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

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許博雲(Po-Yun Hsu) 查詢紙本館藏

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化學學系

論文名稱

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
(Synthesis of Novel Thiocyanate-free Ru-Base Photosensitizer for Dye-sensitized Solar Cell Applications)

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摘要(中)

染料是染料敏化太陽能電池中的重要組成，扮演著決定光電流大小
的角色。以釕金屬為中心的高效率錯合物染料通常是以兩個雙芽基
bipyridine 及兩個單芽基 Thiocyanate ligand (NCS)所組成的六配位錯合物，但單芽基的 NCS 配位穩定度低。本論文的研究重點即用bipyridine-pyrazolate ligand 取代NCS ligand合成出含一個4,4′-dicarboxy-2,2′-bipyrdine (dcbpy)及兩個 bipyridine-pyrazolate 之六配位釕錯合物 CYC-B29。CYC-B29 有三種異構物 CYC-B29-1、CYC-B29-2、CYC-B29-3，本論文利用 1H-NMR 鑑定 CYC-B29-1、CYC-B29-2 及 CYC-B29-3 的結構。UV-Vis 測量其吸收光譜，三個異構物有不同的最大吸收波長分別為539 nm、520 nm 及 521 nm，但DFT 理論計算所得到的前沿軌域電子雲分布相似，HOMO 皆主要落於金屬中心，LUMO 則落於 dcbpy。由 CYC-B29-1、CYC-B29-2 CYC-B29-3 所組成之 DSSCs 電池元件光電轉換效率分別為 4.71 %、1.03 %及4.84 %。CYC-B29-3 有最小的暗電流且在光陽極有最多的染料吸附量而有最高的光電轉換效率。

摘要(英)

Dye is an important component in the dye-sensitized solar cells which determine the photocurrent of the device. The Ruthenium, based on high-efficiency dyes are, usually six-coordinated complexes are composing of two Bidentate bipyridine ligands and two monodentate Thiocyanate(NCS) ligands. However, the stability of thiocyanate is poor. This thesis focused on using bipyridinepyrazolate ligand to replace NCS
ligand. A Ru-based 6-coordintated complex (CYC-B29) coating 4,4’’-dicarboxy-2,2’’-bipyridine (dcbpy) ligand and two bipyridine-pyrazolate ligands has been prepared. Unsymmetric CYC-B29 has three isomers CYC-B29-1, CYC-B29-2, and CYC-B29-3. The structure of CYC-B29 was determined by 1H-NMR spectroscopy. UV-Vis absorption
spectrum showed that the absorption maxima of the three isomers were 539 nm, 520 nm, and 521 nm respectively. Nevertheless the electron density distribution of the frontier orbital calculated by the density functional theory (DFT), for CYC-B29-1, CYC-B29-2, and CYC-B29-3 are similar. HOMO contributed mainly on the metal centre, and LUMO contributed from dcbpy ligand. The conversion efficiency of dye sensitized solar cells based on CYC-B29-1, CYC-B29-2, and CYC-B29-3 are 4.71 %, 1.03 %, and 4.84 % respectively. CYC-B29-3 has the smallest dark current and the largest dye-loading in photoanode, therefore has the highest photo-to-current conversion efficiency.

關鍵字(中)

★ 染料
★ 太陽能
★ 染料敏化
★ 釕金屬

關鍵字(英)

