臺灣博碩士論文加值系統

提升太陽能染料電池的光電轉換效率，一直是科學家努力的目標。本篇研究針對 [Ru(dcbpy)2 (8-OQN)]+ (dcbpy=4, 4'-dicarboxy-2, 2' bipyridyl, and 8-OQN = 8-oxyquinolate)錯合物與 I- 進行電子轉移的分析，模擬過去文獻中染料與 I-/I3- 氧化還原對的反應機制，藉由 [Ru(dcbpy)2(5,7-di-X-8-OQN)]+ (X=H, F, Cl, Br, I, Me)系列的錯合物來計算，觀察推拉電子基對電子轉移能障的影響。

The enhancement of the photoelectric conversion efficiency of dye-sensitized solar cells(DSSC) has been a consistently significant topic to scientist. In this work, we analyze the electron transfer of [Ru(dcbpy)2(8-OQN)]+ (dcbpy=4,4'-dicarboxy-2,2' bipyridyl, and 8-OQN=8-oxyquinolate) with I- , Simulating the reaction mechanism of dye and redox couple (I- /I3- ). Also, we change the complex to [Ru(dcbpy)2(5,7-di-X-8-OQN)]+ (X=H, F, Cl, Br, I, Me) to study the difference of the barrier of electron transfer with different electron push-pull functionalities.

總目錄
圖目錄 IV
表目錄 VI
PART_1
中文摘要 1
Abstract 1
第一章 緒論 2
1-1 前言 2
1-2 染料敏化太陽能電池的發展背景 3
1-3 染料敏化太陽能電池的結構與工作原理 4
1-4 氧化態染料被電解質還原的反應機制 7
第二章 計算原理 9
2-1 量子力學 9
2-2 計算化學的理論及方法 10
2-2-1 密度泛函理論 (DENSITY FUNCTIONAL THEORY) 10
2-2-2 基底函數 (BASIS SETS) 11
2-3 計算方法 12
2-3-1單點能量 (SINGLE POINT ENERGY) 12
2-3-2幾何優化 (GEOMETRY OPTIMIZATIONS) 12
2-3-3振動頻率 (FREQUENCY) 13
2-3-4溶劑效應 13
2-4 本論文使用的計算方法 14
第三章 結果與討論 15
3-1 研究目標 15
3-2 幾何結構討論 15
3-3 染料和第一個I-電子轉換 18
3-3-1 YE05_X和第一個I-的電子轉換能障分析 18
3-3-2 RU-8-OQN_Y和第一個I-的電子轉換能障分析 23
3-4染料和第二個I-電子轉換 28
3-4-1 YE05_X和第二個I- 的電子轉換能障分析 28
3-4-2 RU-8-OQN_Y和第二個I- 的電子轉換能障分析 33
3-5 I- 單獨與官能基的結合能 38
第四章 結論 40
第五章 參考文獻 41
PART_2
SYNOPSIS
ABSTRACT 45
中文摘要 46
Introduction 47
Results and Discussion 51
Synthesis. 51
Computational analysis 52
UV/Vis electronic absorption spectra and TDDFT. 56
Electrochemistry 61
EPR and UV/Vis/NIR spectroelectrochemistry 64
Conclusions 70
Experimental Section 71
Computational Details 72
References 78
Supporting Information 82
Supporting Information Contents 83






