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研究生：	林均霖 Lin, Jiun-Lin
論文名稱：	以導電性共聚物/奈米碳管複合材料固定化酵素電極於葡萄糖/氧生物燃料電池之研究 Immobilization of enzymes onto the carbon nanotubes/carbon paper electrode by the conducting polymer/carbon nanotubes composite for the investigation of the biofuel cell
指導教授：	許梅娟 Syu, Mei-Jywan
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	69
中文關鍵詞：	生物燃料電池、導電性高分子、EDOT 、pyrrole 、酵素電極、交流阻抗、質子交換膜、碳紙
外文關鍵詞：	enzymatic biofuel cell, conducting polymer, pyrrole, EDOT, impedance, Nafion® 117, carbon paper
相關次數：	點閱：100 下載：0
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　　葡萄糖氧化酵素 (Glucose oxidase) 和漆酵素 (laccase) 以導電性單體行電聚合形成共聚物固定在多壁奈米碳管修飾之碳紙電極上，分別作為燃料電池系統的陽極和陰極。酵素、單體和媒介子 (mediators) 是以循環伏安法(cyclic-voltammetry) 進行單體之電聚合，電池系統以葡萄糖為燃料，陽極所用之媒介子為HQS (8-hydroxyquinoline-5-sulfonic acid) ，陰極則使用ABTS (2,2'-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid))，兩槽體以Nafion® 117 質子交換膜作為分隔，電池功率則是以穩定變電壓方式進行量測。
　　從SEM 觀察表面型態，可比較酸鹼值、溫度對導電性高分子形成之影響，也可看出不同共聚物之表面型態差異；針對不同包埋物質，除了可用SEM 圖比較，亦可透過交流阻抗分析進行討論；高分子之熱穩定性即可使用熱重分析儀(thermo gravimetric analyzer, TGA) 來確認。
　　本研究使用aniline、pyrrole、thiophene、3,4-ethylenedioxythiophene (EDOT) 等四種導電性單體進行共聚合，這些共聚物中，以polyaniline 所製備的高分子酵素電極系統電池效率最差；以 pyrrole/EDOT 共聚合所製備的高分子酵素電極進行放電測試可達到最高輸出功率13.96 μW/cm2。
　　在電極修飾部份，探討了不同酸鹼值、單體比例、電極面積、奈米碳管濃度的影響；電池系統部份，不同的媒介子也會影響電子傳遞，除了使用HQS 和ABTS，於本文中也使用了具有良好氧化還原能力的鐵氰化鉀進行比較；鹽橋也被用於連接陰陽兩極，交流阻抗分析 (alternative current impedance analysis) 得到鹽橋阻抗遠大於Nafion® 117 膜，在放電測試也是Nafion® 117 膜系統優於鹽橋。以質子交換膜作隔間之電池再現性估計也應優於鹽橋。

Cyclic-voltammetric polymerization of monomers, multi-wall carbon nanotubes (MWCNTs), mediators, with glucose oxidase at the anode and with laccase at the cathode, respectively, formed the immobilized enzyme/conducting polymer layer, onto CNT/carbon paper. For the preparation of the electrodes, enzymes, monomers and mediators were dissolved in buffer. Polymerization was induced by cyclic-voltammetry (CV) at a scan rate of 50 mV/s. The biofuel cell system was constructed by two chambers comparted by Nafion○R117 membrane. Glucose was used as the fuel and two mediators, HQS (8-hydroxyquinoline-5-sulfonic acid) and ABTS (2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid)) were added to the anode and the cathode for the purpose of power efficiency, respectively.
Surface morphology of the copolymer layers via different monomers were inspected from SEM images. Alternative current (AC) impedance spectroscopy analysis and thermo gravimetric analysis (TGA) were also applied in this research.
All of the conducting polymers, the polyaniline-based conducting polymers was the worst one and poly(pyrrole-co-3,4-ethylenedioxythiophene) showed the best performance. A maximum power density 13.96 μW/cm2 could be obtained from such a system.
Different factors such as amount of CNTs, the size of electrodes, the ratio of monomers, and pH affecting the power efficiency were all investigated. Additionally, the power efficiency could also be influenced by the types of mediators. It was summarized that HQS and ABTS were the best combination for the glucose enzymatic biofuel cell in this work.
Comparing to the separator of Nafion® 117 membrane, the glucose enzymatic biofuel cell system was also separated by a salt-bridge. The results showed the fuel cell system comparted by Nafion® 117 membrane was superior to the one by a salt-bridge.

