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標題: | 奈米化六氰釕化鐵搭配金屬超分子高分子或紫精應用於電致色變元件 Eletrochromic Devices Based on Nanoparticulated Ruthenium Purple and Metallo-supramolecular Polymer or Viologen |
作者: | Yen-Chun Wang 王彥鈞 |
指導教授: | 何國川 |
關鍵字: | 電致色變元件,普魯士藍類似物,六氰釕化鐵,表面修飾,全波段吸收, Electrochromic device,Prussian blue analogue,Ruthenium purple,Surface modification,Panchromatic, |
出版年 : | 2018 |
學位: | 碩士 |
摘要: | 近年來,一種新穎的普魯士藍類似物六氰釕化鐵逐漸地受到關注,主要是因為其光學吸收的位置靠近可見光的中心(即545 nm),使得人眼對於六氰釕化鐵的顏色變化十分的敏感。
本研究第三章以表面修飾法來對六氰釕化鐵進行改質,此修飾法伴隨著奈米化的過程使得最終獲得的六氰釕化鐵具有奈米級的尺度,同時具有在水中均勻分散的優勢。與未經過修飾的微米級六氰釕化鐵比較後可以發現奈米六氰釕化鐵在電學與光學上均具有明顯的改善。為了將此經過改質的奈米級六氰釕化鐵推向更實際的應用,一種陰極著色材料鐵金屬超分子高分子被選用來與奈米六氰釕化鐵搭配製備出互補式電致色變元件。因為鐵金屬超分子高分子的光學吸收峰的位置(580 nm)與六氰釕化鐵的吸收峰位置十分接近,因此當兩種著色材料在元件中著色時,將會加強整體元件的色彩。此元件在二極式系統0.3 V與1.3 V的操作下具有50.7%之光學穿透度變化、短的著去色響應時間(0.4 s)、高著色效率(512.5 cm2/C),並在10,000圈操作後仍保持其最初96.4%之光學度穿透度變化。 本研究的第四章中利用第三章所得到的奈米六氰釕化鐵來製備可見光全波段吸收的電致色變元件。為了彌補其他波段的光學吸收,苯基紫精被選用來與奈米六氰釕化鐵搭配。在研究過程中利用了不同的普魯士藍類似物與紫精來證明對電極上較低的紫精反應量是受到工作電極上的奈米六氰釕化鐵具有較大電阻的影響。經過實驗的設計也解釋了穿透度變化中所出現的特別的著去色現象,並思考出改進的方式。最終藉著在六氰釕化鐵薄膜中加入奈米碳管來改善電子傳導的能力,成功地提升了紫精在對電極上的反應量。因此元件成功具有可見光全波段吸收的能力,同時在施加不同電壓時會具有不同的色彩。在二極式系統-0.6 V與1.0 V的操作下具有61.6%的光學穿透度變化、短的著去色響應時間(少於3 s)與不錯的長期穩定性(10,000圈保值原本之70.7%)。 A novel Prussian blue analogue, ruthenium purple (Fe4[Ru(CN)6]3, RP), has attracted attention recently. Due to the optical absorbance peak (at 545 nm) locating at the middle of visible region, the vivid color change is sensitive to human eyes. In Chapter 3, we introduce a simple surface modification during RP preparation. Based on this nanoparticulating process, water-dispersible RP nanoparticles (nRP) can be produced. Compared to general micro-scale RP particle (RP) which is without surface modification, the nanoparticle size of nRP results in the better charge transfer and therefore enhance the electrochromic performance. To make a complementary electrochromic device (ECD), a cathodically coloring material, Fe(II)-based metallo-supramolecular polymer (Fe(II)-MEPE), is chosen. Since the maximum absorbance peak of Fe(II)-MEPE (at 580 nm) is close to that of nRP, the synergistic optical change can be achieved. The Fe(II)-MEPE/RP ECD gave a transmittance change (∆T) of 50.7% at 580 nm when switching between 0.3 and 1.3 V in a two-electrode system. Fast bleaching and coloring response times of 0.4 s were obtained for the proposed ECD with an active area of 1.0 x 1.0 cm2. High coloration efficiency (512.5 cm2/C) of ECD was also acquired. This device remained 96.4% of its initial ΔT after 10,000 cycles of switching. In Chapter 4, we aim at fabricating a nRP-based panchromatic ECD. Phenyl viologen (PV) is chosen as a cathodically coloring material in order to compensate the optical absorption at other visible range. Different Prussian blue analogues and viologens are utilized in ECDs to study the low characteristic absorption of viologens at colored state. An experiment, controlled by different potential step, is utilized to discuss a special sudden coloring process and bleaching phenomenon observed during the dynamic transmittance change. An addition of carbon nanotube (CNT) in the nRP film provides an alternative path for the electron transportation, increasing the reacting amount of PV reduction reaction. The modified nRP/Fc+PV ECD exhibited panchromatic absorption and multiple colors under different potential biases. The ECD gave a ΔT of 61.6% at 600 nm upon a potential step between -0.6 to 1.0 V in a two-electrode system, and the fast response times less than 3 s were obtained with an active area of 1.0 x 1.0 cm2. This device remained 70.7% of its initial ΔT after 10,000 cycles of switching. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/7515 |
DOI: | 10.6342/NTU201802723 |
全文授權: | 同意授權(全球公開) |
電子全文公開日期: | 2023-08-14 |
顯示於系所單位: | 化學工程學系 |
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