臺灣博碩士論文加值系統

本篇論文之主體大環乃針對本實驗室在2017年發表於J. Phys. Chem. C 的 LS-11染料進行結構上修飾，特別是對推電子基基團加以改性，成功合成出LS-44及LS-45兩支染料，推電子基基團乃是參考本實驗室在2016年Energy Environ. Sci.發表的LWP13及LWP14兩支染料。LS-11、LS-44與LS-45之拉電子基部分皆以benzoic acid作為錨定基團，LS-11的推電子基為4-ethynyl-N,N-dioctylaniline；LS-44為dioctylamino group；LS-45則為diarylamino group。另外還參考LS-01染料，成功合成出LS-01'及LS-01''兩支具有多酸根的染料，希望能提高它們的水溶性。
LS-44及LS-45兩支染料皆已通過核磁共振光譜儀1H-NMR及13C-NMR、MALDI TOF 質譜儀、元素分析 (EA) 的鑑定，確認了這兩支染料的結構及分子量。
藉由 DFT 理論計算、電化學性質、紫外光-可見光譜儀的協助，我們觀察到 LS-44 及 LS-45 染料具有成為染料敏化太陽能電池中敏化劑的優勢。

In this work, LS-44, LS-45, LS-01' and LS-01'' were successfully synthesized, characterized, and studied.
The macrocycles of this thesis are chromophores with structurally modified structures of the LS-11 dye (J. Phys. Chem. C, 2017). The electron-donating groups of the new dyes are based on those of our 2016 Energy Environ. Sci. paper, namely the LWP13 and LWP14 dyes. LS-11, LS-44 and LS-45 all use a benzoic acid as the anchor group. The electron-donating group of LS-11 is 4-ethynyl-N,N-dioctylaniline; LS-44 uses a dioctylamino group; and LS-45 uses a diarylamino group.
Both LS-44 and LS-45 dyes have been characterized by 1H and 13C-NMR, MALDI TOF mass spectrometry and elemental analysis.
Through DFT calculations, electrochemical measurements, UV-visible absorptions and fluorescent emissions, the experimental data show that the LS-44 and LS-45 dyes are adeguate dyes for dye-sensitized solar cells.

謝誌 i
摘要 ii
Abstract iii
目次 iv
表目次 vi
圖目次 vii
第一章 序論 1
1-1 前言 1
1-2 光動力療法 3
1-3 太陽能電池 4
第二章 染料敏化太陽能電池簡介 8
2-1 染料敏化太陽能電池簡介 8
2-2 染料敏化太陽能電池結構 9
2-3 染料敏化太陽能電池工作原理 14
2-4 染料光敏劑之研究 16
2-4-1 釕金屬錯合物光敏劑 16
2-4-2 有機分子敏化劑 18
2-4-3 紫質敏化劑 22
2-4-4 菌綠素敏化劑 28
2-5 染料堆疊情況 34
2-6 染料敏化太陽能電池之光伏性質測量 35
2-7 入射單色光子-電子轉換效率 (IPCE) 36
2-8 交叉耦合反應 (Sonogashira cross-coupling) 37
2-8 研究動機 38
第三章 實驗部分 40
3-1 實驗材料及儀器設備 40
3-2 管柱層析法 45
3-3 量子產率計算 45
3-4 莫耳吸收係數測定 46
3-5 染料光敏劑之合成步驟與鑑定資料 47
3-5-1 化合物 LS-00 合成步驟 47
3-5-2 化合物 Br-BC-TIPS 合成步驟 48
3-5-3 化合物 LS-44 合成步驟 49
3-5-4 化合物 LS-45 合成步驟 50
3-5-5 化合物 LS-01'合成步驟 51
3-5-6 化合物 LS-01''合成步驟 52
第四章 結果與討論 80
4-1 具濃縮推電子基團之菌綠素與紫質敏化劑 80
4-1-1 菌綠素敏化劑溶解於 THF 之紫外光-可見光吸收光譜 81
4-1-2 菌綠素敏化劑吸附於二氧化鈦薄膜之紫外光-可見光吸收光譜 83
4-1-3 菌綠素敏化劑溶於 THF 之螢光放射光譜 84
4-1-4 菌綠素敏化劑溶於 THF 之螢光量子產率 86
4-1-5 菌綠素敏化劑之 density-functional theory (DFT) 理論計算 88
4-1-6 菌綠素敏化劑之電化學性質 89
4-1-7 菌綠素敏化劑之電子能階 92
4-1-8 結論 95
4-2 新穎多酸根之菌綠素與紫質敏化劑 96
4-2-1 菌綠素敏化劑溶解於 THF 之紫外光-可見光吸收光譜 97
4-2-2 菌綠素敏化劑吸附於二氧化鈦薄膜之紫外光-可見光吸收光譜 99
4-2-3 菌綠素敏化劑溶於 THF 之螢光放射光譜 100
4-2-4 菌綠素敏化劑溶於 THF 之螢光量子產率 102
4-2-5 菌綠素敏化劑之 density-functional theory (DFT) 理論計算 104
4-2-6 菌綠素敏化劑之電化學性質 105
4-2-7 結論 107
參考文獻 108
附錄 113
附錄1 氫譜、碳譜與質譜 113
附錄2 元素分析 125

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