Title page for 962203021


[Back to Results | New Search]

Student Number 962203021
Author Chia-Chun Kao(高佳駿)
Author's Email Address No Public.
Statistics This thesis had been viewed 1050 times. Download 609 times.
Department Chemistry
Year 2008
Semester 2
Degree Master
Type of Document Master's Thesis
Language zh-TW.Big5 Chinese
Title Synthesis and Characterization of Mesoporous Silicas With Benzen bridging, amine and phosphonic acid groups
Date of Defense 2009-07-03
Page Count 129
Keyword
  • amine
  • Benzen
  • Mesoporous
  • phosphonic
  • Abstract The thesis is divided into three parts. Studies on functionalization of mesoporous materials. In part one, the mesoporous silica SBA-1 (cubic Pm3n symmetry) functionalized with phenyl groups were synthesized via co-condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) and tetraethoxysilane (TEOS) under acidic conditions using cetyltriethylammonium bromide (CTEABr) as a structure-directing agent. By optimizing the synthesis composition, the resulting materials exhibited much higher surface areas (up to 1210 m2/g) and larger pore volumes (up to 0.64 cm3/g) as compared to the previous analogue, which only exhibited a surface area of 381 cm2/g and a pore volume of 0.11 cm3/g. Two dimensional (2D) 29Si{1H} heteronuclear correlation (HETCOR) NMR spectra, acquired as a function of contact time, provided direct spectroscopic evidence that a single mesophase with various Q (from TEOS) and T silicon species (from BTEB) located randomly within the pore walls via co-condensation of BTEB and TEOS at a molecular level. Such information is often not achievable by other characterization techniques
    In part two, well-ordered cubic mesoporous silica SBA-1 functionalized with amino functional groups have been synthesized via co-condensation of tetraethoxysilane (TEOS), (3-aminopropyl)trimethoxysilane (APTMS) templated by cetyltriethylammonium bromide (CTEABr), under strongly acidic condition by using chlorosulfonic acid as an acidic medium. The materials thus obtained were characterized by a variety of techniques including X-ray diffraction (XRD), solid state 13C and 29Si NMR spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption measurements. Direct NMR evidence for the amine functional groups in close proximity to the Q3 SiOH species in amino-functionalized mesoporous silica SBA-1 is provided by two-dimensional 29Si{1H} HETCOR-based NMR.
    In the third part, highly ordered SBA-15 mesoporous silica contains phosphonic acid groups are synthesized via co-condensation of tetraethylorthosilicate (TEOS) and diethylphosphatoethyltriethoxysilane (PETES) using Pluronic 123 (P123) as a structure-directing agent under acidic conditions. The presence of functional group in th resultant material are confirmed by 29Si{31P} REDOR NMR study.
    Table of Content 中文摘要………………………………………………………………………...I
    英文摘要………………………………………………………………………...III
    目錄……………………………………………………………………………...V
    圖目錄…………………………………………………………………………...VIII
    表目錄…………………………………………………………………………...XI
    第一章 序論…………………………………………………………………….1
    1-1 中孔洞分子篩的歷史與發展………………………………………….1
    1-2 中孔洞分子篩 SBA 系列簡介………………………………………..3
    1-3 SBA-1 形成機制……………………………………………………….6
    1-4 界面活性劑性質簡介………………………………………………….7
    1-5 中孔洞分子篩的應用……………………………….…………………11
    1-6 文獻回顧……………………………………………………………….13
    1-6-1 含苯環官能基之 PMO 材料…………………………………...13
    1-6-2 含胺基官能基之孔洞材料………………………………………16
    1-6-3 含磷酸官能基之孔洞材料………………………………………19
    1-7 研究動機與目的……………………………………………………….21
    第二章 實驗部份……………………………………………………………….22
    2-1 藥品……………………………………………………………………. 22
    2-2 實驗步驟……………………………………………………………….23
    2-2-1 合成界面活性劑 CTEABr………………………………………23
    2-2-2 合成含苯環官能基的 SBA-1 (BTEB-SBA-1) …………………24
    2-2-3 合成含胺基官能基的 SBA-1 (NH2-SBA-1) ……………….......24
    2-2-4 以溶劑萃取法移除具苯環及具胺基官能基之 SBA-1材料孔洞中的模板……………………………………………………………...
