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研究生： 許宏裕
論文名稱： 聯吡啶釕錯合物之性質探討及應用於太陽能電池之研究
指導教授： 張一知
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 200
中文關鍵詞： 釕錯合物 、電解質 、Voc
英文關鍵詞： 3I-/I3-, 2Br-/Br2
論文種類： 學術論文
相關次數： 點閱：87  下載：0 
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    • 在本研究中合成了一系列釕錯合物，Ru(LL)(dcbpy)2+ (LL = dabpy, bpy, dMeObpy, Cl2bpy, dcbpy, deebpy, 5,5’-dcbpy) 與 Fe(dcbpy)32+，並測量它們的 UV-vis、emission 光譜、lifetime 與氧化還原電位，以了解配位基的推拉電子基修飾對電子分布之影響。
    　　此類錯合物作為染料並配合 3I-/I3- + BMII、2Br-/Br2、2Br-/Br2 + BMII 與 2Br-/Br2 + BMIBr 四種電解質，製成光敏性染料太陽能電池並測量其效率。在 3I-/I3- + BMII 與 2Br-/Br2 + BMII 環境下 Ru(dabpy)(dcbpy)2+ 有最好的光電轉換效率，在 2Br-/Br2 與 2Br-/Br2 + BMIBr 的環境下，Ru(bpy)(dcbpy)2+ 與 Ru(phen)(dcbpy)2+ 具有最好的光電轉換效率。
    　　當電解質使用 2Br-/Br2 與 2Br-/Br2 + BMIBr 時可以測得的Voc 最大約為 0.9 V，而 3I-/I3- + BMII 與 2Br-/Br2 + BMII 所測得的 Voc 最高值約為0.6 V。
    　　以 Fe(dcbpy)32+ 製成的光電池 Voc、Isc、ff 與光電轉換效率均趨近於零。
    　　以 N719 為染料，並使用 tetracyanoethylene、ammonium diethyldithiocarbamate、potassium ethylxanthate 與 dimethylaniline 作為電解質所製成之光電池 Voc、Isc、ff 與光電轉換效率均趨近於零。

    A series of Ru(LL)(dcbpy)2+ complexes, where LL = dabpy, dMeObpy, bpy, Cl2bpy, dcbpy and deebpy, and Fe(dcbpy)32+, have been synthesized. UV-vis, emission, electrochemistry and lifetime have been measured for all complexes in order to understand their photophysical and redox properties.
    These complexes, preformed as dye, have been assembled to a solar cell. Electrolytes utilized in the solar cells were 3I-/I3- + BMII, 2Br-/Br2, 2Br-/Br2 + BMII and 2Br-/Br2 + BMIBr. When 3I-/I3- and 2Br-/Br2 + BMII were utilized as electrolyte, Ru(dabpy)(dcbpy)2+ gave the best result. When 2Br-/Br2 and 2Br-/Br2 + BMIBr were utilized as electrolyte, Ru(bpy)(dcbpy)2+ and Ru(phen)(dcbpy)2+ resulted the highest output.
    When using all bromine based electrolytes, such as 2Br-/Br2 and 2Br-/Br2 + BMIBr, the Voc of 0.9 V is measured. In the same condition but with iodide present, 3I-/I3- and 2Br-/Br2 + BMII, the Voc measured was 0.6 V.
    There was no Voc, Isc, ff and conversion efficiency measured when Fe(dcbpy)32+ was utilized as dye.
    In the attempt of finding new series of electrolytes, we found no Voc, Isc, ff nor conversion efficiency measured with tetracyanoethylene, ammonium diethyldithiocarbamate, potassium ethylxanthate and dimethylaniline as electrolytes and N719 as dye.

    表目錄................................................................................................................III 圖目錄.................................................................................................................V 中文摘要.........................................................................................................VIII 英文摘要...........................................................................................................IX 第一章　緒論 　第一節　光敏性染料太陽能電池 (Dye-Sensitized Solar Cells) 的介紹....1 　第二節　聯吡啶釕錯化合物的簡介............................................................11 　第三節　實驗的起源與目的........................................................................15 第二章　實驗部份 　第一節　一般實驗處理................................................................................17 　第二節　儀器設備........................................................................................17 　第三節　藥品................................................................................................21 　第四節　配位基結構與代號........................................................................24 　第五節　錯化合物與代號............................................................................25 　第六節　合成................................................................................................26 　第七節　Nanocrystalline TiO2 film 製作....................................................48 　第八節　Sandwich Solar Cell 製作.............................................................50 第三章　結果與討論 　第一節　合成................................................................................................52 　第二節　UV-vis 吸收光譜..........................................................................53 　第三節　冷光光譜........................................................................................59 　第四節　生命期............................................................................................61 　第五節　電化學............................................................................................64 　第六節　Ru-type complexex 光電池效能的研究......................................70 　第七節　不同電解質對以 N719 為染料之光電池效能的研究...............84 　第八節　X-ray 結構資料............................................................................88 第四章　結論..................................................................................................102 參考文獻..........................................................................................................104 附圖..................................................................................................................112

