臺灣博碩士論文加值系統

本研究論文是利用電化學聚合法，將有序性奈米纖維聚苯胺(Polyaniline, PANi)導電性高分子，製備在以微組裝技術製備所得之Au/Al2O3電極上，再利用電沈積法將Pt製備在聚苯胺奈米纖維上，完成電化學電流式Nafion®/Pt/nano-structured PANi/Au/Al2O3感測器之感測電極製備。
利用SEM分析得知PANi奈米纖維直徑與Pt粒徑大小分別為40-50與5-20 nm。在電化學性質方面，當Pt/nano-structured PANi/Au/Al2O3感測電極之Pt電沉積電量由0.15 C減少至0.009375 C時，電化學活性面積由1.406×10-3 減少至2.90×10-4 m2；粗糙度(電化學活性面積與幾何面積比)由56.24減少至11.60；但Pt之比活性面積則由47.06增加至155.08 m2 g-1，此結果表示在較低之Pt電沉積電量下，藉由奈米結構PANi之分散作用，使Pt奈米粒子得到充分之利用，因而使比活性面積上升。
利用Pt電沉積電量為0.15 C所製備的Nafion®/Pt(0.15 C)/ nano-structured PANi/Au/Al2O3感測電極，當電位大於-0.4 V (vs. Au)時，開始有氫氣氧化電流的發生，表示奈米白金開始進行氫氣的氧化反應；在-0.4 ~ -0.3 V (vs. Au)之間氧化電流隨著電位的提升快速的增加，此區域為電極之反應動力控制區，而電位大於-0.3 V(vs. Au)時，氫氣之反應即達到質傳控制區，其極限電流值為14.528 μA cm-2。
在氫氣感測性質方面，比較Nafion®/Au/Al2O3以及Nafion®/Pt(0.15 C)/nano-structured PANi/Au/Al2O3電極在10,000 ~ 50,000 ppm之氫氣濃度進行感測，結果顯示感測靈敏度由前者電極之1.336 × 10-6 μA ppm-1提升至後者電極的3.654 × 10-4 μA ppm-1，後者為前者之273.5倍。當電沉積電量由0.15 C減少至0.009375 C時，每克白金之比靈敏度由12.21提升至138.80 μA ppm-1g-1。而氣體流量對感測性質影響方面，當流量由200 提升為500 ml min-1 時，Nafion®/Pt(0.009375 C)/nano-structured PANi/Au/Al2O3電極之靈敏度的增加有限，顯示氣體流量大於200 ml min-1時，氣膜擴散阻力可忽略。在Nafion®溶液之使用體積方面，當Nafion®溶液由5 μl減少至3 μl時，因通過Nafion®膜之質傳阻力減少, 使氫氣感測靈敏度大幅提升。感測氣體之相對溼度由100% 減少至23%時，感測靈敏度由4.19 × 10-4 μA ppm-1降低至1.32 × 10-4 μA ppm-1。

In this thesis, the ordered nanofibric polyaniline (PANi) is electropolymerized on Au/Al2O3 electrode prepared by the microfabricated technique. Nafion®/Pt/nano-structured PANi/Au/Al2O3 used as the sensing electrode of the amperometric hydrogen sensor is prepared by electrodepositing Pt on the nano-structured PANi and then casting a suitable amount of Nafion® solution on the surface of electrode.
The diameter of PANi nanofiber and the particle size of electrodeposited Pt analyzed by SEM are found to be 40 – 50 and 5 – 20 nm, respectively. Decreasing the charge for electrodepositing Pt from 0.15 to 0.009375 C the electroactive area and roughness factor of Pt on Pt/nano-structured PANi/Au/Al2O3 electrode decreases from 1.406 × 10-3 m2 and 56.24 to 2.90 × 10-4 m2 and 11.60, respectively. However, decreasing the Pt deposition charge from 0.15 to 0.009375 C the specific Pt electroactive area increases from 47.06 to 155.08 m2 g-1 due to the better distribution of Pt particles onto the nano-structured PANi.
Using Nafion®/Pt(0.15 C)/nano-structured PANi/Au/Al2O3 as sensing electrode, the on-set potential for the anodic oxidation of H2 is found to be -0.4 V (vs. Au). For potential in the range of -0.4 – -0.3 V(vs. Au), the anodic oxidation of H2 is located in kinetic control region and the current increases with potential. The anodic oxidation of H2 is controlled by the mass transfer and the limiting current is obtained to be 14.528 μA cm-2 for the potential greater than -0.3 V (vs. Au).
The sensitivity of amperometric H2 gas sensor based on Nafion®/Pt/nano-structured PANi/Au/Al2O3 found to be 3.654 × 10-4 μA ppm-1 is 273.5 times of that based on Nafion®/Au/Al2O3 with sensitivity of 1.336 × 10-6 μA ppm-1. Using Nafion®/Pt/nano-structured PANi/Au/Al2O3 as sensing electrode, the specific sensitivity of the amperometric H2 gas sensor increases from 12.21 to 138.80 μA ppm-1 g-1 by decreasing the Pt electrodepositing charge from 0.15 to 0.009375 C. The sensitivity of amperometric H2 gas sensor based on Nafion®/Pt (0.009375 C)/nano-structured PANi/Au/Al2O3 changes slightly by increasing the gas flow rate from 200 to 500 ml min-1 due to the insignificant mass transfer resistance witin the gas diffusion layer for gas flow rate greater than 200 ml min-1. On the other hand, decreasing the amount of Nafion® solution from 5 to 3 μl for preparing sensing electrode the significant increase in the sensitivity of amperometric H2 gas sensor is due to the decrease in the mass transfer resistance within the Nafion® film. The sensitivity of amperometric H2 gas sensor decreases from 4.19 × 10-4 to 1.32 × 10-4 μA ppm-1 with decreasing the relative humidity from 100 to 23 %.

