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研究生： 徐以軒
Syu, Yi-Syuan
論文名稱： 氫氣環境下一氧化碳電化學感測行為之研究
Studies on Carbon Monoxide Electrochemical Sensing Behavior in Hydrogen-rich Environment
指導教授： 楊明長
Yang, Ming-Chang
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： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 116
中文關鍵詞： 一氧化碳 、氫氣 、電化學感測
外文關鍵詞： Carbon monoxide, Hydrogen, Electrochemical Detection
相關次數： 點閱：49  下載：2 
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    • 一氧化碳對白金觸媒電極毒化能力相當強，因此研發可感測氫氣中一氧化碳濃度之感測器對質子交換膜型燃料電池是絕對必要的。本研究以Pt/ Nafion®作為感測電極，Nafion®117的另一側填滿硫酸，內含有白金絲對電極和Ag/AgCl參考電極，探討在富氫環境下對一氧化碳之電化學行為，並探討不同一氧化碳感測方法的特性。
    線性電位掃描在純氫氣下-0.3 ~ 0.9 V (vs. Ag/AgCl) 間，電流與電位呈線性關係，當一氧化碳存在氫氣中，電流在比0.4 V (vs. Ag/AgCl) 負的電位出現毒化現象，接近0.4 V (vs. Ag/AgCl)時為定值，且電流在50 ppm CO/H2內變化劇烈。當電位較0.4 V (vs. Ag/AgCl) 正時，CO開始氧化剝除而使白金去毒化，電流與電位回復線性關係。
    本研究採取兩種定電位法週期式感測方法，方法一是將感測電流對濃度對數作感測曲線，方法二是將感測電流除以背景電流之電流下降百分比對濃度對數作感測曲線；感測濃度範圍在100 ~ 1000 ppm CO/H2內，兩種方法皆可得良好線性，方法一靈敏度隨電位趨正而提升，於0.8 V (vs. Ag/AgCl) 下有最大靈敏度19.53 mA/ln[CO]；方法二之靈敏度在0.6 ~ 0.9 V (vs. Ag/AgCl) 內為定值10.4 %/ln[CO]。
    週期式感測選用基準濃度可消彌電流回復到無毒化過久的問題，選用基準濃度感測高濃度CO可得較短的應答時間與回復時間，分別為30秒內及100秒內，比現有CO/H2感測器都快。
    在0.8V (vs. Ag/AgCl) 下以定電位法探討濕度與流速對感測行為之影響，相對濕度32.8% ~ 100%之間的感測電流為定值，回復時間則由0%溼度之142秒拉長到100%濕度之403秒；在50 ~ 200ml/min的流速不影響感測電流，由溼度與流速對感測電流影響不大，可推論ㄧ氧化碳毒化現象非擴散控制。
    評估兩種感測方式，評估以電流下降百分比作為感測方式具有0.6 ~ 0.9 V (vs. Ag/AgCl) 下固定的靈敏度、600秒快速連續式感測之優勢，且相較於現有文獻之感測方法，具有高耐水性和成本較低等商業化潛力。

    Carbon monoxide is highly poisonous to platinum catalyst, so developing a sensor to detect CO in hydrogen is necessary. The sensing device in this study was composed of Pt/Nafion® as working electrode, a Pt wire as counter electrode and Ag/AgCl reference electrode which was immersed in sulfuric acid divided by Nafion® membrane. This research focused on the CO electrochemical behavior and the sensing method in H2-rich environment.
    Current was linear to vlotage in the range of -0.3 ~ 0.9 V (vs. Ag/AgCl) in linear voltammogram. When CO existed in H2, current lost linearity due to CO-posioning when the potential was more negative than 0.4 V (vs. Ag/AgCl). The current varied tremendously within 0 ~ 50ppm CO/H2. When the voltage was more positive than 0.4 V (vs. Ag/AgCl), CO oxidized on platinum and current regained linearity to voltage.
    This study defined two sensing methods as calibration curve in periodical chronoamperogram: method I is taking sensing current versus logarithmic of CO concentration, method II is taking current decreased ratio versus logarithmic of CO concentration. Both two methods had good linearity. In method I, sensitivity increased with applied potential and the maximum sensitivity is 19.53 mA/ln[CO] at 0.8 V (vs. Ag/AgCl). In method II, sensitivity was constant, 10.4 %/ln[CO], for applied potential in the range of 0.6 ~ 0.9 V (vs. Ag/AgCl).
    Periodical sensing by chronoamperogram using a specific CO concentration as background concentration solved the problem that long recover time. The response time was lower than 30 sec and recover time was lower than 100 sec, much smaller than other CO/H2-type sensors.
    In chronoamperogram, humidity only effected rescover time. When humidity varied from 0% to 100%, recover time increased from 142 sec to 403 sec. The flow rate in the range of 50 and 200ml/min did not influence the sensing current and recover time. The detection method was not diffusion control due to the indepence of flow rate and humidity on the current.
    The method with current decreased ratio versus logarithmic of CO concentration have several advantages: constant sensitivity in the range of 0.6 ~ 0.9 V (vs. Ag/AgCl), quick detection within 600sec, low cost and high humidity endurance compared to the other existing detection methods. By these advantages and good linearity, the detection in this study was promising.

