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研究生: 林芸丘
LIN YUN-CHIOU
論文名稱: 苯胺修飾電極之電流調節應用與敏光性含鈷化合物之光電去溴反應探討
Current Rectification with substituted aromatic amine diazonium modified electrodes and photodebromination with photosensitive cobalt complex
指導教授: 王忠茂
Wang, Chong-Mou
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2006
畢業學年度: 94
語文別: 中文
論文頁數: 126
中文關鍵詞: 苯胺修飾電極光電去溴反應
英文關鍵詞: aromatic amine diazonium modified electrodes, photodebromination
論文種類: 學術論文
相關次數: 點閱:157下載:2
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  • 由於苯胺衍生物(R-ph-NH2,R = H, ph-N=N-, NH2-)可於與亞硝酸鈉反應時被還原而吸附於電極表面,本論文於是藉由此一特性,先將苯胺及三苯胺等苯胺衍生物偶氮化,再將之還原固定於電極表面上。結果分析顯示:苯胺衍生物似乎以近乎單層、垂直方式附著於電極表面,並可因此將醌類化合物,如苯醌、維生素K3與蒽醌吸附於其中,使之間接被吸附於碳電極表面。我們也發現:利用此一方式所製作的維生素K3修飾電極,對溶液中的pH值變化極為敏感,具有催化還原氧氣之能力,並可與含氯化合物進行錯合反應。此外,我們也發現:被吸附的維生素K3也可作為電子傳遞媒介者,規範電極與電解質溶液間的電子傳遞方向,具電子傳送整流的應用潛力。
    本論文也嘗試將含鈷化合物,如Tris(5-aminophenanthroline)cobalt(II) hexafluorophosphate,與胺基芘等感光分子結合,使其成為敏光性的含鈷化合物,藉以模擬維生素B12,進行去鹵化反應(Dehalogenation reaction)。實驗結果顯示:所合成的含鈷錯合物在照光下,可有效還原有機雙溴化合物,如雙溴丁烷(Dibromobutane,簡稱DBB),使之分解成低毒性的衍生物。

    Aromatic amines can be converted to diazonium salts, and can thus be cathodically deposited on carbon electrodes. In the light of this, we prepared chemically modified electrodes (CME) with aromatic amines, such as aniline and p-terphenylamine, via the diazonium pathway, and utilized them to rectify the flow of electric current from electrodes to electrolyte solutions. Experimental results based on cyclic voltammetry (CV), electrochemical quartz-crystal-microbalance analysis (EQCM), electrochemical impedance analysis (EIS), and totally-attenuated- reflectance Infrared absorption spectral (ATR-IR) analysis indicated that the CMEs prepared in this manner seem to be free of pin holes on the electrode surface, and can, in advance, be employed to microsolvate electron mediators, like benzoquinone (BQ), vitamin K3 (VK3) and anthraquinone (AQ), for further applications, such as for current rectification.
    Besides, we also attempted to mimic vitamin B12 for the dehalogenation of dibromobutane. Cobalt complexes such as tris(5-aminophenanthroline) cobalt(II) hexafluorophosphate (Co(NH2-phen)32+) show application potential in this aspect. By attaching light-absorption chromophores, like pyrene, with Co(NH2-phen)32+, we, in addition, found that the resultant derivative (denoted py-Co(NH2-phen)32+ ) can be reduced at less negative potential, ca. -0.6 V vs. Ag/AgCl under UV irradiation in DMSO, and then, cause dibromobutane (DBB) to be reductively decomposed into less toxic products.

    圖目錄 圖目錄-------------------------------------------------------------------------- I 中文摘要---------------------------------------------------------------------- 1 英文摘要---------------------------------------------------------------------- 2 第一章緒論----------------------------------------------------------------- 3 1.1 偶氮苯胺修飾電極------------------------------------------------- 3 1.2 醌(Quinones)與維生素K3 簡介------------------------------ 6 1.3 維生素B12 ------------------------------------------------------------ 8 1.4 含鹵有機物的分解------------------------------------------------ 10 1.5 交流阻抗原理------------------------------------------------------ 11 1.6 研究目的------------------------------------------------------------ 16 第二章實驗------------------------------------------------------- 17 2.1 化學藥品----------------------------------------------------------- 17 2.2 實驗設備----------------------------------------------------------- 20 2.3 修飾電極製備----------------------------------------------------- 22 2.4 敏光性含鈷化合物製備----------------------------------------- 26 第三章實驗結果與討論---------------------------------------------- 28 3.1 苯胺修飾電極----------------------------------------------------- 28 3.1.1 苯胺(diazo-An)修飾電極製備-------------------- 29 3.1.2 Diazo-An 修飾電極電化學特性探討--------------- 33 (一) 電化學石英振盪天平--------------------------- 33 (二) 循環伏安圖譜分析------------------------------ 35 (三) 交流阻抗分析------------------------------------ 38 (四) 薄膜紅外線吸收光譜分析--------------------- 51 3.1.3 偶氮化苯胺修飾電極穩定度測試------------------ 54 3.2 偶氮化苯胺修飾電極與電子媒介探討---------------------- 55 3.2.1 含VK3 偶氮化苯胺修飾電極電化學分析-------- 59 (一) 掃瞄速率變化分析----------------------------- 59 (二) pH 值影響---------------------------------------- 61 (三) 含VK3 偶氮化苯胺修飾電極電子傳遞媒 的應用與探討----------------------------------- 64 (四) 含VK3 偶氮化苯胺修飾電極對生化感測 之探討-------------------------------------------- 79 3.2.2 其他苯胺修飾電極製備與探討-------------------- 87 3.2.2.1 偶氮化二胺苯-苯胺(diazo-PDA-An ) 修飾電極與偶氮化苯基偶氮苯胺 (diazo-PAA)修飾電極之比較---------- 89 3.3 維生素B12(Vitamin B12,簡稱VB12)人工模擬與應用 -------------------------------------------------------------------- 97 3.3.1 敏光性類VB12 之合成----------------------------- 98 3.2.2 Py-Co(NH2-phen)3 2+對DBB 還原分解之探討 ----------------------------------------------------------- 105 第四章結論----------------------------------------------------------- 114 附錄一modified pyrene 之質譜圖----------------------------- 115 附錄二人工合成B12 之質譜圖---------------------------------- 116 附錄三diazo-PDA-An(A)與diazo-PAA(B)之ATR/IR 對照圖。(a) 與表面垂直的偏極光;(b)為以 與表面平行的偏極光所得圖譜。----------------- 117 第五章參考文獻---------------------------------------------------- 118

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