染敏電池用之非對稱釕錯合物之輔助配位基的設計與合成

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：9

、訪客IP：18.206.92.240

姓名

蔡嘉鴻(Jia-Hung Tsai) 查詢紙本館藏

畢業系所

化學學系

論文名稱

染敏電池用之非對稱釕錯合物之輔助配位基的設計與合成
(Design and Sythesis of Ancillary Ligands on Heteroleptic Ruthenium Complexes for Dye-sensitized Solar Cells)

相關論文

★ 導電高分子應用於鋁質電解電容器之研究	★ 異参茚并苯衍生物合成與性質之研究
★ 含雙吡啶或二氮雜啡衍生物配位基之釕金屬錯合物的合成與其在染料敏化太陽能電池之應用	★ 新型噻吩環戊烷有機染料於染料敏化太陽能電池之應用
★ 應用於染料敏化太陽能電池之新型釕金屬錯合物的合成與性質探討	★ 釕金屬光敏化劑的設計與合成及其在染料敏化太陽能電池之應用
★ 含雙噻吩環戊烷之電變色高分子的研究	★ 含噻吩衍生物非對稱方酸染料應用於染料敏化太陽能電池
★ 高品質導電聚苯胺薄膜的合成及應用	★ 染料敏化太陽能電池用導電高分子聚苯胺及聚二氧乙基噻吩陰極催化劑的探討
★ 具多功能性之非對稱型釕錯合物的設計與合成並應用於染料敏化太陽能電池	★ 含乙烯噻吩固著配位基之非對稱型釕金屬錯合物應用於染料敏化太陽能電池
★ 染料敏化太陽能電池用二茂鐵系統電解質的探討	★ 合成含喹啉衍生物非對稱方酸染料應用於染料敏化太陽能電池
★ 合成新穎輔助配位基於無硫氰酸釕金屬光敏劑在染料敏化太陽能電池上的應用	★ Design and Synthesis of Ruthenium Dyes for High Open-circuit Voltage Dye-sensitized Solar Cells

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

至系統瀏覽論文 ( 永不開放)

摘要(中)

本論文主要探討不同輔助配位基之光學特性對非對稱型釕錯合物染料的光學性質之影響，希望以精確的輔助配位基設計來合成高效率釕錯合物染料。我們藉由分析本實驗室所合成出的釕錯合物染料和輔助配位基之光學性質的比較，以及染料組裝成電池元件時的光電效能，設計及合成出兩個含新結構輔助配位基Ligand-B16，Ligand-B17的非對稱型釕金屬錯合物染料SJW-B16，SJW-B17。Ligand-B16的結構是雙吡啶上接上vinylthiophene來延長其共軛長度，末端接上咔唑當推電子基。Ligand-B17的結構是雙吡啶上接上雙噻吩環來延長其共軛長度，末端接上三個碳及咔唑來微調末端推拉電子的能力。兩個配位基再分別使用”一步”合成法製備成非對稱型染料。Ligand-B16
Ligand-B17的最大吸收波長為380 nm和375 nm，SJW-B16，SJW-B17的最大吸收波長與吸收係數各別為536 nm、21000 M-1cm-1 和552 nm、22000 M-1cm-1。最後以SJW-B16及SJW-B17當光敏化劑組裝成染料敏化太陽能電池元件，在AM 1.5光源照射下，光電轉換效率分別為5.3 %，4.9 %（相較於N719電池的5.4 %）

摘要(英)