    中文摘要........................................................................................................................I 英文摘要.......................................................................................................................II 總目錄.........................................................................................................................III 圖目錄.........................................................................................................................VI 表目錄...........................................................................................................................X 第一章 序論................................................................................................................1 1-1 燃料電池技術簡介........................................................................................1 1-1-1 燃料電池的種類............................................................................1 1-1-2 燃料電池的發展優勢....................................................................1 1-2 重組氣............................................................................................................5 1-3 一氧化碳之毒化現象....................................................................................5 1-3-1 使用合金觸媒................................................................................5 1-3-2 使一氧化碳毒化情形下再回復....................................................6 1-3-2a 加入氧化性物質....................................................................6 1-3-2b 自發性氧化............................................................................7 1-4 一氧化碳的特性............................................................................................7 1-5 一氧化碳感測器之種類與原理....................................................................8 1-5-1 觸媒燃燒型....................................................................................8 1-5-2 金屬氧化物半導體型....................................................................8 1-5-3 場效電晶體型一氧化碳感測器....................................................9 1-5-4 石英震盪型一氧化碳感測器........................................................9 1-5-5 光學式一氧化碳感測器..............................................................10 1-5-6 電化式一氧化碳感測器..............................................................10 1-5-7 電位式一氧化碳感測器..............................................................11 1-5-8 電流式一氧化碳感測器..............................................................12 1-6 Nafion®簡介................................................................................................12 1-7 Nafion上白金之製備方法..........................................................................13 1-7-1 熱壓法..........................................................................................13 1-7-2 真空濺鍍法..................................................................................14 1-7-3 無電鍍法（化學還原法）..........................................................14 1-7-3a 擴散還原法（T-T法）.......................................................14 1-7-3b 含浸還原法..........................................................................14 1-8 研究動機與目的..........................................................................................16 第二章 原理與文獻回顧..........................................................................................18 2-1 一氧化碳在白金上之反應機構..................................................................18 2-1-1 無氫環境下之反應機構..............................................................18 2-1-2 富氫環境下之反應機構..............................................................21 2-2 氫氣與一氧化碳競爭氧化造成之電流變化..............................................23 2-2-1 在有氫環境下CO濃度改變之影響..........................................23 2-2-2 在無氫環境下CO濃度改變之影響..........................................26 2-2-3 在無CO環境下氫氣濃度改變之影響......................................27 2-2-4 一氧化碳毒化與時間之關係......................................................29 2-3 文獻回顧......................................................................................................31 第三章 實驗設備與步驟..........................................................................................36 3-1 藥品與材料..................................................................................................36 3-2 儀器設備......................................................................................................37 3-3 感測電極之製備..........................................................................................38 3-3-1 Nafion® 117質子交換膜前處理.................................................38 3-3-2 Pt/Nafion®電極製備....................................................................38 3-4 感測系統之組裝..........................................................................................40 3-5 感測電極之電化學分析..............................................................................41 3-5-1 線性掃描法(Linear Sweep)........................................................41 3-5-2 定電位法(Chronoamperogram)................................................42 3-5-2a 週期式感測..........................................................................42 3-5-2b 連續式感測..........................................................................42 第四章 結果與討論..................................................................................................43 4-1 線性掃描法..................................................................................................43 4-1-1 CO/H2濃度在100 ppm以內.....................................................43 4-1-2 CO/H2濃度在100 ~ 1000 ppm之間.........................................44 4-1-3 掃描速率之影響..........................................................................46 4-1-4 CO濃度對線性掃描之綜合討論...............................................46 4-2 以定電位法探討Pt/Nafion®對CO/H2的感測特性................................48 4-2-1 定電位法空白放電測試..............................................................48 4-2-2 應答時間與回復時間..................................................................49 4-2-3 感測回復能力測試......................................................................50 4-2-3a 回復時間探討.....................................................................52 4-2-3b 極化曲線.............................................................................52 4-3 週期式定電位法感測.................................................................................54 4-3-1 100 ~ 1000 ppm CO/H2之感測行為.........................................54 4-3-1a 不同基準濃度比較測試.....................................................55 4-3-1b 施加電位之影響.................................................................57 4-3-2 低於100 ppm CO/H2之感測行為............................................62 4-3-2a 不同基準濃度比較測試.....................................................62 4-3-2b 施加電位之影響.................................................................64 4-4 階梯式定電位法感測.................................................................................68 4-4-1 山谷狀階梯式濃度升降之感測行為.........................................68 4-4-2 高濃度返回低濃度之感測行為.................................................71 4-5 其他系統變因對感測行為之影響.............................................................72 4-5-1 氣體流速影響.............................................................................72 4-5-2 氣體濕度影響.............................................................................73 4-5-3 再現性與穩定性.........................................................................78 4-6 感測方法綜合評估.....................................................................................80 第五章 結論與建議.................................................................................................81 參考文獻.....................................................................................................................82 附錄.............................................................................................................................88 附錄A 電極特性分析.....................................................................................88 附錄B 循環伏安法........................................................................................103 附錄C PPy/Pt/Nafion®修飾電極之感測行為.............................................104 附錄D 交流阻抗分析....................................................................................108

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