氣等溫吸脫附的結果………………………………97
4-10.3 13C CP/MAS NMR 結果……………………………100
4-10.4 29Si MAS NMR 結果……………………………102
4-10.5 實驗值與元素分析數據之比較………………106
4-10.6 SEM 結果…………………………………………108
4-11 在 273 K 下以硫酸合成 SO3H-PMO-SBA-1……………110
4-11.1 XRD 結果…………………………………………110
4-11.2 氮氣等溫吸脫附的結果…………………………113
4-11.3 13C CP/MAS NMR 結果…………………………116
第五章 結論……………………………………………………118
參考文獻.…………………………119

1.McBain, J. N. “The Sorption of Gases and Vapors by Solids”, George
Rutledge and Sons Ltd., London, 1932.
2.Freude, D.; Hunger, M.; Pfeifer, H. Z. Phys. Chem. 1987, 152, 171.
3.(a) Yang, S. M.; Wu, S. T.; Chin, J. Am. Chem. Soc., 1988, 35, 141.
(b) Hedge, S.G.; Ratnasamy, P.; Kustov, L. M.; Kazansky, V. B. Zeolites, 1988, 8, 137.
(c) Davis, M. E.; Montes, C.; Garces, J. M. ACS symposium series, 1989, 399, 291.
4.(a) Kresge, C. T.; Leonowicz, M. E.; Roth, E. J.; Vartuli, J. C.; Beck, J. S. Nature, 1992, 359, 710-712.
(b) 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.; Schlenkert, J. L. J. Am. Chem. Soc. 1992, 114, 10834-10843.
5.(a) Busio, K.; Jänchen, J.; Van Hooff, J. H. C. Microporous Mater. 1995, 5, 211-218.
(b) Weglarski, J.; Datka, J.; He, H.; Klinowski, J. J. Chem. Soc. Faraday Trans. 1996, 92, 5161-5164.
(c) Kosslick, H.; Lischke, G.; Walther, G.; Storek, W.; Martin, A.; Fricke, R. Microporous Mater. 1997, 9, 13-33.
(d) Cheng, C.-F.; Klinowski, J. J. Chem. Soc. Faraday Trans. 1996, 92, 289-292.
(e) Luan, Z.; He, H.; Zhou, W; Cheng, C.-F.; Klinowski, J. J. Chem. Soc. Faraday Trans. 1995, 91, 2955-2959.
(f) Mokaya, R.; Jones, W. Chem. Commun., 1996, 983-984.
6.(a) Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G.D. Science. 1998, 279, 548-552.
(b) Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024-6036.
7.Pluronic poly(alkene oxide) triblock copolymers are trademarked products of BASF, Mt. Olive, NJ.
8.(a) Huo, Q.; Margolese, D. I.; Ciesla, U.; Feng, P.; Gier, T. E.; Sieger, P.; Leon, R.; Petroff, P. M.; Schüth, F.; Stucky, G. D. Nature. 1994, 368, 317-321.
(b) Chen, C.; Li, H.; Davis, M. E. Microporous Mater. 1993, 2, 17.
(c) Attard, G. S.; Glyde, J. C. Nature. 1995, 378, 366-368.
(d) Göltner, C. G.; Antonietti, M. Adv. Mater. 1997, 9, 431-436.
9.(a) Tanev, P. T.; Pinnavaia, T. J. Science. 1995, 267, 865-867.
(b) Bagshaw, S. A.; Prouzet, E.; Pinnavaia. T. J. Science. 1995, 269, 1242-1244.10. Tanford, C. “The Hydrophobic Effect: Formation of Micelles and Biological Membranes”, Wiley, New York, 1973.
10.(a) Prouzet, E.; Pinnavaia. T. J. Angew. Chem. Int. Ed.; 1997, 36, 516-518.
(b) Antonietti, M.; Göltner, C. G. Angew. Chem. Int. Ed.; 1997, 36, 910-928.
(c) Firouzi, A.; Atef, F.; Oertli, A. G.; Stucky, G. D.; Chmelka, B. F. J. Am. Chem. Soc. 1997, 119, 3596-3610.
11.(a) Imperor-Clerc, M.; Davidson, P.; Davidson, A. J. Am. Chem. Soc. 2000, 122, 11925-11933.
