臺灣博碩士論文加值系統

本論文主要探討不同的製備參數進行三元金屬觸媒電極之製備；即不同的金屬前驅物種類與濃度、電沈積法、基材與鍍後鍛燒溫度。並探討不同製備條件下所製備的三元金屬觸媒電極，對於葡萄糖電催化氧化之效能，並對反應機構、動力與質傳行為做探討，以及材料特性分析。
以三種不同電化學沈積法(定電流法、循環伏安法、多電位階法) 製備的RhxMoyOs(1-x-y)Oz/Pt電極對於葡萄糖電催化氧化效果中，實驗最佳製備條件為：鍍浴銠、鉬、鋨前驅物莫耳比Rh:Mo:Os=1:0.6:0.1，使用循環伏安法電沈積觸媒(電位掃瞄區間為-1.2~0V vs. Ag/AgCl/3M KCl，掃瞄速率50 mV s-1，掃瞄沈積圈數100圈)，使用Pt基材，並於鍍後經過150℃鍛燒90分鐘，所製備的RhxMoyOs(1-x-y)Oz/Pt電極，在鹼性條件下0.1M Na2CO3+0.1M NaHCO3緩衝液(pH=9.8)含50mM葡萄糖，於低電位-0.45V vs. Ag/AgCl/3M KCl就可使葡萄糖脫氫氧化，並可產生21.1 mA cm-2 (6.53 mA/mg)的氧化電流密度，而在中性條件下0.01M磷酸鹽緩衝液(phosphate buffer solution)(pH＝7.4)含50mM 葡萄糖，於低電位-0.45V vs. Ag/AgCl/3M KCl就可使葡萄糖脫氫氧化，並可產生13.2 mA cm-2 (4.09 mA/mg)的氧化電流密度。
將不同電沈積法製備的RhxMoyOs(1-x-y)Oz/Pt電極，進行SEM表面分析，電極表面形態皆具有多孔性。由表面電荷分析，使用循環伏安法分析所製備的RhxMoyOs(1-x-y)Oz/Pt電極，擁有最大的表面電荷( =1825 C)，即擁有最大的電化學活性面積。EDS分析，以最佳條件製備之RhxMoyOs(1-x-y)Oz/Pt電極，其觸媒組成亦符合所配置之金屬前驅物比例。XRD分析證實，三種不同電化學沈積法所製備的RhxMoyOs(1-x-y)Oz/Pt電極，大部分Rh、Mo與Os為合金狀態，單一金屬粒子大小約41 nm。

This investigation is focus on the preparation of the biomimetic catalysts、RhxMoyOs(1-x-y)Oz/Pt、used as anode for Biological fuel cells with electrochemically deposition in aqueous solution. Further、factors that affected the oxidation of glucose and the characteristics of RhxMoyOs(1-x-y)Oz/Pt were explored including the various precuster；deposition method；base material and calcinations temperature and so on. Further、the kinetics and diffusion model matched well by theoretical analysis and experimental results、the oxidation rate of glucose were shown as in equations (1) and (2),
Surface reaction : r2=(8.71*10^-5)CG/(1+0.843CG) (1)
Diffusion control : Ix,i=-FziDi(dci/dx) (2)
The experimental results revealed that the oxidation current of glucose was up to 21.1 mA‧cm-2 in the presence of 0.1 M Na2CO3+NaHCO3 base solution. On the other hand、in a neutral solution、i.e.、0.01 M phosphate buffer solution、the current was 13.2 mA‧cm-2 、respectively.
In addition、the surface morphologies and compositions of the prepared RhxMoyOs(1-x-y)Oz/Pt anode material were examined with SEM、XRD and EDS respectively. The increasing of the surface area of RhxMoyOs(1-x-y)Oz/Pt by electro-chemical process was detected by cyclometry method.
The optimum operating conditions using RhxMoyOs(1-x-y)Oz/Pt as a anode catalysts for bio-fuel cell system were 、Rh:Mo:Os(mol ratio) = 1:0.6:0.1、using 100 cycle number deposition、Pt base、150 ℃ calcination temperature for 90 min.

