博碩士論文 88223023 詳細資訊


姓名 葉明珠( Ming-Zhu Ye)  查詢紙本館藏   畢業系所 化學學系
論文名稱 應用固態核磁共振方法鑑定Mordenite沸石脫鋁反應後的酸性
檔案 [Endnote RIS 格式]    [Bibtex 格式]    [檢視]  [下載]
  1. 本電子論文使用權限為同意立即開放。
  2. 已達開放權限電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。
  3. 請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。

摘要(中) 沸石可經各種不同的修飾法來改變骨架結構或組織,以改善其對反應的催化活性。其中脫鋁反應屬於最常被使用的一種方法,所以吾人嘗試利用酸萃取法與矽取代法對沸石進行骨架結構或組織改變,以尋求更好的催化活性。
本研究主要是利用探測分子-三甲基磷(Trimethylphosphine簡稱為TMP) 及三烷基磷氧化物(Trimethylphosphine oxide簡稱為TMPO),將其吸附於H-MOR沸石及脫鋁後的樣品,並利用魔角旋轉固態核磁共振儀,觀測1H、29Si、27Al及31P等核種之核磁共振訊號,對H-MOR沸石及脫鋁後的樣品中的酸性位置分佈及大小加以探討。
摘要(英) The composition such as Si/Al ratio of zeolites can be modified through different methods to improve the activity and selectivity of these materials in heterogeneous catalysis. Dealumination of zeolites is one of the methods that is most widely used. Therefore, acid leaching and subsequent chemical agent (with (NH4)2SiF6) treatments have been employed to dealuminate H-mordenite for seeking the best catalytic activity.
The purpose of this work is to characterize the dealuminated mordenite samples with multinuclear solid-state magic angle spinning (MAS) NMR, for example, 1H, 29Si, and 27Al NMR. Furthermore, the nature, type, and distribution of Bronsted and Lewis acid sites in dealuminated mordenite samples has been investigated by using trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO) as 31P NMR probes.
關鍵字(中) ★ 固態和磁共振儀
★ 脫鋁反應
★ 沸石
★ 探測分子
★ 三甲基磷
★ 三烷基磷氧化物
關鍵字(英) ★ NMR
★ Dealumination
★ Probe molecules
論文目次 中文摘要 ----------------------------------------------------------------------------- Ⅰ
中文摘要 ----------------------------------------------------------------------------- Ⅱ
目錄 ----------------------------------------------------------------------------------- Ⅲ
表目錄 -------------------------------------------------------------------------------- Ⅴ
圖目錄 ------------------------------------------------------------------------------- Ⅵ
第一章 緒論-------------------------------------------------------------------- 1
1-1 前言------------------------------------------------------------------ 1
1-2 沸石與分子篩------------------------------------------------------------- 3
1-2.1 Mordenite沸石的結構-------------------------------------------------- 7
1-3 脫鋁反應------------------------------------------------------------------ 9
1-4 固態核磁共振儀---------------------------------------------------------- 10
1-4.1 Zeeman作用力-------------------------------------------------- 11
1-4.2 非均向化學位移----------------------------------------------- 12
1-4.3 偶極-偶極交互作用力---------------------------------------- 13
1-4.4 四極矩作用力--------------------------------------------------- 14
1-5 去耦合作用----------------------------------------------------------- 16
1-6 魔角旋轉----------------------------------------------------------- 16
1-7 核磁共振儀應用於沸石上------------------------------------------ 18
1-7.1 1H MAS NMR--------------------------------------------------- 18
1-7.2 29Si MAS NMR------------------------------------------------- 19
1-7.3 27Al MAS NMR------------------------------------------------- 21
1-7.4 探測分子應用於核磁共振儀上---------------------------- 23
參考文獻----------------------------------------------------------- 24
第二章 實驗----------------------------------------------------------- 27
2-1研究動機與目的------------------------------------------------ 27
2-2實驗藥品--------------------------------------------------------- 29
2-3 實驗步驟--------------------------------------------------------------------- 30
2-4 實驗儀器設備及參數----------------------------------------------------- 32
參考文獻----------------------------------------------------------- 36
第三章 結果與討論---------------------------------------------------------- 37
3-1 XRD結果-------------------------------------------------------- 37
3-2 1H MAS NMR光譜-------------------------------------------------------- 38
3-2.1 1H MAS NMR結果-------------------------------------------------- 38