(b) Kruk, M.; Jaroniec, M.; Ko, C. H.; Ryoo, R. Chem. Mater.; 2000, 12, 1961-1968.
(c) Ryoo, R.; Ko, C. H.; Kruk, M.; Antochshuk, V.; Jaroniec, M. J. Phys. Chem. B. 2000, 104, 11465-11471.
(d) Ravikovitch, P. I.; Neimark, A. V. J. Phys. Chem. B. 2001, 105, 6817-6823.
12.Kim, J. M.; Sakamoto, Y.; Hwang, Y. K.; Kwon, Y.-U.; Terasaki, O.; Park, S.-E.; Stucky, G. D. J. Phys. Chem. B. 2002, 106, 2552-2558.
13. IUPAC. “Manual of Symbols and Serminology for Physicochemical Quantities and Units. Appendix II : Denitions, Terminology and Symbols in Colloid and Surface Chemistry part I”, Pure Appl. Chem., 1972, 31, 579.
14.Bond, G. C. ‘‘Heterogeneous Catalysis:Principles and Applications.’’ 2nd ed. Clarendon Press, Oxford, UK,1987.
15.Miessler, G. L.; Tarr, D.A. ‘‘Inorganic Chemistry’’ , 2nd ed, Prentice Hall, New York, 1999. pp. 498.
16.Satterfield, C. N. ‘‘Heterogeneous Catalysis in practice.’’, McGrew-Hill, New York, 1980.
17.Todros, T. F. “Surfactant”, Academic Press, London, 1984.
18.Holmerg, K.; Jönsson, B.; Kronberg, B.; Lindman, B. “Surfants and Polymers in Aqueous Solution” 2nd ed., John Wiley & Sons Ltd, England, 2003.
19.Israelachvili, J. N.; Mitchell, D. J.; Ninham, B. W. J. Chem. Soc. Faraday Trans. 1976, 72, 1525-1568.
20.Tanford, C. “The Hydrophobic Effect: Formation of Micelles and Biological Membranes”, Wiley, New York, 1973.
21.Evans, F. D.; Wennerstrom, H. “The Colloidal Domain”, 2nd Ed, VHC, New York, 1999.
22.Qi, L.; Ma, J.; Cheng, H.; Zhao, Z. “Colloids and Surfaces A”, 1996, 111, 195-202.
23.Firouzi, A.; Kumar, D.; Bull, L. M.; Besier,T.; Sieger, P.; Huo, Q.; Walker, S. A.; Zasadzinski, J. A.; Glinka, C.; Nicol, J.; Margolese, D.; Stucky, G. D.; Chmelka, G. F. Science. 1995, 267, 1138-1143.
24.Huo, Q.; Margolese, D. I.; Ciesla, U.; Feng, P.; Gier, T. E.; Sieger,P.; Leon, R.; Petroff, P. M.; Schüth, F.; Stucky, G. D. Nature. 1994, 368, 317-321.
25.Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.; Stucky, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 449-453.
26.Schubert, U.; Husing, N. Synthesis of inorganic materials, chapter 4 , Wiley-Interscience publications: New York, 2000.
27.Schierbaum, K. D.; Weiss, T.; Velzen, E. U. T. van; Engbersen, J. F. J.; Reinhoudt, D. N.; Gopel, W. Science. 1994, 265, 1413-1415.
28.Liu, J. Feng, X.; Fryxell, G. E.; Wang, L.-Q.; Kim. A. Y.; Gong, M. L. Adv. Meter. 1998, 10, 161-165.
29.Stein, A.; Melde, B. J.; Schroden, R. C. Adv. Meter. 2000, 12, 1403-1419.
30.Steel, A.; Carr, S. W.; Anderson, M. W. Chem. Mater. 1995, 7, 1829-1832.
31.Fowler, C. E.；Burkett, S. L.；Mann, S. Chem. Commun. 1997, 1769.
32.Juan A. Melero,* Rafael van Grieken, and Gabriel Morales. Chem. Rev. 2006, 106, 3790-3812.
33.(a) Van Rhijn, W. M.; De Vos, D. E.; Sels, B. F.; Bossaert, W. D.; Jacobs, P. A. Chem. Commun. 1998, 317.