The objective of this thesis is to prepare high efficiency ruthenium based dyes via proper design of the ancillary ligands. The ancillary ligand was designed by carefully studying the effect of the optical properties of the ancillary ligands on the light harvesting properties and therefore the resulting photovoltaic performance of the corresponding ruthenium complexes prepared in our laboratory. We design and synthesize two novel ancillary ligands, Ligand-B16 and Ligand-B17 based on the previous data. The corresponding complexes SJW-B16 and SJW-B17 were then synthesized with a typical “one-pot” process. The structure of Ligand-B16 composed of a vinylthiophene substituted bipyridine and a t-butyl-carbazole terminal group. The structure of Ligand-B17 is formed by a bipyridine substituted with a bithiophene which connected with a propylene chain and a t-butyl-carbazole at the terminal. Ligand-B16 and Ligand-B17 have the λmax of 380 nm and 375 nm, respectively. The λmax, absorption coefficient of SJW-E16 and SJW-E17 are 536 nm, 21000 M-1cm-1and 552 nm, 22000 M-1cm-1, respectively. The conversion efficiencies of the dye sensitized solar cells based on SJW-B16 and SJW-B17 dyes are 5.3 % and 4.9 %, respectively under the AM 1.5 simulated sunlight (100 mWcm-2) illumination. The efficiency for N719 dye is 5.4 % under the same cell fabrication and photovoltaic performance measuring conditions.

關鍵字(中)

★ 染料敏化太陽能電池

關鍵字(英)

