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| 題名: | 新型三吡啶鋨錯合物染料 合成與配位基效應之探討 |
| 作者: | 黃品嘉;Huang, Pin-Chia |
| 貢獻者: | 化學學系 |
| 關鍵詞: | 鋨錯合物 |
| 日期: | 2022-09-26 |
| 上傳時間: | 2022-10-04 11:01:50 (UTC+8) |
| 出版者: | 國立中央大學 |
| 摘要: | 在染料敏化太陽能電池(Dye-sensitized solar cells，DSCs)的研究中，鋨錯合物的探討極為稀少，但重原子效應(Heavy atom effect)具有可使鋨錯合物更有效地吸收近紅外光光子的優點，有機會藉此拓展其敏化電池元件的響應波長範圍與提高光電流密度。本研究以CYC-33O為基礎，合成兩個新型鋨錯合物染料(CYC-45Cl及CYC-45I)，其分子設計是透過在固著配位基的吡啶4號位上以2-Methylthiophene取代原有的羧基，搭配在雙吡啶(bpy)的4、4’位置連接Hexyl-EDOT作為輔助配位基，並在單牙基分別以氯離子與碘離子進行配位，期望藉此剖析與鋨原子同為重原子的碘元素能否進一步提高敏化元件的響應波長範圍。在CYC-45Cl的部分，我們嘗試了三種合成條件，最終發現以正丁醇+乙二醇的條件分別進行固著及輔助配位基的配位，另搭配40當量氫氧化鉀及四氫呋喃進行水解可順利得到最終產物。CYC-45I的合成則是以氫碘酸搭配(NH4)2OsCl6進行碘離子置換，合成出(TBA)2OsI6作為配位反應的起始物，並依循CYC-45Cl的合成條件且延長反應時間(16 h)與升高溫度(至195 oC)，再搭配5當量氫氧化鉀及四氫呋喃進行水解反應。CYC-45系列由於固著配位基擁有較高共軛程度，吸收係數及吸收範圍相較CYC-33O都有明顯提高，其中以CYC-45Cl具最高吸收係數(30900 M-1 cm-1，波長548 nm)以及最寬廣吸光波段(onset為941 nm)。對比於CYC-45Cl與CYC-33O， CYC-45I可使元件IPCE具最優異的光子轉換電流效率，Jsc值達11.38 (mA cm-2)，且由於CYC-45I移除了CYC-33O輔助配位基的硫原子，進一步降低了電荷再結合的發生，也因此CYC-45I敏化元件的Voc值(531 mV)亦為三者最高，整體效能達4.11%。經初步優化TiO2層數與電解液中的BMII濃度，CYC-45I敏化元件效率可分別提高至4.24%與4.76%，此展現CYC-45I的高應用潛力。;The study of osmium complexes for dye-sensitized solar cells (DSCs) is extremely rare. However, heavy atom effect can endow osmium complexes with efficient absorption capacity at near infrared region, having the opportunity to expand the spectral response for the sensitized cells and to increase the short-circuit current density. In this study, based on CYC-33O, two new osmium complex dyes (coded CYC-45Cl and CYC-45I) were synthesized. The molecular design for improving light-harvesting ability of osmium complexes and exploring the heavy atom effect is substituting 2-methylthiophene at the 4-position of pyridine of the anchoring ligand, attaaching Hexyl-EDOT at the 4,4′ positions of the ancillary bipyridine ligands, and using respectively chloride and iodide as monodentate. For the preparation of CYC-45Cl, three synthesis conditions were tested. It was finally found that the conditions of using n-butanol and ethylene glycol as solvent for coordinating the anchoring and ancillary ligands respectively. 40 eq. of potassium hydroxide and tetrahydrofuran were apprpriate for the hydrolysis. For CYC-45I, (TBA)2OsI6 were preparing by (NH4)2OsCl6 and hydriodic acid were used as the starting material for the coordination, followed by the similar synthesis conditions as those for CYC-45Cl. Practically, the reaction time for CYC-45I was prolonged (16 h) with higher temperature of 195 oC, and then 5 eq. of potassium hydroxide and tetrahydrofuran were used for hydrolysis. Owing to the highly conjugating anchoring ligand, CYC-45 series of osmium complexes display that the absorption coefficient and wavelength range are both superior to those of CYC-33O. Among them, CYC-45Cl shows the highest absorption coefficient (30900 M-1 cm-1) at 548 nm and the broadest absorption band (onset of 941 nm). Compared with CYC-45Cl and CYC-33O, the IPCE spectrum of CYC-45I sensitized device shows the best conversion of photon to current, which attribute to the highest Jsc value of 11.38 mA cm-2. The device based on CYC-45I also provide the highest Voc value of 531 mV and the best power conversion efficiency (PCE) of 4.11%, which should be ascribed to that the removal of sulfur atoms in CYC-33O could reduce charge recombination. After preliminary optimization of device fabrication condition (the number of TiO2 layers and the concentration of BMII in electrolyte), the PCE based on CYC-45I increased to 4.24%, and 4.76%, respectively. These results indicate the high application potential of CYC-45I. |
| 顯示於類別: | [化學研究所] 博碩士論文
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