(b) Lim, M. H.; Blanford, C. F.; Stein, A. Chem. Mater. 1998, 10, 467.
(c) Van Rhijn, W. M.; De Vos, D. E.; Bossaert, W. D.; Bullen, J.; Wouters, B.; Grobet, P.; Jacobs, P. A. Stud. Surf. Sci. Catal. 1998, 117, 183.
34.Margolese, D.; Melero, J. A.; Christiansen, S. C.; Chmelka, B. F.; Stucky, G. D. Chem. Mater. 2000, 12, 2448.
35.(a) Inagaki, S.; Guan, S.; Fukushima, Y.; Ohsuna, T.; Terasaki, O. J. Am. Chem. Soc. 1999, 121, 9611.
(b) Melde, B. J.; Holland, B. T.; Blandford, C. F.; Stein, A. Chem. Mater. 1999, 11, 3302.
36.Hamoudi, S. ; Kaliaguine, S. Microporous and Mesoporous Materirals 59 (2003) 195-204.
37.Mbaraka, I. K. ; Radu, D. R. ; Shanks, B. H. Journal of Catalysis 219 (2003) 329-336.
38.Lee, J. F. ; Cheng, S. F. Journal of Catalysis 223 (2004) 152-160.
39.Yang, Q. ; Liu, J. ; Yang, J. ; Mahendra, P. K. ; Shinji I. Journal of Catalysis 228 (2004) 265-272.
40.Shimizu, K. I. ; Eidai, H. ; Tsuyoshi H. ; Tatsuya, K. ; Tomoya, H. Journal of Catalysis 231 (2005) 131-138.
41.Liu, J. ; Yang, Q. ; Mahendra P. K. ; Norihiko, S. ; Shinji, I. ; Yang, J. ; Zhang, L. J. Phys. Chem. B. 2005, 109, 12250-12256.
42.Yang, L. M. ; Wang, Y. J. ; Luo, G. S. ; Dai, Y. Y. Microporous and Mesoporous Materirals 84 (2005) 275-282.
43.Kiyotaka, N. ; Ikuyoshi, T. ; Michikazu, H. ; Shigenobu, H. ; Kazunari, D. ; Junko, N. K. Catalysis Today 116 (2006) 151-156.
44.Reddy, S. S. ; David R. ; Kumar, V. S. ; Padmasri, A. H. ; Narayanan, S. ; Rama, K. S. Catalysis Communications 8 (2007) 261-266.
45.Yang,L.M. ; Wang,Y.J. ; Luo, F.S. ; Dai ,Y.Y. Micropor. and Mesopor. Mater. 2005, 84, 275-282.
46.Wang, J. ; Yu, N. ; Zheng, A. ; Yang, J. ; Wu, D. ; Sun, Y. ; Ye, C.; Deng, F. Micropor. and Mesopor. Mater. 2006, 89, 219-226.
47.Lan Zhao, Guangshan Zhu, Daliang Zhang, Yan Di, Yue Chen, Osamu Terasaki,† and Shilun Qiu*. J. Phys. Chem. B 2005, 109, 764-768.
48.Engelhardt, G.; Michel, D. “High-Resolution Solid-State NMR of Silicates and Zeolites”, John Wiley & Sons Inc, New York. 1988.
49.D. Margolese,† J. A. Melero,† S. C. Christiansen,§ B. F. Chmelka,‡,§ and G. D. Stucky*†, Chem. Mater. 2000, 12, 2448-2459.
50.Isabel D´ýaz, Federico Mohino, Joaqu´ýn Pérez-Pariente, Enrique Sastre. Thermochimica Acta 413 (2004) 201–207.
51.Hamoudi, S.; Kaliaguine, S. Micropor. and Mesopor. Mater. 2003, 59, 195-204.
52.S. Hamoudi, S. Kaliaguine *Microporous and Mesoporous Materials 59 (2003) 195–204.
53.國家同步輻射中心 (NSRRC), 新竹市, 台灣省
54.Lowe, I. J. Phys. Rev. Lett. 1959, 2, 285.
55.Pines, A.; Gibby, M. G.; Waugh, J. S. J.Chem.Phys. 1972, 56, 1776.
56.Cassiers,* K.; Van Der Voort, P. and Vansant, E. F. Chem. Commun., 2000, 2489–2490.