臺灣博碩士論文加值系統

本研究中以玻璃碳、白金、鎢…等電極探討金屬(如：錳與銀)與導電高分子(如：polycarbazole與polypyrrole)於離子液體中的電化學行為，並且將研究中所有電沉積得到的樣品以掃描式電子顯微鏡(SEM)與能量分散光譜儀(EDS)進行表面結構的觀測與元素的分析。實驗中使用的離子液體種類如下：
(1) BMI-PF6 (1-butyl-3-methylimidazolium hexafluorophosphate)
(2) BMP-Tf2N (N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfonyl)imide)
(3) BMP-DCA (N-butyl-N-methylpyrrolidinium dicyanamide)
錳的電化學行為於BMP-DCA離子液體中進行探討，因為發現離子液體組成中的DCA陰離子具有很好的錯合配位能力，可以幫助氯化錳(MnCl2)溶解於離子液體中，提供不同於傳統上氧化電解金屬錳塊以提供Mn(II)離子的來源途徑。錳的鍍層樣品藉由定電位的方式電沉積於銅絲、銅片上，並且利用粉末X光繞射光譜儀(XRD)來觀察鍍層的晶格排列。成功於BMP-DCA離子液體中製備出高純度且沒有晶形的錳鍍層。
我們從BMI-PF6與BMP-TF2N離子液體中製備出高品質的polycarbazole(PCz)電致色變薄膜。其結構穩定、附著性強，同時氧化狀態下(深綠色)與還原狀態下(淡綠色) 表現出不同強度的顏色。另外在兩種離子液體中探討Cz單體與PCz薄膜的電化學行為以及PCz薄膜的電致色變現象。Indium tin oxide (ITO)電極上的PCz薄膜以定電位、電位脈衝、循環伏安法等電化學方式來製備。本實驗以離子液體作為PCz的聚合環境，克服了Cz在有機溶劑或水溶液中聚合時所遭遇的困擾(如：聚合薄膜呈現粉末狀、結構不穩定、附著性差、聚合物製備的量有限)，所得之結構穩定且導電的PCz材料，有機會成為包覆觸媒的導電材料。
Pyrrole(Py)與銀的電化學行為於BMI-PF6與BMP-TF2N離子液體中詳加探討。利用定電位與電位脈衝的方式將PPy/Ag複合薄膜沉積於鎢絲上。發現以電位脈衝方式得到的複合材料，其PPy鍍層均勻的將銀包覆其中。結果發現可以藉著電位脈衝的方式製備出多孔、結構穩固的PPy/Ag複合薄膜，同時此PPy/Ag的複合材料有機會用於電化學催化。

This thesis reports the electrochemical behavior of metals (such as manganese and silver) and conducting polymers (such as polycarbazole and polypyrrole) in room-temperature ionic liquids at tungsten, platinum and glassy carbon electrodes, respectively. Ionic liquids used in this thesis include BMI-PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), BMP-Tf2N(N-butyl-N-methylpyrrolidinium bis((trifluoromethyl)sulfon-
yl)imide), and BMP-DCA (N-butyl-N-methylpyrrolidinium dicyanamide). All the electrodeposition samples were analyzed with scanning electron microscope (SEM) and energy-dispersive spectrometer (EDS). The electrochemistry of manganese was studied in BMP-DCA. It was found that dicyanamide anions exhibit good complexing ability that can assist MnCl2 to dissolve. The manganese coatings were prepared by controlled-
potential electrodeposition at copper foil or wire. Highly pure and amorphous Mn coatings can be obtained in BMP-DCA. The high-quality electrochromic polycarbazole (PCz) film that is stable, strongly adhesive, and show different color depth between oxidative state (deep green) and reductive state (light green) was obtained in BMP-Tf2N and BMI-PF6, respectively. The electrochemical behavior of Cz monomer and the PCz films and the electrochromic behavior of the PCz films in both ionic liquids were also investigated. The PCz films were electrodeposited at indium tin oxide (ITO) electrode by cyclic voltammetry, controlled-potential and potential pulse techniques. It is expected that the stable, conductive, and strongly adhesive PCz films are appropriate materials to eucapsulate catalysts upon electrode surface. The electrochemistry of pyrrole (Py) and silver (Ag) was studied in BMP-Tf2N and BMI-PF6, respectively. The PPy/Ag composite films were electrodeposited at tungsten wire by controlled-potential and potential pulse techniques. A porous, rigid structure of PPy/Ag composite films can be prepared by potential pulse electrodeposition and this material is possible to be used for electrocatalysis.

一、 緒論 1
1.1 融鹽的發展 1
1.2 室溫離子液體 2
1.3 室溫離子液體之發展與應用 5
二、 研究目的與方向 12
2.1 室溫離子液體中錳的研究 12
2.2 室溫離子液體中咔唑的研究 14
2.3 室溫離子液體中聚吡咯/銀之複合電極材料的研究 16
三、 實驗相關資料 21
3.1 實驗材料 21
3.2 離子液體的製備 27
3.2.1 BMI-PF6室溫離子液體 27
3.2.2 BMP-TF2N室溫離子液體 27
3.2.3 BMP-DCA室溫離子液體 28
3.3 實驗裝置儀器 30
3.3.1 實驗裝置 30
3.3.2 實驗儀器 31
3.4 電化學原理與方法 33
3.5 BMP-DCA室溫離子液體其黏度、密度的量測 36
四、 結果與討論 38
4.1 室溫離子液體的電位窗 38
4.1.1 BMI-PF6離子液體 38
4.1.2 BMP-TF2N離子液體 39
4.1.3 BMP-DCA離子液體 39
4.2 錳在BMP-DCA離子液體的電化學探討 48
4.2.1 錳金屬塊在BMP-DCA離子液體中的陽極溶解反應 48
4.2.2 氯化錳(MnCl2)在BMP-DCA離子液體中的溶解測試 51
4.2.3 Mn(II)在BMP-DCA離子液體中的電化學行為 51
4.2.4 電沉積錳鍍層的表面型態觀測、EDS與XRD分析 60
4.2.5 結果分析與討論 61
4.3 於離子液體內製備電致色材料─咔唑電聚合膜 66
4.3.1 咔唑單體在離子液體中的電化學行為 66
4.3.2 咔唑的電聚合方法及其聚合膜的電化學行為 67
4.3.3 電化學聚合咔唑導電高分子的機制 68
4.3.4 不同方法下製備的聚咔唑薄膜其表面結構的探討 75
4.3.5 ITO上的聚咔唑薄膜於離子液體中的變色現象探討 76
4.3.6 咔唑單體於離子液體中的光學性質探討 77
4.3.7 ITO上咔唑聚合膜的UV/VIS吸收及螢光表現 78
4.3.8 咔唑於濕潤離子液體中的測試 79
4.3.9 結果分析與討論 80
4.4 聚吡咯/銀複合材料 94
4.4.1 吡咯單體於離子液體中的電化學行為 94
4.4.2 離子液體中吡咯單體的擴散因子 96
4.4.3 聚吡咯高分子膜的電化學行為 97
4.4.4 電化學聚合吡咯高分子膜的機制與其導電結構 98
4.4.5 離子液體中銀絲的電解與轉移電子數的決定 99
4.4.6 銀離子於離子液體中的電化學行為 100
4.4.7 聚吡咯/銀修飾電極的表面結構觀測 102
4.4.8 聚吡咯/銀複合電極對氯仿之電催化還原反應測試 120
4.4.9 結果分析與討論 123
五、 結論 127
參考文獻 129

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