    01. Grätzel, M. Nature 2001, 414, 338.
    02. Honda, K.; Fujichima, A. Nature 1972, 238, 37.
    03. Tufts, B.J.; Abrahams, I. L.; Santangelo, P. G.; Ryba, G. N.; Casagrande, L.G.; Lewis, N.S. Nature 1987, 326, 861.
    04. Heller, A. Acc. Chem. Res. 1981, 14, 154.
    05. Tributsch, H.; Bennet, J. C. J. electroanal. Chem. 1977, 81, 97.
    06. Bard, A. J. Science 1980, 207, 139.
    07. O’Regan, B.; Grätzel, M. Nature 1991, 353, 737.
    08. Nazeeruddin, Md. K.; Kay, A.; Rodicio, 1.; Humpbry-Baker, R., Müller, E. ; Liska, P.; Vlachopoulos, N.; and Grätzel, M. J. Am. Chem. Soc. 1993, 115, 6382.
    09. (a) Heimer, T.A.; Castellano, F. N.; Meyer, G. J. J. Phys. Chem. B 1997, 101, 2591. (b) Kelly, C.A.; Farzad, F.; Thompson, D. W.; Meyer, G. J. Langmuir 1999, 15, 731. (c) Gholamkhass, B.; Koike, K.; Negishi, N.; Hori, H.; Takeuchi, K. Inorg. Chem. 2001, 40, 756. (d) Hara, K.; Sugihara, H.; Tachibana, Y.; Islam, A.; Yanagida, M.; Sayama, K.; Arakawa, H. Langmuir 2001, 17, 5992. (e) Renouard, T.; Grätzel, M. Tetrahedron 2001, 57, 8145. (f) Barolo, C.; Nazeeruddin, Md. K.; Fantacci, S.; Censo, D. Di; Comte, P.; Liska, P.; Viscardi, G.; Quagliotto, P.; Angelis, F. De; Ito, S.; Grätzel, M. Inorg. Chem. 2006, 45, 4642.
    10. Hara,K.; Sato, T.; Katoh, R.; Furube, A.; Ohga, Y.; Shinpo, A.; Suga, S.; Sayama, K.; Sugihara, H.; Arakawa, H. J. Phys. Chem. B 2003, 107, 597.
    11. Huber, R.; Spö1rlein, S.; Moser, J. E.; Grätzel, M.; Wachtveitl, J. J. Phys. Chem. B 2000, 104, 8995.
    12. Ehret, A.; Stuhl, L.; Spitler, M. T. J. Phys. Chem. B 2001, 105, 9960.
    13. Robel, I; Subramanian, V.; Kuno, M.; Kama,t P. V. J. Am. Chem. Soc. 2006, 128, 2385.
    14. Peter, L. M.; Wijayantha, K. G. U.; Riley, D. J.; Waggett, J. P. J. Phys. Chem. B 2003, 107, 8378.
    15. Zaban, A.; Mićić, O. I.; Gregg, B. A.; Nozik, A. J. Langmuir 1998, 14, 3153.
    16. Nazeeruddin, M. K.; Péchy, P.; Renouard, T.; Zakeeruddin, S. M.; Humphry-Baker, R.; Comte, P.; Liska, P.; Cevey, Le; Costa, E.; Shklover, V.; Spiccia, L.; Deacon, G. B.; Bignozzi, C. A.; Grätzel, M. J. Am. Chem. Soc. 2001, 123, 1613.
    17. Nazeeruddin, Md. K.; Kalyanasundaram, K.; Grätzel, M. Inorg. Synth. 1998, 32, 181.
    18. Barbè, C.; Arendse, F.; Comte, P.; Jirousek, M.; Lenzmann, F.; Shklover, V.; Grätzel, M. J. Am. Ceram. Soc. 1997, 80, 3157.