★ Dye sensitized
★ DSSCs
★ ruthenium dye
★ thiocyanate free

論文目次

目錄
中文摘要…………………………………………………………………I
英文摘要………………………………………………………………II
目錄……………………………………………………………………III
圖目錄…………………………………………………………………VII
表目錄…………………………………………………………………X
壹、緒論…………………………………………………………………1
1-1、前言………………………………………………………………1
1-2、太陽能電池的種類………………………………………………2
1-3、光電效率的測量…………………………………………………2
1-3-1、IPCE (Incident Photo to Current Conversion………… Efficiency)……………………………………………………………3
1-3-2、總光電轉換效率 (η)…………………………………………4
1-4、染料敏化太陽能電池 (Dye-Sensitized Solar Cells, DSSCs)……………………………………………………………………………4
1-5、染料敏化太陽能電池的工作原理………………………………6
1-6、光敏化劑-染料概述………………………………………………7
1-6-1、釕金屬錯合物染料(Ruthenium Matal Complex)……………8
1-6-2、輔助配位基(Ancillary Ligand)的修飾……………………10
1-6-2-1、使用疏水性長碳鏈，增加電池元件長時間穩定性………10
1-6-2-2、利用共軛單元，增加染料分子吸光能力…………………12
1-6-3、固著配位基(Anchoring Ligand)的修飾……………………16
1-6-4、Thiocyanate ligand在釕金屬配位錯合物上的穩定性……20
1-6-5、不含Thiocyanate ligand的釕金屬錯合物…………………21
1-7、研究動機…………………………………………………………25
貳、實驗部份
2-1、實驗藥品…………………………………………………………27
2-2、儀器分析與樣品製備……………………………………………31
2-2-1、核磁共振光譜儀 (NMR)………………………………31
2-2-2、紫外光/可見光吸收光譜儀 (UV/VisSpectrometer)31
2-2-3、紅外光吸收光譜儀 (FT-IRSpectrometer)…………32
2-2-4、Electrochemical Measurement；電化學測量裝置
(AUTOLAB PGSTAT30,電流/電位儀)…………………33
2-2-5、螢光光譜儀；Emission Spectroscopy (FluoroMax-4
spectro-fluorometer (HORIBA JOBIN YVON))…33
2-3、合成步驟…………………………………………………………35
2-3-1、4-Bromopyridine的製備……………………………36
2-3-2、合成4-Bromopyridine N-oxide……………………36
2-3-3、合成4-Bromo-2-pyridine-carbonitrile…………37
2-3-4、合成5-Thiohexyl-(3,4-ethylenedioxy) …………
thiophene………………………………………………37
2-3-5、合成(5-Thiohexyl-(3,4-ethylenedioxy thiophene-
2-yl))trimethylstannane……………………………38
2-3-6、合成(5-Thiohexyl-(3,4-ethylenedioxy thiophene- 2-yl))picolinonitrile………………………………39
2-3-7、合成1-(4-(5-Thiohexyl-(3,4-ethylenedioxy………
thiophene-2-yl))pyridinine-yl)ethanone………40
2-3-8、合成4-(5-Thiohexyl-(3,4-ethylenedioxy…………
thiophene-2-yl))-2-(3-(trifloeomethyl-1H-……
pyrazol-5-yl)pyridine……………………………42
2-4、合成釕金屬錯合物(CYC-B29-OEt)……………………………44
2-4-1、合成 [Ru(diethyl2,2’’-bipyridine-4,4’’-…………
dicarboxylate) (p-cymene)(Cl)]+…………………………45
2-4-2、合成 Ru(L29)2(diethyl2,2’’-bipyridine-…………
4,4’’dicarboxylate)…………………………………………46
2-5、合成釕金屬錯合物CYC-B29-1、CYC-B29-2及CYC-B29-3…49
叁、結果與討論………………………………………………………50
3-1、L29與CYC-B29系列合成探討……………………………………50
3-2、CYC-B29-1、CYC-B29-2及CYC-B29-3光學性質探討…………53
3-3、由理論計算所得之CYC-B29-1、CYC-B29-2、CYC-B29-3分子
的前置軌域……………………………………………………58
3-4、CYC-B29-1能階結構探討………………………………………62
3-5、使用CYC-B29-1、CYC-B29-2及CYC-B29-3做為敏化劑所組
裝成之電池元件的效能探討……………………………………64
肆、結論………………………………………………………………70
伍、參考文獻…………………………………………………………71
附錄……………………………………………………………………74

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2012-7-26

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