★ dye
★ dye-sensitized solar cell

論文目次

中文摘要
Abstract
目錄.............................................................................................................I
圖目錄......................................................................................................VI
表目錄......................................................................................................IX
流程圖目錄..............................................................................................XI
壹、序論......................................................................................................1
1-1、前言.....................................................................................................1
1-2、太陽能電池的種類.............................................................................3
1-3、染料敏化太陽能電池（Dye-Sensitized Solar Cell，DSC）的發展.....4
1-4、染料敏化太陽能電池的工作原理.....................................................5
1-5、光電轉換效率（η）的量測...................................................................7
1-5-1、IPCE（incident photon to current conversion efficiency）................9
1-5-2、總光電轉換效率( η ) ......................................................................9
1-6、釕金屬錯合物染料...........................................................................10
1-6-1、釕金屬錯合物染料的概述...........................................................10
1-6-2、代表性的釕金屬錯合物染料：N3、N719......................................10
1-6-3、輔助配位基（ancillary ligand）的設計I：使用疏水性長碳鏈.....13
1-6-4、輔助配位基（ancillary ligand）的設計II：增加共軛單位...........14
1-6-5、輔助配位基（ancillary ligand）的設計III：使用推電子基.........20
貳、實驗部分............................................................................................25
2-1、實驗藥品...........................................................................................25
2-2、儀器分析與樣品製備.......................................................................29
2-2-1、紫外光/可見光吸收光譜儀 (UV/Vis. Spectrometer) .................29
2-2-2、核磁共振光譜儀 (NMR) ............................................................30
2-3、合成步驟...........................................................................................30
2-3-1、3,6-di-tert-butyl-9-(5-((1E)-2-(2-(4-((E)-2-(5-(3,6-di-tert-butyl-
9H-carbazol-9-yl)thiophen-2-yl)vinyl)pyridin-2-yl)pyridine-
4-yl)vinyl)thiophen-2-yl)-9H-carbazole (Ligand-B16)的合成...30
2-3-1-1、3,6-di-tert-butyl-9-(thiophen-2-yl)-9H-carbazole (TDTBC)
的合成......................................................................................33
2-3-1-2、5-(3,6-di-tert-butyl-9H-carbazol-9-yl)thiophene-2-carbalde-
hyde (TDTBCA)的合成...........................................................35
2-3-1-3、3,6-di-tert-butyl-9-(5-(2-(2-(4-(2-(5-(3,6-di-tert-butyl-9H-
carbazol-9-yl)thiophen-2-yl)-2-hydroxyethyl)pyridin-2-yl)- pyridin-4-yl)-1-bromoethyl)thiophen-2-yl)-9H-carbazole- (preligand-B16) 的合成..........................................................37
2-3-1-4、3,6-di-tert-butyl-9-(5-((1E)-2-(2-(4-((E)-2-(5-(3,6-di-tert-butyl-
9H-carbazol-9-yl)thiophen-2-yl)vinyl)pyridin-2-yl)pyridin-4-
yl) vinyl)thiophen-2-yl)-9H-carbazole (Ligand-B16)的合.......39
2-3-2、4,4’-dibromo-2,2’-bipyridine (4,4’-dibromo-bpy)的合成.............41
2-3-2-1、[2,2’]Bipyridinyl-1,1’-dioxide (bpy-dioxide)的合成.................42
2-3-2-2、4,4’-Dinitro-[2,2’]bipyridinyl-1,1’-dioxide(dinitro-
bpy-dioxide)的合成...............................................................43
2-3-2-3、4,4’-Dibromo-2,2’bipyridinyl-1,1’-dioxide(dibromo-bpy-
dioxide)的合成.........................................................................44
2-3-2-4、4,4’-Dibromo-2,2’bipyridine (4,4’-dibromo-bpy)的合成..........45
2-3-3、3,6-di-tert-butyl-9-(3-(5-(5-(2-(4-(5-(5-(3-(3,6-di-tert-butyl-9H-
carbazol-9-yl)propyl)thiophen-2-yl)thiophen-2-yl)pyridin-2-yl)
pyridin-4-yl)thiophen-2-yl)thiophen-2-yl)propyl)-9H-carbazole
（Ligand-B17）的合成..................................................................46
2-3-3-1、2-(3-bromopropyl)-5-(thiophen-2-yl)thiophene (3BrPBT)的
合成..........................................................................................48
2-3-3-2、3,6-di-tert-butyl-9-(3-(5-(thiophen-2-yl)thiophen-2-yl)propyl)-
9H-carbazole (BTPDTDBC)的合成........................................50
2-3-3-3、3,6-di-tert-butyl-9-(3-(5-(5-(trimethylstannyl)thiophen-2-yl)
thiophen-2-yl)propyl)-9H-carbazole（TMeSnBTPDTBC）
的合成......................................................................................52
2-3-3-4、3,6-di-tert-butyl-9-(3-(5-(5-(2-(4-(5-(5-(3-(3,6-di-tert-butyl-
9H-carbazol-9-yl)propyl)thiophen-2-yl)thiophen-2-yl)pyridin-
2-yl)pyridin-4-yl)thiophen-2-yl)thiophen-2-yl)propyl)-9H-
carbazole（Ligand-B17）的合成................................................55
2-3-4、SJW-B16及SJW-B17的合成......................................................57
参、結果與討論........................................................................................58
3-1、preligand的共軛長度對輔助配位基及錯合物光學性質的影響...58
3-2、輔助配位基之光學特性對釕錯合物染料之光學性質的影響.......61
3-2-1、Ligand-B3之光學特性對染料之光學性質的影響......................63
3-2-2、Ligand-E1之光學特性對染料之光學性質的影響.....................64
3-2-3、Ligand-B1之光學特性對染料之光學性質的影響......................65
3-2-4、Ligand-B4之光學特性對染料之光學性質的影響......................66
3-2-5、Ligand-B7之光學特性對染料之光學性質的影響......................67
3-2-6、Ligand-B6S及Ligand-B6L之光學特性對染料之光學性質的
影響.................................................................................................68
3-2-7、如何設計輔助配位基來增加其所相對之釕金屬錯合物的吸收
係數及紅位移其吸收波長........................................................69
3-3、Ligand-B16及Ligand-B17的合成...................................................70
3-4、Ligand-B16及Ligand-B17的質譜鑑定...........................................72
3-5、SJW-B16及SJW-B17的合成及結構鑑定.....................................73
3-6、SJW-B16和SJW-B17邊界軌域（frontier orbitals）分佈的理
論計算探討.....................................................................................73
3-7、SJW-B16的光學性質探討..............................................................77
3-8、SJW-B17的光學性質探討..............................................................79
3-9、使用SJW-B16和SJW-B17當光敏化劑所組裝的電池元件之
效率探討.........................................................................................80
肆、結論....................................................................................................83
伍、參考文獻............................................................................................84