    25
    2-2-5 中孔洞材料 NH2-SBA-1 酸鹼滴定實驗………………………25
    2-2-6 中孔洞材料 NH2-SBA-1 酸化實驗…………………………....25
    2-2-7 合成含磷酸官能基的SBA-15 (PO3H2-SBA-15) ………………25
    2-2-8 以濃硫酸移除 SBA-15 孔洞中的模板…………………….......26
    2-2-9 濃鹽酸水解 PO3H2-SBA-15 實驗……………………...............26
    2-3 實驗設備……………………………………………………………….27
    2-4 鑑定儀器……………………………………………………….28
    2-4-1 同步輻射光束線…………………………………………………28
    2-4-2 X 射線粉末繞射 (Powder X-Ray Diffractometer) …………...29
    2-4-3 氮氣吸脫附等溫曲線、表面積與孔洞特性鑑定………………30
    2-4-4 熱重分析(Thermo Gravimetric Analyzer;TGA) ……………32
    2-4-5 元素分析(Elemental Analyzer;EA) ………………………..33
    2-4-6 固態核磁共振 (Solid State NMR) ……………………………...34
    2-5固態核磁共振光譜技術介紹……………………………………...........35
    2-5-1 去耦合 (decoupling) 作用……………………………………....39
    2-5-2 魔角旋轉 (magic angle spinning,MAS) …………………….....39
    2-5-3 29Si MAS NMR 光譜……………………………………..........40
    2-5-4 1H MAS NMR 光譜……………………………………............41
    2-5-5 交叉極化 (Cross Polarization, CP) ……………………............41
    2-5-6 2D HETCOR (Heteronuclear Correlation) 實驗……….............42
    2-5-7 2D Exchange 實驗……………………………………..............44
    2-5-8 REDOR (Rotational-Echo Double resonance) 實驗...................45
    第三章 結果與討論. ……………….…………………......................................48
    3-1 BTEB-SBA-1……..……………….…………………..........................48
    3-1-1 界面活性劑比例…………………….…………………...............48
    3-1-2 BTEB-SBA-1 系列 XRD..........….…………………................50
    3-1-3 氮氣等溫吸脫附……………….………………….......................52
    3-1-4 13C CP/MAS NMR……..……….…………………....................55
    3-1-5 29Si MAS NMR……..……….………………….........................57
    3-1-6 熱重分析……….…………………...............................................60
    3-1-7 1H MAS NMR…......……….…………………...........................62
    3-1-8 29Si {1H} HETCOR NMR 實驗結果分析……..........................63
    3-1-9 2D 1H-1H Homonuclear Correlation MAS NMR (exchange experiment) ……….………………….....................................................
    67
    3-2 NH2-SBA-1…….…….………………….............................................70
    3-2-1 XRD……….….…………………...............................................70
    3-2-2 氮氣等溫吸脫附…………………................................................72
    3-2-3 13C CP/MAS NMR ……………….............................................75
    3-2-4 29Si MAS NMR …….…………..................................................77
    3-2-5 元素分析………………................................................................80
    3-2-6 酸鹼滴定實驗………………........................................................82
    3-2-7 熱重分析…………........................................................................85
    3-2-8 1H MAS NMR ………………....................................................87
    3-2-9 29Si {1H} HETCOR NMR 實驗結果分析..................................88
    3-3 PO3H2-SBA-15 ……………...................................................................91
    3-3-1 XRD ………………....................................................................91
    3-2-2 氮氣等溫吸脫附………................................................................93
    3-3-3 13C CP/MAS NMR ……..............................................................95
    3-3-4 29Si MAS NMR ……...................................................................97
    3-3-5 31P MAS NMR ……....................................................................101
    3-3-6 29Si {31P} REDOR MAS NMR 實驗結果分析..........................103
    第四章 結論……………………………………………………………………123
    參考文獻………………………………………………………………………..124
    Reference 1.McBain, J. N. “The Sorption of Gases and Vapors by Solids”, George Rutledge and Sons Ltd., London, 1932.
    2.Vaughan, D. E. W. Catal. Today, 1998, 2, 187.
    3.Dailey, J. S.; Pinnavaia, T. J. Chem. Mater. 1992, 4, 855.
    4.Yanagaisawa, T.; Kuroda , K.; Bull, C. K. Chem. Soc. Japn. 1988, 61, 3743
    5.Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuil, J. C.; Beck, J. S. Nature 1992, 359, 710.
    6.Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonwicz, M. E.; Kresge, C. T.; Schmitt, K. D.; Chu, C. T-W.; Olson, D. H.; Sheppard, E. W.; Higgins, S. B.; Schlenker, J. L. J. Am. Chem. Soc. 2002, 114, 10833.
    7.Sayari, A. Chem. Mater. 1996, 8, 1840.
