簡易檢索 / 詳目顯示

研究生: 張育甄
Yu Chen Chang
論文名稱: 敏光劑吸附沸石微粒之光電研究
指導教授: 王忠茂
Wang, Chong-Mou
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2001
畢業學年度: 89
語文別: 中文
中文關鍵詞: 沸石敏光劑氟化反應感光薄膜
英文關鍵詞: Zeolite, photosensitizer, Fluorination, photographic film
論文種類: 學術論文
相關次數: 點閱:224下載:6
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 由於有機敏光劑可於照光時顯現氧化力,本論文於是對多種敏光劑,如:thionine (簡稱TH)、phenosafranin (簡稱PSF)、phenazine methosulfate (簡稱PZM)、rose bengal (簡稱RB)、9-cyanoanthracene (簡稱CA)及9,10-dicyanoanthracene (簡稱DCA)的光電性質進行探討,並將之吸附於載體—Zeolite (NaY)中。根據螢光放射光譜、循環伏安法及暫態螢光光譜實驗,含敏光劑的沸石微粒於照光時可將電子授予者,如diphenylamine (簡稱DPA)氧化。
    利用此一光誘發電子轉移反應,吾人成功地製備出一無銀感光薄膜,此感光薄膜於照光時可催化N,N-diethyl-2-methyl-1,4-phenylenediamine (簡稱DEPD)之氧化,並使其與α-naphthol進行偶合反應而生成藍色產物—Indophenol blue。
    本實驗也將敏光劑之氧化力應用於選擇性氟化反應,實驗結果顯示:多數敏光劑可使有機物如Ph3P與Ph3CH在AgF存在下氟化產生Ph3PF2及Ph3CF。

    In this thesis, many photosensitive compounds, such as thionine (denoted TH), phenosafranin (denoted PSF), phenazine methosulfate (denoted PZM), rose bengal (RB), 9-cyanoanthracence (CA) and 9,10-dicyanoanthracence (DCA), and their zeolite-modified particles have been investigated for their potential in photoelectrochemical applications. According to emission spectroscopy and cyclic voltammetry as well as laser flash photolysis, these dyes showed strong oxidation ability as being brought to their excited states. For instance, most of them can oxidize electron donor, like diphenylamine (denoted DPA), as exposed to irradiation.
    Based on these photochemical properties, a non-silver-based photographic system was developed. Indophenol blue was formed on the surface of the films made with dye-modified zeolite particles, N,N-diethyl –1,4-phenylenediamine (DEPD) and α-naphthol during illumination. Experimental results also showed that organic compounds, like triphenylphosphine (denoted Ph3P) and triphenylmethane (denoted Ph3CH), could be selectively fluorinated in the presence of fluoride ions and these dyes.

    第一章 緒論…………………………………………………………….3 1-1 感光薄膜之反應機構………………………………………….3 1-2 選擇性氟化反應……………………………………………….5 1-3 光誘發電子轉移反應與敏光劑氧化力探討………………….7 1-4 利用O-O bands估算激發態敏光劑之能階……………………9 1-5 Stern-Volmer方程式…………………………………………12 1-6 沸石……………………………………………………………14 第二章 實驗……………………………………………………………17 2-1 化學藥品……………………………………………………..17 2-2 實驗儀器………………………………………………………19 2-3 沸石之前處理及製備………………………………………..20 2-4 Iron(II) tris(1,10-phenanthroline)之合成…………..21 2-5 電極之製備……………………………………………………21 2-6 感光薄膜之製備………………………………………………22 第三章 結果與討論…………………………………………………..23 3-1 激發態有機敏光劑氧化力之探討…………………………..23 3-2 含有機敏光劑沸石之探討……………………………………55 3-3 敏光劑之雷射暫態螢光行為研究……………………………68 3-4 含有機敏光劑沸石之應用……………………………………76 第四章 結論…………………………………………………….……103 第五章 參考文獻……………………………………………….……104