中文摘要.............................................................................................................................I 
Abstract..............................................................................................................................II 
誌謝...................................................................................................................................III 
目錄..................................................................................................................................IV 
圖目錄..............................................................................................................................VII 
表目錄...............................................................................................................................IX 
第一章 緒論........................................................................................................................1 
1 能源..............................................................................................................................1 
2 生物燃料電池簡介..........................................................................................................2 
2.1 生物燃料電池的特點...................................................................................................2 
2.2 生物燃料電池的種類...................................................................................................4 
2.3 電子傳遞機制............................................................................................................5 
3 電極材料......................................................................................................................7 
3.1 Poly(3,4-ethylenedioxythiophene) (PEDOT)...................................................................7 
3.2 奈米碳管 (Carbon nanotube, CNT)...............................................................................8 
3.3 交換膜 (Exchange membrane)....................................................................................8 
4 葡萄糖生物燃料電池.....................................................................................................9 
4.1 酵素...........................................................................................................................9 
4.2 酵素之固定化方法....................................................................................................10 
4.2.1 物理吸附................................................................................................................11 
4.2.2 膠體包埋................................................................................................................11 
4.2.3 共價結合................................................................................................................12 
4.2.4 架橋連結................................................................................................................12 
4.3 酵素於陰陽兩極之反應..............................................................................................13 
4.4 陰陽兩極之電子傳遞者..............................................................................................13 
5 研究動機....................................................................................................................15 
第二章 實驗材料與方法......................................................................................................16 
1 藥品與材料的前處理....................................................................................................16 
1.1 Nafion® 的前處理......................................................................................................16 
1.2 多層奈米碳管的酸化處理...........................................................................................16 
2 酵素電極製備...............................................................................................................16 
2.1 碳紙電極製備............................................................................................................16 
2.2 含有酸化多壁奈米碳管碳紙電極製備...........................................................................16 
2.3 葡萄糖氧化酵素電極製備...........................................................................................16 
2.4 漆酵素電極之製備......................................................................................................17 
3 酵素型生物燃料電池放電測試........................................................................................17 
3.1 使用鹽橋之生物燃料電池之組裝.................................................................................17 
3.2 使用Nafion® 117質子交換膜之生物燃料電池之組裝......................................................17 
3.3 含有鹽橋之生物燃料電池之放電..................................................................................19 
3.4 含有Nafion® 117質子交換膜之生物燃料電池之放電......................................................19 
4 交流阻抗分析..............................................................................................................19 
4.1 各種電極..................................................................................................................19 
4.2 Nafion® 117系統和鹽橋系統之電池系統阻抗分析.......................................................19 
5 以掃描式電子顯微鏡 (SEM) 觀察高分子酵素電極之表面..................................................20 
6 實驗藥品與材料...........................................................................................................21 
7 實驗器材....................................................................................................................22 
第三章 結果與討論.............................................................................................................24 
1 酸鹼值對葡萄糖氧化酵素電極之影響-單電極測試.............................................................24 
2 SEM表面觀測圖...........................................................................................................26 
2.1 酸鹼值對導電性高分子型態之影響..............................................................................27 
2.2 包埋酵素與媒介子前後之型態差異..............................................................................29 
2.3 溫度對導電性高分子型態影響.....................................................................................31 
3 以熱重分析儀 (Thermo gravimetric analyzer, TGA) 進行polypyrrole-based polymer之分析....33 
4 不同奈米碳管濃度對生物燃料電池放電功率之影響..........................................................35 
4.1 Nafion® 117 system, polypyrrole................................................................................35 
5 不同媒介子對酵素電池效能之影響.................................................................................38 
6 使用不同單體製備固定化酵素電極.................................................................................44 
7 不同單體比例..............................................................................................................50 
8 不同電極面積..............................................................................................................52 
9 使用質子交換膜或鹽橋之燃料電池系統比較....................................................................54 
10 電化學阻抗光譜圖 (Electrochemical impedance spectroscopy, EIS) 之交流阻抗分析........57
第四章 結論.......................................................................................................................62 
參考文獻...........................................................................................................................64

                                    

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