    8.Neumann, R.; Khenkin, K. Chem. Commun. 1996, 2643.
    9.Charkaborty, B.; Pulikottil, A. C.; Viswanathan, B. Catal. Lett. 1996, 39, 63.
    10.Harthmann, M.; Popll, A.; Kenvan, L. J. Phys. Chem. 1996, 100, 9906.
    11.Corma, A.; Navarro, M. T.; Pariente, J. P.; Sanchez, F. Stud. Surf. Sci.  Catal. 1994, 84, 69.
    12.Reddy, J. S.; Sayari, A. Chem. Commun. 1995, 2231.
    13.Wu, C.-G.; Bein, T. Science 1994, 264, 1757.
    14.Wu, C.-G.; Bein, T Science, 1994, 266, 1013.
    15.Wu, C.-G.; Bein, T. Chem. Mater., 1994, 6, 1109.
    16.(a) Lee, Y. S.; Surjadi, D.; Rathman, J. F. Langmuir 1996, 12, 6202.(b) Ko, C. H.; Ryoo, R. J. Chem. Soc. Chem. 1996, 2467.
    17.Tsang,S. C.; Davis, J. J.; Green, M. L. H.; Hill, H. A. O.; Leung, Y. C.Sadler, P. j. Chem. Commun. 1995, 1803.
    18.Abe, T.; Tachibana, Y.; Uemtsu, T.; Iwamoto, M. Chem. Commun. 1995, 1617.
    19.Busio, K.; Janchen, J.; van Hooff, J. H. C. Microporous Mater. 1995, 5, 211.
    20.Luan, Z.; Zhou, W.; Cheng, C.-F.; Klinowski, J. Faraday Trans. 1996, 91, 5161.
    21.Kosslick, H.; Lischke, G.; Walther, G.; Storek, W.; Martin, A.; Fricke, R. Microporous Mater. 1997, 9, 133.
    22.Weglarski, J.; Datka, J.; He,H.; Kilnowski, J. Faraday Trans. 1996, 92, 5161.
    23.Mokaya, R.; Jones, W. Chem. Commun. 1996, 983.
    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.
    25.Kim, M. J.; Ryoo, R. Chem. Mater. 1999, 11, 487.
    26.Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.; Stucky, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 449.
    27.(a) Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.;Chmelka, B. F.; Stucky, G.D. Science. 1998, 279, 548.(b) Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024.
    28.Pluronic poly(alkene oxide) triblock copolymers are trademarked products of BASF, Mt. Olive, NJ.
    29.(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.(b) Chen, C.; Li, H.; Davis, M. E. Microporous Mater. 1993, 2, 17.(c) Attard, G. S.; Glyde, J. C. Nature. 1995, 378, 366.(d) Göltner, C. G.; Antonietti, M. Adv. Mater. 1997, 9, 431.
    30.(a) Tanev, P. T.; Pinnavaia, T. J. Science. 1995, 267, 865.(b) Bagshaw, S. A.; Prouzet, E.; Pinnavaia. T. J. Science. 1995, 269, 1242.
    31.(a) Prouzet, E.; Pinnavaia. T. J. Angew. Chem. Int. Ed.; 1997, 36, 516.(b) Antonietti, M.; Göltner, C. G. Angew. Chem. Int. Ed.; 1997, 36, 910.(c) Firouzi, A.; Atef, F.; Oertli, A. G.; Stucky, G. D.; Chmelka, B. F J. Am. Chem. Soc. 1997, 119, 3596.
    32.(a) Imperor-Clerc, M.; Davidson, P.; Davidson, A. J. Am. Chem. Soc. 2000, 122, 11925. (b) Kruk, M.; Jaroniec, M.; Ko, C. H.; Ryoo, R. Chem. Mater.; 2000, 12, 1961. (c) Ryoo, R.; Ko, C. H.; Kruk, M.; Antochshuk, V.; Jaroniec, M. J. Phys. Chem. B. 2000, 104, 11465.(d) Ravikovitch, P. I.; Neimark, A. V. J. Phys. Chem. B. 2001, 105, 6817.
    33.Schubert, U.; Husing, N. Synthesis of inorganic materials, chapter 4 , Wiley-Interscience publications: New York, 2000.
    34.Todros, T. F. “Surfactant”, Academic Press, London, 1984.
    35.Sakamoto, Y.; Kaneda, M.; Terasaki, O.; Zhao, D. Y.; Kim, J. M.; Stucky, G.; Shin, H. J.; Ryoo, R. Nature 2000, 408, 449.
