請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/40920
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 黃慶怡 | |
dc.contributor.author | Shan-Ni Wen | en |
dc.contributor.author | 溫珊妮 | zh_TW |
dc.date.accessioned | 2021-06-14T17:06:49Z | - |
dc.date.available | 2013-08-15 | |
dc.date.copyright | 2011-08-15 | |
dc.date.issued | 2011 | |
dc.date.submitted | 2011-08-11 | |
dc.identifier.citation | [1] http://only-perception.blogspot.com/2010/02/5.html
[2] J. Kawakita, QUARTERLY REVIEW 2010, 35, 70-82. [3] http://www.crunchgear.com/tag/mitsubishi-chemical/ [4] T. M. Clarke, J. R. Durrent, Chem. Rev. 2010, 110, 6736–6767. [5] A. Hagfeldt, G. Boschloo, L. Sun, et al. Chem. Rev. 2010, 110, 6595–6663. [6] B. O’Regan, M. Grätzel, Nature 1991, 353, 737-740. [7] D. Kuang, S. Ito, B. Wenger, et al. J. Am. Chem. Soc. 2006, 128, 4146-4154. [8] K. Hara, Y. Dan-oh, C. Kasada, et al. Langmuir 2004, 20, 4205-4210. [9] M. K. Nazeeruddin, A. Kay, I. Rodicio, et al. J. Am. Chem. Soc. 1993, 115, 6382-6390. [10] M. K. Nazeeruddin, P. Pechy, M. Grätzel. Chem. Commun. 1997, 1705-1706. [11] M. K. Nazeeruddin, P. Pechy, T. Renouard, et al. J. Am. Chem. Soc. 2001, 123, 1613-1624. [12] M. K. Nazeeruddin, S. M. Zakeeruddin, R. Humphry-Baker, et al. Inorg. Chem. 1999, 38, 6298-6305. [13] A. Mishra, M. K. R. Fischer, P. Bauerle, Angew. Chem. Int. Ed. 2009, 48, 2474 – 2499. [14] Y. Ooyama, Y. Harima, Eur. J. Org. Chem. 2009, 2903–2934. [15] K. Hara, K. Sayama, Y. Ohga, et al. Chem. Commun. 2001, 569–570. [16] K. Hara, M. Kurashige, Y. Dan-oh, et al. New J. Chem., 2003, 27, 783–785. [17] T. Horiuchi, H. Miura, S. Uchida, Chem. Commun. 2003, 3036-3037. [18] T. Horiuchi, H. Miura, K. Sumioka, et al. J. Am. Chem. Soc. 2004, 126, 12218-12219. 103 [19] W. H. Howie, F. Claeyssens, H. Miura, et al. J. Am. Chem. Soc. 2008, 130, 1367-1375. [20] S. M. Zakeeruddin, M. Grätzel, Adv. Funct. Mater. 2009, 19, 2187–2202. [21] W. Zeng, Y. Cao, Y. Bai, et al. Chem. Mater. 2010, 22, 1915–1925. [22] N. Cai, S. Moon, L. Cevey-Ha, et al. Nano Lett. 2011, 11, 1452–1456. [23] Q. Yu, Y. Wang, Z. Yi, et al. ACS Nano 2010, 4, 6032-6038. [24] H. Choi, C. Baik, S. O. Kang, et al. Angew. Chem. Int. Ed. 2008, 47, 327 –330. [25] N. Koumura, Z. Wang, S. Mori, et al. J. Am. Chem. Soc. 2006, 128, 14256-14257. [26] Z. Wang, N. Koumura, Y. Cui, et al. Chem. Mater. 2008, 20, 3993-4003. [27] X. Zhang, Y. Cui, R. Katoh, et al. J. Phys. Chem. C 2010, 114, 18283–18290. [28] D. P. Hagberg, J. Yum, H. Lee, et al. J. Am. Chem. Soc. 2008, 130, 6259–6266. [29] C, Yang, S. Liao, Y. Sun, et al. J. Phys. Chem. C 2010, 114, 21786-21794. [30] L. H. Thomas, Proc. Cambridge Philos. Soc. 1927, 23, 542-548. [31] E. Fermi, Z. Phys. 1928, 48, 73-79. [32] P. Hohenberg, W. Kohn, Phys. Rev. 1964, 136, B864-B871. [33] P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys.Chem. 1994, 98, 11623-11627. [34] A. D. Becke, J. Chem. Phys.1993, 98, 5648-5652. [35] C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-789. [36] M. E. Casida, C. Jamorski, K. C. Casida, D. R. Salahub, J. Chem. Phys. 1998, 108, 4439-4449. [37] J. F. Haw, J. B. Nicholas, W. Song, et al. J. Am. Chem. Soc. 2000, 122, 4763-4775. 104 [38] W. Deng, J. R. Cheeseman, M. J. Frisch, J. Chem. Theory Comput. 