    1. Cray, H. B. ; Simon, J. D. ;Trogler, W. C. Ed. 〝Braving the
    Elements〞, 1995, pp. 300~314, University SCIENCE
    Books:Sausalito.
    2. Ronald, D. T. ; Sosnovsky, G. Chem. Rev. 1997, 97, 83.
    3. Swarts, F. Bull. Soc. Chem. Belg. 1896, 15, 1134.
    4. Mann, J. Chem. Soc. Rev. 1987, 16, 381.
    5. Marais, J. S. C. Onderstepoort J. Vet. Sci. Anim. Ind. 1943,
    18, 203.
    6. Welch, J. T. Tetrahedron. 1987, 43, 3123.
    7. Wilkinson, J. A. Chem. Rev. 1992, 92, 505.
    8. Baroux, P. ; Tardivel, R. ; Simonet, J. Tetrahedron Lett.
    1995, 36, 3851.
    9. Sano, M. ; Fuchigami, T. J. Electroanal. Chem. 1996, 414, 81.
    10. Suryanarayanan, V. ; Noel, M. J. Fluorine Chem. 1998, 91,
    153.
    11. Hou, Y. ; Higashiya, S. ;Fuchigami, T. J. Org. Chem. 1999,
    64, 6735.
    12. Hou, Y. ; Higashiya, S. ;Fuchigami, T. Electrochimica. Acta
    2000, 45, 3005.
    13. Maeda, H. ; Ohmori, H. Acc. Chem. Res. 1999, 32, 72.
    14. Ignatev, N. ; Sartori, P. J. Fluorine Chem. 2000, 57, 103.
    15. Babait, M. ; Steenken, S. ; Mcclelland, R. A. J. Am. Chem..
    Soc. 1986, 108, 7023.
    16. Faria, J. L. ; Steenken, S. J. Am. Chem. Soc. 1990, 112,
    1277.
    17. Wang, C. M. ; Mallouk, T. E. J. Am. Chem. Soc. 1990, 112,
    2016.
    18. Lai, C. ; Kim, Y. I. ; Wang, C. M. ; Mallouk, T. E. J. Am.
    Chem. Soc. 1993, 1393.
    19. Jana, A. K. Photochem. Photobiol. A: Chem. 2000, 132, 1.
    20. Paul, A. H. ; Marwijn, P. T. ; Martijn, M. W. ; Jan, M. K.
    ; Rene, A. J. J. Phys. Chem. B 1999, 103, 4352.
    21. Bertolotti, B. G. ; Previtali, C. M. Photochem. Photobiol.
    A: Chem. 1997, 103, 115.
    22. Eriksen, J. ; Foote, C. S. J. Phys. Chem. 1978, 82, 2659.
    23. Eriksen, J. ; Foote, C. S. J. Am. Chem. Soc. 1980, 102,
    6083.
    24. Vauthey, E. J. Phys. Chem. A 1997, 101, 1635.
    25. Lanzalunga, O. ; Crescenzi, C. ; Baciocchi, E. Tetrahedron
    1997, 53, 4469.
    26. Shiraishi, Y. ; Taki, Y. ; Hirai, T. Chem. Commun. 1998,
    2601.
    27. Barker, G. C. ; Jenkins, I. L. Analyst 1952, 77, 685.
    28. Lithgow, A. M. ; Riefkohl, J. L. ; Rodriguez, L. A. ;
    Romero, L. ; Souto, F. A. J. Org. Chem. 1985, 50, 596.
    29. Li, X. ; Ramamurthy, V. J. Am. Chem, Soc. 1996, 118, 10666.
    30. Riefkohl, J. L. ; Rodriguez, L. A. ; Romero, L. ; Sampoll,
    G. ; Souto, F. A. J. Org. Chem. 1986, 51, 2468.
    31. Gopidas, K. R. ; Kamat, P. V. J. Phys. Chem. 1990, 94, 4723.
    32. Mylon, S. E. ; Smirnov, S. N. ; Brann. C. L. J. Phys. Chem.
    A 1998, 102, 6558.
    33. Leray, I. ; Ayadim, M. ; Ottermans, C. ; Jiwan, J. H. ;
    Soumillion, J. P. Photochem. Photobiol. A 2000, 132, 43.
    34. Domenech, A. ; Casades, I. ; Garcia, H. J. Org. Chem. 1999,
    64, 3731.
    35. Ellison, E. H. ; Thomas, J. K. J. Phys. Chem. B 2001, 105,
    2757.
    36. Masui, M. ; Ueda, C. ; Maeda, H. ; Ohmori, H. Chem. Pharm.
    Bull. 1988, 36, 1865.
    37. Hasbrouck, L. J. ; Carlin, C. M. ; Risley, J. M.
    Inorganica. Chimica. Acta 1997, 258, 123.
    38. Mochida, K. ; Okano, M. Chem. Lett. 1991, 819.
    39. 劉亞汶,國立台灣師範大學化學研究所碩士論文,1999.
    40. 洪瑞和,國立台灣師範大學化學研究所碩士論文,2000.

    QR CODE