    19. Tachibana, Y.; Moser, J. E.; Grätzel, M.; Klug, D. R.; Durrant, J. R. J. Phys. Chem. 1996, 100, 20056.
    20. Hannappel, T.; Burfeindt, B.; Storck, W. J. Phys. Chem. B 1997, 101, 6799.
    21. Hilgendorff, M.; Sundström, V. J. Phys. Chem. B 1998, 102, 10505.
    22. Burfeindt, B.; Hannappel, T.; Storck, W.; Willig, F. J. Phys. Chem. 1996, 100, 16463.
    23. Wachtveitl, J.; Hyber, R.; Spörlein, S.; Moser, J. E.; Grätzel, M. J. Photoenerg. 1999, 1, 153.
    24. Damrauer, N. H.; Cerullo, G.; Yeh, A.; Boussie, T. R.; Shank, C. V.; McCusker, J. K. Science 1997, 275, 54.
    25. Tachibana, Y.; Haque, S. A.; Mercer, I. P.; Durrant, J. R. ; Klug, D. R. J. Phys. Chem. B 2000, 104, 1198.
    26. Fessenden, R. W.; Kamat, P. V. J. Phys. Chem. 1995, 99, 12902.
    27. Haque, S. A.; Tachibana, Y.; Klug, D. R.; Durrant, J. R. J. Phys. Chem. B 1998, 102, 1745.
    28. Sengupta, A.; Jiang, B.; Mandal, K. C.; Zhang, J. Z. J. Phys. Chem. B 1999, 103, 3128.
    29. Cherepy, N. J.; Smestad, G. P.; Grätzel, M.; Zhang, J. Z. J. Phys. Chem. B 1997, 101, 9342.
    30. Haque, S. A.; Tachibana, Y.; Willis, R. L. ; Moser, J. E.; Grätzel, M.; Klug, D. R.; Durrant, J. R. J. Phys. Chem. B 2000, 104, 538.
    31. Mor, G. K.; Shankar, K.; Paulose, M.; Varghese, O. K.; Grimes, C. A. Nano Lett, 2006, 6, 215.
    32. Park, J.; Bauer, S.; Mark, K. V. D.; Schmuki, P. Nano Lett, 2006, 7, 1686.
    33. Zhu, K.; Neale, N. R.; Miedaner, A.; Frank, A. J. Nano Lett, 2007, 7, 69.
    34. Rensmo, H.; Södergren, S.; Patthey, L.; Westermark, K.; Vayssieres, L.; Kohle, O.; Brühwiler, P.; Hagfeldt, A.; Siegbahn, H. Chem. Phys. Lett. 1997, 274, 51.
    35. Alebbi, M.; Bignozzi, C. A.; Heimer,T. A.; Hasselmann,G.M.; Meyer, G. J. J. Phys. Chem. B 1998, 102, 7577.
    36. Sapp, S. A.; Elliott, C. M.; Contado, C.; Caramori, S.; Bignozzi, C. A. J. Am. Chem. Soc. 2002, 124, 11215.
    37. Bach, U.; Lupo, D,; Comte, P.; Moser, J. E.; Weissörtel, F.; Salbeck, J.; Spreitzer, H.; Grätzel, M. Nature 1998, 395, 538.
    38. Snaith, H. J.; Moule, A. J.; Klein, C.; Meerholz, K.; Friend, R. H.; Gra1tzel, M Nano Lett, 2007, 7, 3372.
    39. Hager, G. D.; Crosby, G. A. J. Am. Chem. Soc. 1975, 97, 7031.
    40. Hipps, K. W.; Crosby, G. A. J. Am. Chem. Soc. 1975, 97, 7042.
    41. Houten, J. V.; Watts, R. J. J. Am. Chem. Soc. 1976, 98, 4853.
    42. Demas, J. N.; Taylor, D. G. Inorg. Chem. 1979, 18, 3177.
    43. Caspar, J. V.; Meyer, T. J. J. Am. Chem. Soc. 1983, 105, 5583.
    44. Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin Complexes, Academic Press, Lodon, 1992.
    45. Hahm, S.; Durham,B.; Millett, F. Biochemistry 1992, 31, 3472.
    46. Barton, J. K.; Goldberg, J. M.; Kumar, C. V.; Turro, N. J. J. Am. Chem. Soc. 1986, 108, 2081.
    47. Rehmann, J. P.; Barton, J. K. Biochemistry 1990, 29, 1701.
    48. Rehmann, J. P.; Barton, J. K. Biochemistry 1990, 29, 1710.
    49. Jenkins, Y.; Barton, J. K. J. Am. Chem. Soc. 1992, 114, 8136.
    50. Schulman, L. S., Bossmann, S. H.; Turros, N. J. J. Phys. Chem. 1995,99, 9283.
    51. Moucheron, C. ; Mesmaeker, A. K.; Choua, S. Inorg. Chem. 1997, 36, 584.
    52. Brennaman, M. K.; Alstrum-Acevedo, J. H.; Fleming, C. N.; Jang, P.; Meyer, P. J.; Papanikolas, J. M. J. Am. Chem. Soc. 2002, 124, 15094.