2006, 2, 1028-1037. [39] M. B. Ponce, F. M. Cabrerizo, S. M. Bonesi, R. Erra-Balsells, Helvetica Chimica Acta 2006, 89, 1123-1139. [40] A. Kiss, Z. Hell, M. Balint, Org. Biomol. Chem. 2010, 8, 331-335. [41] O. Paliulis, J. Ostrauskaite, V. Gaidelis, et al. Macromol. Chem. Phys. 2003, 204, 1706-1712. [42] D. V. Allen, Methodology and Mechanism: Reinvestigating the Ullmann Reaction. 2004. [43] F. M. Deane, C. M. Miller, A. R. Maguire, F. O. McCarthy, J. Heterocyclic Chem. 2011, 48, 814-823. [44] E. Sperotto, G. P. M. van Klink, G. van Koten, J. G. de Vries. Dalton Trans. 2010, 39, 10338-10351. [45] J. C. Li, S. H. Lee, Y. B. Hahn, et al. Syn. Metals, 2008, 158, 150-156. [46] H. Dressler, J. E. Graham, J. Org. Chem. 1967, 32, 985-990. [47] M. Velusamy, K. R. Justin Thomas, J. T. Lin, et al. Org. Lett. 2005, 7, 1899-1902. [48] K. R. Justin Thomas, P. Singh, A. Baheti, et al. Dyes and Pigments, 2011, 91, 33-43. [49] A. Dreuw, M. Head-Gordon, J. Am. Chem. Soc. 2004, 126, 4007-4016. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/40920 | - |
dc.description.abstract | 本研究以donor-π bridge-acceptor為主要的設計架構,合成出一系列的有機染料-NW、NHW、NS與NHS。Donor以carbazole為主,共軛長度的延伸以thiophene為主,搭配強拉電子基benzothiadiazole,最後以常見的cyanoacetic acid當作注入基團。合成之中間體與化合物以核磁共振儀與質譜儀鑑定其分子結構,搭配紫外光-可見光光譜儀與循環伏安法量測染料分子的吸收係數、最大吸收波長、能隙值與HOMO、LUMO的能階值。最後以理論基礎DFT和TD-DFT輔助分析染料的光學與電化學性質,結構最佳化構形和分子軌域電荷分佈情形。
吸收光譜的表現上,染料的確隨著共軛長度的延伸而使得吸收譜線愈紅位移,能隙值愈小。導入推電子基carbazole也會使得吸收譜線愈紅位移。從CV圖可以發現,在不延伸共軛長度的前提下(NHW與NHS),推電子基carbazole對於HOMO能階值的提升很有限,因為carbazole不是一個強推電子基,不過還是可以看到HOMO值有些微的提升,LUMO值有些微的下降。在延伸共軛長度的前提下(NW與NS),HOMO值雖然也有些微的提升,但LUMO值隨著能隙變得更小而降低。從以上的結果得知延伸共軛長度,能有效的縮減能隙,讓分子的LUMO值隨之降低。理論計算出的結果,可以發現不管是導入donor或是延伸共軛長度,皆可以提升HOMO值,與有效的降低能隙,達到更紅位移的效果。吸收光譜的理論計算波長相對大小與實驗值實際測得的數據相對大小趨勢一致。 | zh_TW |
dc.description.abstract | A series of new organic dyes, 2-cyano-3-(5-(7-(5-(9-ethyl-9H-carbazol-3-yl) thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)acrylic acid (NW), 3-(5- (7-(5-(9H-carbazol-9-yl)thiophen-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic acid (NHW), 2-cyano-3-(5-(7-(5'-(9-ethyl-9H-carbazol-3-yl) -3'-hexyl -2,2'-bithiophen-5-yl)benzo[c][1,2,5]thiadiazol-4-yl)thiophen-2-yl)acrylic acid (NS) and 3-(5-(7-(5'-(9H-carbazol-9-yl)-3'-hexyl-2,2'-bithiophen 5-yl)benzo[c][1,2,5] thiadiazol-4-yl)thiophen-2-yl)-2-cyanoacrylic acid (NHS), were designed and synthesized based on the structure of donor-π bridge-acceptor. Herein, carbazole, benzothiadiazole and cyanoacetic acid were used as donor, acceptor and anchoring group, respectively, in these dye molecules. All intermediates and final products were fully characterized using 1H-NMR, 13C-NMR and ESI mass. UV-vis spectrometer was employed to measure the extinction coefficient, absorption spectrum, and optical bandgap of N series organic dyes. The energy levels of HOMO and LUMO were also determined by cyclic voltammetry. Experimental results clearly indicated that the extension ofπ-conjugation length and the incorporation of carbazole as donor red-shifted the absorption spectrum and lowered the optical bandgap. Both NHW and NHS have similar conjugation length but the incorporation of carbazole in them had little effect on up-shifting the HOMO level. This is probably because carbazole is not a strong donor group. Moreover, comparing NW and NS showed the increment of conjugation length mainly down-shifted the LUMO level but kept HOMO almost unchanged, thus leading to the decrease in bandgap.
