臺灣博碩士論文加值系統

本研究的主要目的是利用電聚合的方式製作聚苯胺導電性高分子薄膜於石英晶體微天秤與氧化銦錫電極上，以電化學石英晶體微天秤與光譜技術觀測聚苯胺材料之離子辨識性。以六種電解質來探討各種大小不同的陰離子在進行離子摻雜與去摻雜時之光電化學變化，並藉此詳細分析離子大小、結構、摻雜方式對於分子辨識的影響，另外再選擇幾種代表性的苯胺衍生物進行相關特性探討，結果顯示聚苯胺仍然最適於分子辨識之用，能有效區別各種摻雜陰離子及其摻雜行為。在鑑定分析上，本實驗以三種方式來探討離子摻雜之現象，首先以循環伏安法偵測，當電壓約為0.5 V時正好為離子摻雜時之電壓，由實驗的結果得知，當離子越大其波峰電壓越大，而波峰電流值越小，此現象恰好符合離子大小之順序：Cl-＜SO42-＜ClO4-＜pTSA-。因此我們推論循環伏安法為有效辨識離子大小的工具。其次再以紫外光-可見光譜法偵測，當聚苯胺摻雜離子後其吸收值為820 nm，而由吸收值的大小及吸收值對電壓的斜率也可分辨離子的摻雜量，摻雜量越多的吸收值越大、斜率也越大。最後使用電化學石英晶體微天秤來量測，它是直接的以頻率變化來顯示離子的摻雜與去摻雜現象，藉由計算頻率的變化可知重量的增加與減少，進而可轉換為莫耳數比，正確地推知離子摻雜的多寡，其結果也可用來作為離子摻雜方式的探討。
再來我們以原子力顯微鏡與掃描式電子顯微鏡來觀測聚苯胺薄膜之表面狀態，它會因電壓與陰離子的不同而有所改變，可大概的推測，如果離子不易摻雜與去摻雜時，則聚苯胺在-0.2 V與0.4 V時之表面狀態是一致的。

The electropolymerization thin film of polyaniline(PAn) on the quartz crystal microbalance(QCM) crystal and Indium Tin Oxide ( ITO ). EQCM and spectrum techniques were used to investigate the ionic recognition. The doping and dedoping characteristics of six anions included inorganic and organic electrolytes on electrochemical and optical properties were observed to realize the effects of size, structures and dopant behaviors. In addition, polyaniline and its substituted derivatives were exploited, and it shows that Pan is superior than the others in ionic recognition.
The order of ionic size in doping was Cl-＜SO42-＜ClO4-＜pTSA-, when the ion size is large, the positive Epa, and smaller Ipa, was obtained using cyclic voltammetry. The absorbance of 820nm was indicated the doping process, and smaller size, strong abs., greater slope of Δabs/ΔE in UV–Vis spectrum. The amounts of doping anions are based on the anion size. Finally, the frequency changes were collected during the ionic doping/dedopoing processes, and the amounts of dopant or doping behavior could be calculated and distinguished by this method in EQCM.
In AFM and SEM experiments, the electrode surfaces of polyaniline with dopant were found the difference in -0.2 and 0.4V potential applied. If the surfaces were the same, it indicated there were no doping/ dedopoing anion at all. Furthermore, the results were compared with respect to possible correlations between optical and electronic properties, and the identity of the polymerization methods being present during formation the polymer was also compared in recognition properties.

謝誌……………………………………………………………………………i
中文摘要……………………………………………………………………...ii
英文摘要……………………………………………………………………..iii
目錄…………………………………………………………………………..iv
表目錄………………………………………………………………………viii
圖目錄………………………………………………………………………..ix

1、緒論………………………………………………………………………..1
1.1、聚苯胺及其衍生物簡介………………………………………………1
1.2、聚苯胺及其衍生物之合成………………………………………….....3
1.3、聚苯胺氧化還原機制………………………………………………….5
1.4、電化學原理……………………………………………………………5
1.5、電顯色 ( electrochromism ) 簡介…………………………………….6
1.6、原子力顯微鏡 ( Atomic Force Microscope , AFM ) 簡介……………8
1.7、石英晶體微天秤 ( Quartz Crystal Microbalance , QCM ) 簡介……..9
1.8、圓二色極化光譜儀 ( circular dichroism , CD ) 簡介……………….12
1.9、掃瞄式電子顯微鏡 ( Scanning Electron Microscopy, SEM ) 簡介...12
1.10、pH影響聚苯胺之結構........................................................................13
1.11、First cycle effect效應..........................................................................13
1.12、聚苯胺、聚鄰-甲基苯胺與聚鄰-乙基苯胺薄膜之孔洞大小與陰離子的尺寸與結構................................................................................14
1.13、聚苯胺掌性的形成............................................................................15