參考文獻

1.http://zh.wikipedia.org/w/index.php?title=%E5%86%8D%E7%94%9F%E8%83%BD%E6%BA%90&variant=zh-tw
2.http://www.newenergy.org.cn/
3.http://zh.wikipedia.org/w/index.php?title=%E5%A4%AA%E9%99%BD%E8%83%BD&variant=zh-tw
4.http://mypaper.pchome.com.tw/news/gachen/3/1309448186/20080806095650/
5.http://tw.myblog.yahoo.com/cck1818tw/article?mid=445&prev=644&next=444&l=f&fid=39
6.http://cdnet.stpi.org.tw/techroom/market/energy/2008/energy_08_003.htm
7.M. A. Green, K. Emery, Y. Hishikawa, and W. Warta, Prog. Photovolt : Res. Appl. 2009, 17, 85-94.
8.B. O’Regand, and M. Gratzel, Nature 1991, 353, 737-740.
9.M. Gratzel, Nature 2001, 414, 338-344.
10.M. Gratzel, Inorg. Chem. 2005, 44, 6841-6851.
11.http://www.energyharvestingjournal.com/glossary/am_designation_297.asp?sessionid=1
12.M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, and M. Gratzel, J. Am. Chem. Soc. 1993, 115, 6382-6390.
13.M. K. Nazeeruddin, R. Splivallo, P. Liska, P. Comte, and M. Gratzel, Chem. Comm. 2003, 1456-1457.
14.M. K. Nazeeruddin, F. D. Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, B. Takeru, and M. Gratzel, J. Am. Chem. Soc. 2005, 127, 16835-16847.
15.P. Wang, S. M. Zakeeruddin, J.-E. Moser, and M. Gratzel, J. Phys. Chem. B 2003, 107, 13280-13285.
16.P. Wang, S. M. Zakeeruddin, J.-E. Moser, M. K. Nazeeruddin, T. Sekiguchi, and M. Gratzel, Nature Materials 2003, 2, 402-407.
17.P. Wang, S. M. Zakeeruddin, J.-E. Moser, R. Humphry-Baker, P. Comte, V. Aranyos, A. Hagfeldt, M. K. Nazeeruddin, and M. Gratzel, Adv. Mater., 2004, 16,1806-1811.
18.P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin, and M. Gratzel, J. Am. Chem. Soc. 2005, 127, 808-809.
19.M. K. Nazeeruddin, Q. Wang, L. Cevey, V. Aranyos, P. Liska, E. Figgemeier, C. Klein, N. Hirata, S. Koops, S. A. Haque, J. R. Durrant, A. Hagfeldt, A. B. P. Lever, and M. Gratzel, Inorg. Chem. 2006, 45, 787-797.
20.Z. Fei, D. Kuang, D. Zhao, C. Klein, W. H. Ang, S. M. Zakeeruddin, M. Gratzel, and P. J. Dyson, Inorg. Chem. 2006, 45, 10407-10409.
21.D. Kuang, S. Ito, B. Wenger, C. Klein, J.-E. Moser, R. Humphry- Baker, S. M. Zakeeruddin, and M. Gratzel, J. Am. Chem. Soc. 2006, 128, 4146-4154.
22.D. Kuang, C. Klein, S. Ito, J.-E. Moser, R. Humphry-Baker, S. M. Zakeeruddin, and M. Gratzel, Adv. Funct. Mater. 2007, 17, 154–160.
23.C.-Y. Chen, S.-J. Wu, C.-G. Wu, J.-G. Chen, and K.-C. Ho, Angew. Chem. Int. Ed. 2006, 45, 5822–5825.