Additionally, the theoretical calculations of these dye molecules were performed in vacuum system. All the electronic absorption characteristics and HOMO, LUMO energy level were calculated by TD-DFT- B3LYP/ 6-31G / + / (d ) level of theory. We V can get the optimized structure and molecular orbital about electron distribution condition of the ground state and exicted state. The calculated HOMO level would be raised by inducing donor and extending the conjugation length. The absorption spectrum is in consistent with the experiment data. | en |
dc.description.provenance | Made available in DSpace on 2021-06-14T17:06:49Z (GMT). No. of bitstreams: 1 ntu-100-R98549035-1.pdf: 8340361 bytes, checksum: a77922ff7114b9f4c3f7e63fa4b27ca2 (MD5) Previous issue date: 2011 | en |
dc.description.tableofcontents | 謝誌 I
中文摘要 III 英文摘要 IV 目錄 VI 圖目錄 VIII 表目錄 XI 流程目錄 XI 化合物的結構圖與編號 XII 第一章、 緒論 1 1-1. 太陽能電池的簡介 1 1-2. 染料敏化太陽能電池的介紹 4 1-3. 有機染料的文獻回顧 6 1-4. 理論計算背景 13 1-5. 研究動機與方向 15 第二章、 實驗 17 2-1. 實驗藥品 17 2-2. 實驗儀器 19 2-3. 合成路徑 20 2-4. 合成方法 24 2-5. 理論計算 44 第三章、 結果與討論 46 3-1. 合成分析與氫譜分析 46 3-2. 2D-NMR分析 60 3-2-1. 化合物13之2D-NMR分析 61 VII 3-2-2. NHW之2D-NMR分析 68 3-2-3. NS之2D-NMR分析 73 3-3. 光電學性質分析 82 3-3-1. 紫外光可見光光譜分析 82 3-3-2. 循環伏安法 89 3-4. 理論計算分析 94 3-5. 元件數據 100 第四章、 結論 101 第五章、 參考文獻 102 附錄I 化合物之核磁共振光譜圖 105 附錄 Ⅱ N系列染料之電灑游離質譜圖 121 附錄 Ⅲ 二維核磁共振光譜圖 123 | |
dc.language.iso | zh-TW | |
dc.title | 新穎咔唑衍生有機染料之合成、性質分析與理論計算 | zh_TW |
dc.title | Synthesis、Characterization and Simulation of Novel Carbazole Derivative Organic Dyes | en |
dc.type | Thesis | |
dc.date.schoolyear | 99-2 | |
dc.description.degree | 碩士 | |
dc.contributor.coadvisor | 王立義 | |
dc.contributor.oralexamcommittee | 梁文傑,林金福 | |
dc.subject.keyword | 有機染料,染料敏化太陽能電池,咔,唑,苯并噻,二唑,密度泛函理論,時間相關密度泛函理論, | zh_TW |
dc.subject.keyword | organic dyes,dye-sensitized solar cells,carbazole,benzothiadiazole,density functional theory (DFT),time-dependent density functional theory (TD-DFT), | en |
dc.relation.page | 127 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2011-08-12 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
顯示於系所單位: | 高分子科學與工程學研究所 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-100-1.pdf 目前未授權公開取用 | 8.14 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。