氧化鋯擔載奈米金觸媒之製備與應用研究

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謝文祥(Wen-Hsiang Hsieh) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

氧化鋯擔載奈米金觸媒之製備與應用研究
(Preparation and application of ZrO2 supported nanosized Au catalyst)

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摘要(中)

本研究以氧化鋯為擔體，利用共沈澱法以及沈澱固著法製備成奈米氧化鋯擔體金觸媒(簡稱為Au/ZrO2觸媒)，同時利用感應耦合電漿原子放射光譜儀(ICP-AES)、氮吸附法、X射線繞射儀(XRD)、熱重分析儀(TGA)、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、光電子光譜儀(XPS)等各項儀器與分析技術，分別對擔體及觸媒進行鑑定，並利用甲醇部分氧化反應做為催化活性的測試，藉以評估Au/ZrO2觸媒產生氫氣並應用於質子交換膜燃料電池的可行性。
實驗結果得知，以共沈澱法製備的Au/ZrO2觸媒，其觸媒前趨物至少在698 K下鍛燒才會完全分解形成氧化鋯。由氮吸附結果指出，沈澱固著法所製備的Au/ZrO2觸媒，BET比表面積的幾乎不變；共沈澱法製備的金觸媒，隨著載量的增加使BET比表面積下降。從XRD圖譜結果，發現沈澱固著法所製備的金觸媒，不論鍛燒溫度的高低都可以觀察到金的繞射峰出現；共沈澱法製備的金觸媒只有在高載量才能出現金的繞射峰。從TEM分析結果，發現不論以共沈澱法或是沈澱固著法製備的Au/ZrO2觸媒，都可以在照片中找到圓球形的金晶粒。而XPS分析的結果指出，共沈澱法製備的Au/ZrO2觸媒表面皆為金屬態的金；但是沈澱析出法製備的Au/ZrO2表面都會有金屬態的金和氧化態的金存在，而隨著鍛燒溫度的增加金屬態對氧化態的金比例會逐漸上升。經過活性測試，我們認為氧化態的金為觸媒反應的活性位置，沈澱固著法為較佳的製備方法。而鍛燒的條件會影響觸媒活性，最佳的鍛燒溫度為573 K。以沈澱固著法製備的2 wt% Au/ZrO2觸媒在563 K下進行甲醇部分氧化反應，能發揮最佳的活性和氫氣選擇率。最後和文獻上的銅觸媒、鈀觸媒的催化結果做比較，Au/ZrO2觸媒不僅擁有不錯的催化活性，且沒有CO的產生(小於500 ppm)。顯然地，Au/ZrO2觸媒在甲醇部分氧化反應中能夠選擇性氧化CO，使得氫氣產物中幾乎沒有CO的污染。

摘要(英)

In this work, zirconium oxide (ZrO2) was used as a catalyst support. ZrO2 supported nanosized Au catalysts (Au/ZrO2) were prepared by the deposition-precipitation (DP) and co-precipitation method (CP). The supported Au catalysts were characterized by inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray diffraction (XRD), thermogravimetric analyzer (TGA), nitrogen adsorption method, scanning electron microcopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).
The thermal decomposition of the Au catalyst precursor starts above 698K. The specific surface area of the calcined catalysts prepared by CP method decreases with increasing the Au loading but catalysts prepared by DP method do not show any difference. From the image of TEM, we can see the black spherical Au crystallites clearly and good dispersion in both two preparation methods. Furthermore, the mean size of Au crystallites increases with an increase in calcination temperature only occurring in Au/ZrO2 prepared by CP method. In XPS analysis, Au catalysts prepared by DP method shows that not only have metallic Au but also oxidative Au in catalysts surface. As calcination temperature is getting higher, the ratio of metallic Au to ionic Au becomes larger.
Zirconium oxide supported Au catalysts was tested by the partial oxidation of methanol (POM) at 503-563K. The results indicate that the optimal preparation method and operating conditions are DP method, 2 wt% in Au loading, 573 K in calcination temperature, and 563 K in reaction temperature.
Compare to copper and palladium catalysts in POM reaction, Au/ZrO2 catalysts display good activity and hydrogen selectivity. Furthermore, Au/ZrO2 catalysts show no CO present. Nanosized Au/ZrO2 may have an opportunity to apply in proton exchange membrane fuel cell.