24.K.-J. Jiang, N. Masaki, J.-B. Xia, S. Nodab, and S. Yanagida, Chem. Comm. 2006, 2460–2462.
25.C.-Y. Chen, J.-G. Chen, S.-J. Wu, J.-Y. Li, C.-G. Wu, and K.-C. Ho, Angew. Chem. Int. Ed. 2008, 120, 7452–7455.
26.C.-Y. Chen, S.-J. Wu, J.-Y. Li, C.-G. Wu, J.-G. Chen, and K.-C. Ho, Adv. Mater. 2007, 19, 3888–3891.
27.A. Abbotto, C. Barolo, L. Bellotto, F. D. Angelis, M. Gratzel, N. Manfredi, C. Marinzi, S. Fantacci, J.-H. Yumd, and M. K. Nazeeruddin, Chem. Comm. 2008, 5318–5320.
28.A. Hameurlaine, and W. Dehaen, Tetrahedron Lett. 2003, 44, 957-959.
29.A. Abbotto, L.Belloto, F. D. Angelis, N.Manfredi, and C. Marinzi, Eur. J. Org. Chem. 2008, 5047-5054.
30.I. Murase, and N. Kagaku, Zasshi 1956, 77, 682-689.
31.G. Maerker, and F. H. Case, J. Am. Chem. Soc., 1958, 80, 2745-2748.
32.D. Wenkert, and R. B. Woodward, J. Org. Chem. 1983, 48, 283-289.
33.A. Padwa, D. Hertzog, and W. R. Nadler, J. Org. Chem. 1994, 59, 7072-7084.
34.T. Xu, R. Lu, M. Jin, X. Qiu, P. Xue, C. Bao, and Y. Zhao, Tetrahedron Letters, 2005, 46, 6883-6886.
35.S.-R. Jang, C. Lee, H. Choi, J. J. Ko, J. Lee, R. Vittal, and K.-J. Kim, Chem. Mater. 2006, 18, 5604-5608.
36.M. K. Nazeeruddin, S. M. Zakeeruddin, R. Humphry-Baker, S. I. Gorelsky, A. B. P. Lever, and M. Gratzel, Coord. Chem. Rev. 2000, 208, 213-225.
37.T. Renouard, R. A. Fallahpour, M. K. Nazeeruddin, R. Humphry- Baker, S. I. Gorelsky, A. B. P. Lever, and M. Gratzel, Inorg. Chem. 2002, 41, 367-378.
38.E. Figgemeier, V. Aranyos, E. C. Constable, R. W. Handel, C. E. Housecroft, C. Risinger, A. Hagfeldt, and E. Mukhtar, Inorg. Chem. Comm. 2004, 7, 117-121.
39.H. Rensmo, S. Sodergren, L. Patthey, K. Westmark, L. Vayssieres, O. Khole, P. A. Bruhwiler, A. Hagfeldt, and, H. Siegbahn, Chem. Phy. Lett. 1997, 274, 51-57.
40.C. Daul, E. J. Baerends, and, P. Vernooijs, Inorg. Chem. 1994, 33, 3538-3543.
41.J. E. Monat, J. H. Rodrigues, and J. K. McCusker, J. Phys. Chem. A 2002, 106, 7399-7406.
42.J. F. Guillemoles, V. Barone, L. Joubert, and C. Adamo, J. Phys. Chem. A 2002, 106, 11354-11360.
43.H. Zabri, I. Gillaizeau, C. A. Bignozzi, S. Caramori, M. F. Charlot, J. Cano-Boquera, and F. Odobel, Inorg. Chem. 2003, 42, 6655-6666.
44.S. Fantacci, F. De Angelis, and A. Selloni, J. Am. Chem. Soc. 2003, 125, 4381-4387.
45.H. Choi, C. Baik, S. Kim, M.-S. Kang, X. Xu, H. S. Kang, S. O. Kang, J. Ko, M. K. Nazeeruddin, and M. Gratzel, New J. Chem.2008, 32, 2233–2237.
46.數據由本實驗室博班學長陳家原、吳錫章及李政穎提供。

指導教授

吳春桂(Chun-Guey Wu)

審核日期

2009-7-22

推文