3-3 29Si MAS NMR光譜------------------------------------------------------- 44
3-3.1 29Si MAS NMR結果----------------------------------------------- 44
3-4 27Al MAS NMR光譜------------------------------------------------------ 54
3-4.1 1H MAS NMR結果------------------------------------------------ 54
3-5 31P MAS NMR光譜-------------------------------------------------------- 57
3-5.1 1H MAS NMR結果---------------------------------------------- 58
參考文獻----------------------------------------------------------------------------- 66
第四章 結論--------------------------------------------------------------------------- 68
參考文獻 1. IUPAC Manual of Symbols and Terminology, appendix 2, Part 1, Colloid and Surface Chemistry, Pure Appl. Chem., 1972, 31, 578.
2. Breck, D. W. “Zeolite Molecular Sieves”, Wiley :New York, 1974.
3. Farneth, W. E.; Gorte, R. J. Chem. Rev. 1995, 95, 615.
4. 國立台灣大學化學系,蔡佳龍碩士論文,88年6月。
5. Weige D.; Steinhoff, Z. Kristallogr. 1925, 61, 125.
6. McVain, J. W. “The Sorption of Gases and Vapors by solids”, Ruthedge and Sons, London, Chapter 5 1932.
7. Bennett, J. M.; Blackwell, C. S.; Cox, D. E. Interzeolite Chemistry, Am. Chem. Soc. Symp. Ser.218, American Chemical Society, Washington, D. C., 1983.
8. Meier, W. J.; Olson D. “Altas of Zeolite Structure Types” , Butterworths, London, 1987 and 1992.
9. Meier, W. M. “The crystal structure of mordenite (ptilolite) ”, Z. Kristallogr., 1961, 115, 439.
10. Parikh, P.A.; Subrahmanyam, N.; Bhat, Y.S.; Halgeri, A.B. J. Mol. Catal. 1994, 88, 85.
11. Maache, M., Janin, A., Lavally, J.C., and Joly, J.F. Zeolites 1993, 13, 419.
12. Apelllian, M.R.; Fung, A.S.; Kennedy, G.J.; Degnan, T.F. J. Phys. Chem. 1996, 100, 16577.
13. Weitkamp, J.; Sakuth, M.; Chen, C.; Ernst, S. J. Chem. Soc. Chem. Commun. 1989, 1908.
14. Bowes, E.; Pelrine, B.P. US Patent 1983, 4388177.
15. Beyerlein, R.A.; Kugler, E.L.; Tunison, M.E.; Vaughan, D.E.W. EP Patent 1991, 0259526B1.
16. Apelian, M.R.; Degnan, T.F.; Fung, A.S.; Kennedy, G.J. US Patent 1993, 5200168
17. Apelian, M.R.; Degnan, T.F. US Patent 1993, 5238677.
18. Mehring, M.; “High Resolution NMR of Solids, ” Springer-Verlag, Berlin, 1983.
19. Ernst, R.R.; Bodenhausen, G.; Wokann, A. “Principle of Nuclear Magnetic Resonance in One and Two Dimensions”, Clarendon :Oxford, 1987.
20. Blum, K. “Density Matrix Theory and Applications”, Plenum: New York, 1981.
21. Brink, D.M.; Satchler, G.R. “Angular Momentum”, University Press: Oxford, 1962.
22. Bloembergen, N.; Purcell, E. M.; Pound, R. V. Phys. Rev. 1948, 73, 679.
23. Rose, M. E. “Elementary Theory of Angular Momentum”, Wiley: New York, 1957.
24. Engelhard, G.; Michel D. “High-Resolution Solid-State NMR of Silicates and Zeolite”, John Wiley & Son Ltd., 1987.
25. Ripmeester, J. A. J. Am. Chem. Soc. 1983, 105, 2925.
26. Lunsford, J. H.; Rothwell, W. P.; Shen, W. J. Am. Chem. Soc. 1985, 107, 1540.
27. Earl, W. L.; Tritz, P. O.; Gibson, A. A.; Lunsford, J. H.; J. Phys. Chem. 1987, 91,2091.
28. Jacobs, W. P. J. H.; de Haan, J. W.; van de Ven, L. J. M.; van Santen, R. A. J. Phys. Chem. 1993, 97, 10394.
29. Meinhold, R. H.; Parker, L. M.; Bibby, D. M. Zeolites 1986, 6, 491.
30. Dawson, W. H.; Kaiser, S. W.; Ellis, P. D.; Inners, R. R. J. Phys. Chem. 1982, 86, 867.
31. Michel, D.; Germanus, A.; Pfeifer, H. J. Chem. Soc.,Faraday Trans. 1, 1982, 78, 237.
32. Haw, J. F.; Chuang, I. S.; Hawkins, B. L.; Maciel, G. E. J. Am. Chem. Soc. 1983, 105, 7206.
33. Coster, D.; Blumenfeld, A. L.; Fripiat, J. J. J. Phys. Chem. 1994, 98, 6201.
34. Maciel, G. E.; Haw, J. F.; Chuang, I. S.; Hawkins, B. L.; Early, T. A.; McKay, D. R.; Petrakis, L. J. Am. Chem. Soc. 1983, 105, 5529.
指導教授 高憲明(Hsien-Ming Kao) 審核日期 2001-7-16
推文 facebook   plurk   twitter   funp   google   live   udn   HD   myshare   reddit   netvibes   friend   youpush   delicious   baidu   

若有論文相關問題,請聯絡國立中央大學圖書館推廣服務組 TEL:(03)422-7151轉57407,或E-mail聯絡