    36.Tanford, C. “The Hydrophobic Effect: Formation of Micelles and Biological Membranes”, Wiley, New York, 1973
    37.Evans, F. D.; Wennerstrom, H. “The Colloidal Domain”, 2nd Ed, VHC, New York, 1999.
    38.Qi, L.; Ma, J.; Cheng, H.; Zhao, Z. “Colloids and Surfaces A”, 1996, 111, 195.
    39.Liu, J. ; Feng, X.; Fryxell, G. E.; Wang, L.-Q.; Kim. A. Y.; Gong, M. L. Adv. Meter. 1998, 10, 161.
    40.Stein, A.; Melde, B. J.; Schroden, R. C. Adv. Meter. 2000, 12, 1403.
    41.Steel, A. ; Carr, S. W.; Anderson, M. W. Chem. Mater. 1995, 7, 1829.
    42.Fowler, C. E.;Burkett, S. L.;Mann, S. Chem. Commun. 1997, 1769.
    43.(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.
    44.Nakajiam ,K. ; Tomita, I. ; Hara, M. Adv.Mater.2005,17,1839.
    45.Kapoor ,M.P. ; Yang,Q. ; Inagaki ,S. Chem. Mater., Vol. 16, No. 7, 2004, 1213.
    46.Li,.C ; Yang ,J. ; Shi ,X. ; Liu ,J. ; Yang ,Q. Microporous and Mesoporous Materials xxx 2006, 220.
    47.Chong, A. S. Maria.; Zhao, X. S. J. Phys. Chem.B. 2003, 107, 12650
    48.Lei, C.; Shin, Y.; Magnuson, J.; fryxell, G.; Lasure, L.; Elliott, D.; Liu, J.; Ackerman, E. Nanotechnology. 2006, 17, 5531
    49.Wang, X.; Lin, K.S.K.; Chan, J.C.C.; Cheng, S. J. Phys. Chem. B 2005, 109, 1763.
    50.Corriu, J. P.; Datas, L.; Guari, Y.; Mehdi, A.; Reyéa, C.; Thieuleux, C. Chem. Commun., 2001, 763.
    51.Yang, Q. ; Yang, J. ; Liu, j. ; Li, Y. ; Li, C. Chem. Mater. 2005, 17, 3019.
    52.Zhao, Xiu S.; (Max) Lu , G. Q.; Millar, G. J. Ind. Eng. Chem. Res. 1996, 35, 2075.
    53.Goto, Y. ; Inagaki, S. Microporous and Mesoporous Materials 2006 89, 103.
    54.Wang, J. ; Yu, N. ; Zheng, A. ; Yang, J. ; Wu, D. ; Sun, Y. ; Ye, C.; Deng, F. Micropor. and Mesopor. Mater. 2006, 89, 219.
    55.Walcarius, A. ; Etienne, M. ; Lebeau, B. Chem. Mater. 2003, 15, 2161.
    56.國家同步輻射中心 (NSRRC), 新竹市, 台灣。
    57.Baiker, A. International Chem. Eng., 1985, 17, 25
    58.Brunauer, S.; Deming, L. S.; Deming, W. S.; Teller, E. J. Am. Chem. Soc., 1940, 62, 1723
    59.Barrett, E. P.; Joyner, L. S.; Halenda, P. P. J. Am. Chem. Soc., 1951, 73, 373.
    60.Gregg, S. J.; Sing, K. S. W.; Adsorption, Surface Area and Porosity, 2nd Ed., Academic press, New York, NY, 1982.
    61.Levitt, M. H.; Freeman, R.; Frenkiel, T. J. Magn. Reson. 1982, 50,157.
    62.Shaka, A.J.; Barker, P.B.; Freeman. R. J. Magn. Reson. 1985, 64, 547.
    63.Bennett, A.E.; Rienstra, C.M.; Auger, M.; Lakshmi, K.V.; Griffin, R.G. J. Chem. Phys. 1995, 103. 6951.
    64.Gullion, T.; Poliks, M.D.; Schaefer, J. J. Magn. Reson. 1988, 80, 553.
    65.Yang, C.M.; Zibrowius, B.; Schmidt, W.; Schüth, F. Chem. Mater. 2004, 16. 2918.
    Advisor
  • Hsien-Ming Kao(高憲明)
  • Files
  • 962203021.pdf
  • approve in 2 years
    Date of Submission 2009-08-04

    [Back to Results | New Search]


    Browse | Search All Available ETDs

    If you have dissertation-related questions, please contact with the NCU library extension service section.
    Our service phone is (03)422-7151 Ext. 57407,E-mail is also welcomed.