2、實驗部分………………………………………………………………...17
2.1、試藥部份…………………………………………………………….17
2.2、儀器設備…………………………………………………………….17
2.3、實驗步驟…………………………………………………………….18
2.3.1、以循環伏安法，作為離子選擇性的辨識………………………18
2.3.1.1、電聚合方法..............................................................................18
2.3.1.2、循環伏安法偵測……………………………………………..19
2.3.1.3、聚苯胺電化學活性的測試.....................................................19
2.3.2、電化學配合紫外光-可見光光譜來作為離子選擇性的辨識…..19
2.3.2.1、電聚合方法..............................................................................19
2.3.2.2、電化學配合紫外光-可見光光譜偵測…………....................20
2.3.3、製備觀測AFM、SEM下所需的聚苯胺試片………………….21
2.3.4、製備具掌性的聚苯胺……………………………………………22
2.3.4.1、電聚合方法.............................................................................22
2.3.4.2、圓二色極化光譜偵測……………………………………….22
2.3.4.3、以循環伏安法偵測………………………………………….22

3、結果與討論………………………………………………………………23
3.1、過氯酸與苯胺單體分別以循環伏安法與定電位法電聚合……….23
3.1.1、在過氯酸之電解液中以循環伏安法電聚合苯胺單體…………23
3.1.2、在過氯酸之電解液中以定電位法電聚合苯胺單體……………23
3.1.3、聚苯胺之反應機制………………………………………………24
3.2、探討聚苯胺薄膜離子摻雜的效應…………………………………26
3.2.1、聚苯胺以循環伏安法摻雜陰離子……………………………...26
3.2.2 、離子摻雜的效應………………………………………………..27
3.2.3 、在不同厚度的聚苯胺中探討波峰電位與波峰電流的關係…..28
3.2.4 、聚苯胺電化學活性測試………………………………………..30
3.2.5、定電位聚合之聚苯胺以循環伏安法摻雜陰離子………………30
3.3 、硫酸與苯胺單體以循環伏安法及定電位電聚合………………….31
3.3.1 、以循環伏安法電聚合聚苯胺薄膜……………………………...31
3.3.2 、摻雜陰離子的討論……………………………………………...31
3.4 、聚苯胺、聚鄰-甲基苯胺、聚鄰-乙基苯胺的討論………………..32
3.4.1 、分別以苯胺、甲基苯胺、乙基苯胺單體在過氯酸電解質溶液中以循環伏安法電聚合，探討聚合的差異……………………..32
3.4.2 、分別以苯胺、甲基苯胺、乙基苯胺單體在硫酸電解質溶液中以循環伏安法電聚合，探討聚合的差異………………………..34
3.4.3 、聚鄰-甲基苯胺、聚鄰-乙基苯胺摻雜陰離子的討論…………34
3.5 、紫外光-可見光光譜量測……………………...................................35
3.5.1 、以紫外光-可見光 ( UV-Vis ) 光譜做光譜掃描同時配合定
電位儀………………………………………………………….36
3.5.2 、在UV-Vis光譜儀中施以循環伏安法做光譜掃描……………37
3.6 、原子力顯微鏡 ( AFM )與掃瞄式電子顯微鏡 ( SEM )…………..37
3.6.1 、試片製作的條件………………………………………………..37
3.6.2 、觀測以循環伏安法、定電壓法所聚合的聚苯胺其表面特性及探
討結構上的差異………………………………………………...38
3.7 、電化學石英晶體微天秤( EQCM )…………………………………39
3.7.1 、以電化學石英晶體微天平做質量吸附的探討………………..39
3.7.2 、聚苯胺薄膜摻雜不同的陰離子………………………………..40
3.7.3 、不同方式的摻雜與頻率變化的關係…………………………..40
3.8 、聚苯胺掌性鑑定……………………………………………………42
3.8.1 、電聚合及其結構探討…………………………………………..42

4 、結論與未來展望……………………………………………………….43

5 、參考文獻……………………………………………………………….76

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