圖目錄
PART_1
Figure 1: DSSC的結構圖。 4
Figure 2: DSSC工作原理的路徑圖。 5
Figure 3: DSSC 運作機制的相對時間圖。 6
Figure 4:勢能面（Potential Energy Surface, PES）的示意圖。 13
Figure 5: RuIII-8-OQN、RuIII-8-OQN-I-和RuII-8-OQN-I2-的幾何結構。 16
Figure 6: YE05+2、YE05+2-I- 和YE05+1-I2- 的幾何結構。 17
Figure 7: YE05_X (X=H、F、Cl、Br、I、Me)的幾何結構。 18
Figure 8-13: YE05_X+1跟I- 之間的相對距離和能量；YE05_X跟I．之間的相對距離和能量(X= H、F、Cl、Br、I、Me)。 19-21
Figure 14: Ru-8-OQN_Y (Y=H、F、Cl、Br、I、Me)的幾何結構。 23
Figure 15-20: Ru-8-OQN_Y+1跟I- 之間的相對距離和能量；Ru-8-OQN_Y跟I．之間的相對距離和能量(X= H、F、Cl、Br、I、Me)。 24-26
Figure 21: [YE05_Y．I-] (Y=H、F、Cl、Br、I、Me)的幾何結構。 28
Figure 22-27: [YE05_X+1．I-]跟I-之間的相對距離和能量；[YE05_X．I-]跟I．之間的相對距離和能量(X= H、F、Cl、Br、I、Me)。 29-31
Figure 28: [Ru-8-OQN_X．I-] (X=H、F、Cl、Br、I、Me)的幾何結構。 33
Figure 29-34: [Ru-8-OQN_Y+1．I-]跟I-之間的相對距離和能量；[Ru-8-OQN_Y．I-]跟I．之間的相對距離和能量(X= H、F、Cl、Br、I、Me)。 34-36
PART_2
Figure 1: Structures of [Ru(bpy)2(R-OQN)]+ complexes 2+ – 8+ here investigated including the [Ru(bpy)3]2+ reference complex 12+. 50
Figure 2: Aerial and side-on perspective views of both the HOMO and HOMO-3 levels for 2+ illustrating the π-bonding/anti-bonding combination of Ru(dπ) and OQN(π) systems. 53
Figure 3: Percentage contributions of Ru, OQN, TPA and bpy fragments to frontier molecular orbitals of 8+. 54
Figure 4: A plot of molecular orbital energy levels (eV) for complexes 12+ - 8+. 55
Figure 5: Overlay of UV/Vis electronic absorption spectra of select complexes (for clarity) recorded in acetonitrile. 56
Figure 6: An overlay of experimental and theoretical TD-DFT spectra for 8+ in acetonitrile. 57
Figure 7: Select molecular orbitals for 8+ determined responsible for the major UV/Vis electronic transitions by TD-DFT analysis. 58
Figure 8: Overlay of cyclic voltammograms for 12+ [Ru(bpy)3]2+, and the 5,7-substituted [Ru(bpy)2(R-OQN)]+ derivatives 6+, 7+ and 8+. 63
Figure 9: X-band EPR (9.5 GHz) spectroelectrochemical data for 62+ and 82+. 66
Figure 10: Mulliken spin-density analysis illustrating hole-delocalization onto the R-OQN ligands of 22+ - 82+, relative to the spin-localized [RuIII(bpy)3]3+ system 13+. 67
Figure 11: UV/Vis/NIR electronic absorption data of 82+. 69
Figure 12: Overlay of UV/Vis/NIR electronic absorption data recorded following controlled potential electrolysis of 13+ and complexes 22+, 32+, 62+, 72+ and 82+. 70
表目錄
PART_1
Table 1: RuIII-8-OQN、RuIII-8-OQN-I-和RuII-8-OQN-I2-的鍵長鍵角表。 16
Table 2: YE05+2、YE05+2-I-和YE05+1-I2-的鍵長鍵角表。 17
Table 3: YE05_X (X=H、F、Cl、Br、I、Me)與I-電子轉移的能量障礙與相對距離表。 22
Table 4: Ru-8-OQN_Y (X=H、F、Cl、Br、I、Me)與I-電子轉移的能量障礙與相對距離表。 27
Table 5: [YE05_Y．I-] (Y=H、F、Cl、Br、I、Me)與第二I-電子轉移的能量障礙與相對距離表。 32
Table 6: [Ru-8-OQN_X．I-] (Y=H、F、Cl、Br、I、Me)與第二I-電子轉移的能量障礙與相對距離表。 37
Table 7:利用B3LYP、MP2與CCSD(T) functional計算出結合能和相對距離。 38
PART_2
Table 1: Metal-ligand contributions (%) to the HOMO of complexes 12+- 8+. 53
Table 2: Electronic absorption and phosphorescence emission data for complexes 12+-8+. 59
Table 3: Electrochemical data for selected complexes 12+ - 8+. 63
Table 4: EPR data of complexes following one electron oxidation. 66
Table 5: UV/Vis/NIR electronic absorption data for complexes 13+- 82+. 69

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