    53. Friedman, A. E.; Chambron, J. C.; Sauvage, J. P.; Turro, N. J.; Barton, J. K. J. Am. Chem. Soc. 1990, 112,4960.
    54. Jenkins, Y.; Friedman, A. E.; Turro, N. J.; Barton, J. K.; Biochemistry 1992, 31, 10809.
    55. Turro, C.; Bossmann, S. H.; Jenkins, Y.; Barton, J. K.; Turro, N. J. J. Am. Chem. Soc. 1995,117, 9026.
    56. Sabatani, E.; Nikol, H. D.; Gray, H. B.; Anson, F. C. J. Am. Chem. Soc. 1996, 118, 1158.
    57. Erkkila, K. E.; Odom, D. T.; Barton, J. K. Chem. Rev. 1999, 99, 2777.
    58. Schäfer, B.; Görls, H.; Presselt, M.; Schmitt, M.; Popp, J.; Henry, W.; Vosc, J. G.; Rau, S. J. Chem. Soc., Dalton Trans., 2006, 2225.
    59. Maheswari, P. U.; Rajendiran, V.; Palaniandavar, M.; Parthasarathi, R.; Subramanian, V. J. Inorg. Biochem. 2006, 100, 3.
    60. Liu, X. W.; Li, J.; Li, H.; Zheng, K. C.; Chao, H.; Ji, L. N. J. Inorg. Biochem. 2005, 99, 2372.
    61. Chang, I. J.; Gray, H. B.; Winkler, J. R. J. Am. Chem. Soc. 1991, 113, 7056.
    62. Stemp, E. D. A.; Arkin, M. R.; Barton, J. K. J. Am. Chem. Soc. 1997, 119, 2921.
    63. 張世琦, 國立台灣師範大學化學研究所碩士論文, 2003 年.
    64. Kavanagh, P.; Leech, D. Tetrahedron Letters 2004, 45, 121.
    65. Eskelinen, E.; Luukkanen, S.; Haukka, M.; Ahlgrén, M.; Pakkanen, T. A. J. Chem. Soc., Dalton Trans. 2000, 2745.
    66. Nazeeruddin, M. K.; Kay, A.; Rodicio, l.; Humpbry-Baker, R.; Miiller, E.; Liska, P.; Vlachopoulos, N.; Gratzel, M. J. Am. Chem. Soc. 1993,115, 6382.
    67. Belser, p.; Zelewsky, A. V. Helvetica Chimica Acta 1980, 63, 1675.
    68. 陳麗如, 國立台灣師範大學化學研究所碩士論文, 2006 年.
    69. Su,C. H.; Chen, H. Y.; Tsai, K. Y. D.;Chang, I J. J. Phys. Chem. B 2007, 111, 6857.
    70. Winkler, K.; McKnight, N.; Fawcett, w. R. J. Phys. Chem. B 2000, 104, 3575.
    71. 廖家翎, 國立台灣師範大學化學系專題研究報告, 2007 年.
    72. 錢大恩, 國立台灣師範大學化學研究所碩士論文, 2006 年.
    73. Cook, M. J.; Lewis, A. P.; McAuliffe, G. S. G.; Skarda, V.; Thomson, A. J. J. Chem. Soc. Perkin Trans. II 1984, 1293.
    74. Nazeeruddin, M. K.; Liska, P.; Moser, J.; Vlachopoulos, N.; Grätzel, M. Helvetica Chimica Acta 1990, 73, 1788.
    75. Conan, F.; Gall, B. L.; Kerbaol, J. M.; Stang, S.L.; Sala-Pala, J.; Mest, Y. L.; Bacsa, J.; Ouyang, X.; Dunbar, K. R.; Campana, C. F. Inorg. Chem. 2004, 43, 3673.
    76. Mizoguchi, T.; Adams, R. N. J. Am. Chem. Soc. 1961,84, 2058.
    77. Deronzier, A.; Meyer, T. J. Inorg. Chem. 1980, 19, 2912.
    78. (a) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.; Mueller, E.; Liska, P.; Vlachopoulos, N.; Grätzel, M. J. Am. Chem. Soc. 1993, 115, 6382. (b) Nazeeruddin, M. K.; Zakeeruddin, S. M.; Humphry-Baker, R.; Jirousek, M.; Liska, P.; Vlachopoulos, N.; Shklover, V.; Fischer, C.-H.; Grätzel, M. Inorg. Chem. 1999, 38, 6298.

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