關鍵字(中)

★ 金觸媒
★ 甲醇部分氧化反應
★ 燃料電池
★ 氧化鋯

關鍵字(英)

★ Au catalyst
★ partial oxidation of methanol reaction
★ fuel cell
★ zirconium oxide

論文目次

摘要 I
ABSTRACT III
目錄 V
圖索引 IX
表索引 XV
第一章緒論 1
1.1 前言 1
1.2 燃料電池 1
1.3 甲醇製氫 5
1.4 金觸媒 6
1.5 研究內容與論文架構 7
第二章文獻回顧 8
2.1 製備方法 8
2.2 鍛燒程序 12
2.3 擔體效應 13
2.4 金的活性位置 13
2.5 金觸媒的應用 15
2.5.1 一氧化碳氧化反應 16
2.5.2 有機揮發物質氧化反應 18
2.5.3 水氣轉移反應 18
2.5.4 碳氫化合物選擇性氧化反應 19
2.5.5 甲醇部分氧化反應 19
第三章實驗方法與裝置 21
3.1 擔體金觸媒的製備 21
3.1.1 觸媒製備程序 21
3.1.2 觸媒代號說明 24
3.2 擔體金觸媒的鑑定分析 25
3.2.1 感應耦合電漿原子放射光譜儀(ICP-AES)分析 25
3.2.2 BET比表面積 26
3.2.3 X-射線繞射分析(XRD) 29
3.2.4 熱重分析(TGA) 30
3.2.5 掃描式電子顯微鏡(SEM) 33
3.2.6 穿透式電子顯微鏡(TEM) 34
3.2.7光電子光譜儀(XPS) 34
3.3 觸媒的活性測試-甲醇部分氧化 35
3.4 實驗流程與操作變數 38
3.5 數據的計算與實例 38
3.5.1 擔體金觸媒理論載量的定義與計算 38
3.5.2 轉化率的定義與計算 41
3.5.3 選擇率的定義與計算 44
3.6 藥品、氣體及儀器設備 46
3.6.1 藥品 46
3.6.2 氣體 46
3.6.3 儀器設備 46
第四章結果與討論 48
4.1 Au/ZrO2觸媒製備條件的探討 48
4.1.1 不同製備方法對金金屬載量的影響 48
4.1.2 鍛燒條件的選擇 48
4.2 Au/ZrO2觸媒的特性分析 51
4.2.1 觸媒總表面積的測定結果 51
4.2.2 X-射線繞射(XRD)的分析結果 52
4.2.3 穿透式電子顯微鏡(TEM)的分析結果 58
4.2.4 光電子光譜儀(XPS)的分析結果 66
4.3 Au/ZrO2觸媒的化性分析 70
4.3.1 Au/ZrO2觸媒的金屬載量對活性以及氫氣選擇性的影響 70
4.3.2 Au/ZrO2觸媒的鍛燒溫度對活性以及氫氣選擇性的影響 73
4.3.3 Au/ZrO2觸媒的製備方法對活性以及氫氣選擇性的影響 76
4.3.4 反應溫度對甲醇部分氧化反應的活性以及氫氣選擇性影響 76
4.4.5 反應時間對Au/ZrO2的影響 79
4.3.6 Au/ZrO2觸媒與文獻上銅觸媒和鈀觸媒在甲醇部分氧化反應上分析結果比較 82
第五章結論 86
第六章參考文獻 88

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指導教授

張奉文(Feg-Wen Chang)

審核日期

2004-7-2

推文