摘要 I
Abstract III
致謝 V
目錄 VI
表目錄 XII
圖目錄 XIIII
第一章 緒論 1
1-1感測器之簡介 1
1-2導電性高分子 5
1-2-1導電性高分子之簡介 5
1-2-2導電性高分子之導電理論機制 9
1-2-3 聚苯胺 17
1-2-3-1 聚苯胺之結構 17
1-2-3-2聚苯胺之聚合機制 20
1-2-3-3 聚苯胺之電化學行為 22
1-3 氫氣之簡介 25
1-3-1 氫氣在工業上所扮演的角色 25
1-3-2 氫氣在醫學上所扮演的角色 26
1-3-2-1氫氣應用於疾病之治療 26
1-3-2-2氫氣應用於疾病之預防 28
1-4 氫氣感測器之發展與其現況 31
1-5 貴金屬/導電性高分子奈米複合材料 47
1-5-1貴金屬奈米粒子之特性 47
1-5-2貴金屬/導電性高分子奈米複合材料之特性與應用 49
1-6研究動機與實驗架構 53
第二章 實驗程序與設備 55
2-1 實驗儀器 55
2-2 實驗藥品 57
2-3實驗程序 59
2-3-1感測電極之製備 59
2-3-1-1. Au/Al2O3電極之製備 59
2-3-1-2. Nano-structured PANi/Au/Al2O3電極之製備 63
2-3-1-3. Pt/nano-structured PANi/Au/Al2O3電極之製備 65
2-4感測電極材料性質分析 67
2-4-1電極表面型態分析 67
2-4-2 電極之電化學性質分析 67
2-4-2-1 循環伏安分析 68
2-4-3-2極化曲線分析 74
2-5電流式氫氣感測器之感測性質 79
2-5-1靈敏度 79
2-5-2感測極限 81
2-5-3穩定性 82
2-5-4選擇性 83
第三章 結果與討論 84
3-1 感測電極之性質分析 84
3-1-1 感測電極之表面型態 84
3-1-2 Pt/nano-structure PANi/Au/Al2O3電極之Pt電沉積量電與負載量之關係 110
3-1-3 感測電極之電化學性質分析 114
3-2 氫氣在感測電極上之感測性質 129
3-2-1 氫氣在感測電極上之電化學反應性質 129
3-3 氫氣之感測性質 145
3-3-1 Nafion®/Au/Al2O3電極之感測性質 145
3-3-2 Nafion®/Pt/nano-structured PANi/Au/Al2O3電極 149
3-3-3 製備Nafion®/Pt/nano-structured PANi/Au/Al2O3電極時Pt電沉積電量對感測性質之影響 153
3-3-4 氣體流量對Nafion®/Pt/nano-structured PANi/Au/Al2O3電極之感測性質的影響 163
3-3-5 製備Nafion®/Pt/nano-structured PANi/Au/Al2O3電極時Nafion®溶液體積對感測性質之影響 182
3-3-6 製備Nafion®/Pt/nano-structured PANi/Au/Al2O3電極時PANi電聚合電量對感測性質之影響 199
3-3-7 相對溼度對於Nafion®/Pt/nano-structured PANi/Au/Al2O3電極之感測性質的影響 215
3-3-8 Nafion®/Pt/nano-strctured PANi/Au/Al2O3電極之氫氣感測選擇性 224
3-3-9 Nafion®/Pt/nano-strctured PANi/Au/Al2O3電極之穩定性測試 229
第四章 綜合討論 234
4-1 氫氣在Nafion®/Pt/nano-structured PANi/Au/Al2O3感測電極上之質傳及其影響因素探討 234
4-2 Nafion®/Pt/nano-structured PANi/Au/Al2O3電極之感測性質比較 238
第五章 結論與建議 242
參考文獻 246

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