中文摘要 ----------------------------------------------- i
英文摘要 ----------------------------------------------- iii
誌謝 ----------------------------------------------- v
目錄 ----------------------------------------------- vi
表目錄 ----------------------------------------------- xi
圖目錄 ----------------------------------------------- xiii
第一章 緒論-------------------------------------------- 1
1-1 燃料電池的歷史----------------------------------- 1
1-2 燃料電池的分類----------------------------------- 4
1-3 燃料電池之運作原理-------------------------------- 7
1-4 燃料電池之極化現象與極化曲線----------------------- 11
1-5 陽極材料---------------------------------------- 14
1-5-1 陽極材料的種類----------------------------------- 14
1-5-2 陽極材料製備方法--------------------------------- 17
1-6 電鍍基本原理------------------------------------- 21
1-6-1 電鍍前處理--------------------------------------- 21
1-6-2 電鍍原理---------------------------------------- 23
1-6-3 合金電鍍之原理----------------------------------- 33
1-6-4 直流電電鍍-------------------------------------- 38
1-6-5 循環伏安電沈積法--------------------------------- 40
1-6-6 多電位階電沈積法--------------------------------- 43
1-7 生物燃料電池------------------------------------- 44
1-7-1 生物燃料電池的分類-------------------------------- 45
1-7-2 生物燃料電池性能之影響---------------------------- 49
1-7-3 生物燃料電池特點--------------------------------- 49
1-7-4 生物燃料電池的使用範圍與優點---------------------- 50
1-7-5 生物燃料電池的瓶頸與展望-------------------------- 50
1-8 研究動機---------------------------------------- 52
第二章 理論-------------------------------------------- 55
2-1 葡萄糖的電化學氧化-------------------------------- 55
2-2 葡萄糖於金屬電極表面氧化還原機制------------------- 59
2-3 葡萄糖電氧化之動力學模式-------------------------- 70
第三章 實驗設備、方法與程序------------------------------ 76
3-1 儀器-------------------------------------------- 76
3-2 藥品-------------------------------------------- 78
3-3 實驗程序---------------------------------------- 80
3-3-1 電極前處理--------------------------------------- 80
3-3-2 不同金屬前驅物之實驗------------------------------ 81
3-3-3 不同電化學沈積法之比較---------------------------- 85
3-3-4 基材之影響--------------------------------------- 89
3-3-5 鍍後鍛燒之影響----------------------------------- 89
3-4 RhxMoyOs(1-x-y)Oz/Pt電極材料之測試--------------- 90
3-4-1 循環伏安法--------------------------------------- 92
3-4-2 表面電荷之分析----------------------------------- 92
3-4-3 壽命測試---------------------------------------- 93
3-4-4 葡萄糖電化學氧化之動力實驗------------------------- 93
3-5 材料分析---------------------------------------- 95
3-5-1 材料表面型態分析--------------------------------- 95
3-5-2 材料金屬組成分析--------------------------------- 96
3-5-3 材料結晶型態分析--------------------------------- 96
第四章 結果與討論--------------------------------------- 99
4-1 鍍浴行為---------------------------------------- 99
4-2 金屬前驅物種類與濃度之影響------------------------- 103
4-3 基材之影響--------------------------------------- 125
4-4 鍍後鍛燒之影響----------------------------------- 130
4-5 電化學沈積法之影響-------------------------------- 137
4-5-1 定電流法製備RhxMoyOs(1-x-y)Oz/Pt電極------------- 137
4-5-2 循環伏安法製備RhxMoyOs(1-x-y)Oz/Pt電極------------ 150
4-5-3 多電位階法製備RhxMoyOs(1-x-y)Oz/Pt電極------------ 167
4-5-4 三種不同電化學沈積法之比較------------------------- 176
4-6 表面電荷之分析----------------------------------- 183
4-7 壽命測試---------------------------------------- 196
4-8 動力學之測試------------------------------------- 198
4-8-1 表面反應控制------------------------------------- 207
4-8-2 擴散質傳控制------------------------------------- 213
4-9 材料分析---------------------------------------- 224
4-9-1 EDS分析----------------------------------------- 224
4-9-2 XRD分析----------------------------------------- 228
4-10 不同陽極材料電催化葡萄糖氧化效果之比較-------------- 235
五 結論與建議--------------------------------------- 238
參考文獻 ----------------------------------------------- 244
個人學經歷----------------------------------------------- 256

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