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研究生： 薛敬怡
Hsieh Ching-Yi
論文名稱： 二氧化鈰奈米管的製備與其催化反應之研究
Preparation, Characterization, and Catalytic Studies of Cerium Oxide Nanotubes
指導教授： 簡淑華
Chien, Shu-Hua
何嘉仁
Ho, Chia-Jen
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 113
中文關鍵詞： 二氧化鈰奈米管 、二氧化鈰擔體鉑觸媒 、乙醇重組反應 、一氧化碳氧化反應
英文關鍵詞： cerium oxide nanotubes, Pt/CeO2, ethanol reforming reaction, CO oxidation reaction
論文種類： 學術論文
相關次數： 點閱：113  下載：3 
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    • 本研究係以不同條件製備型態均勻且具高表面積的二氧化鈰奈米管，探討因素包括水熱時間、水洗條件、水熱溫度、鹼液濃度及煅燒溫度。利用粉末X光繞射(XRD) 、掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、氮氣等溫吸脫附為分析工具，探討觸媒組成與其結晶性、型態分佈及表面積。實驗顯示在鹼液濃度為0.6 M，於120 °C水熱24小時，水洗到pH = 9時可得到尺寸分佈一致，直徑約為146 nm，且其表面積最大(S.A. = 73 m2/g)的二氧化鈰奈米管。以450 °C在氧化環境下煅燒可得到具有結構缺陷可促進晶格氧的移動，且完整的二氧化鈰奈米管擔體，以此擔體所製備的鉑觸媒在一氧化碳氧化反應有不錯的活性。
    為了解鉑觸媒之顆粒大小、氯含量與金屬氧化態對一氧化碳氧化反應能力之影響，改變製備方法、前處理與活化條件，實驗顯示以初濕含浸法製備的二氧化鈰奈米管擔體鉑觸媒之鉑顆粒最小(d = 3 nm)，接續以還原水洗前處理之鉑觸媒的殘餘氯含量最少。為得到最佳一氧化碳氧化反應之表現，在還原氣流下以200 °C活化觸媒，可使二氧化鈰奈米管擔體鉑觸媒發揮最佳的活性表現(T50 = 76 °C)。
    以原位光譜分析技術探討二氧化鈰奈米管擔體鉑觸媒之乙醇直接分解（Decomposition of Ethanol, ED)、部分氧化（Partial Oxidation of Ethanol, POE）與蒸氣重組（Steam Reforming of Ethanol, SRE）反應活性與機制。結果顯示在SRE反應中，二氧化鈰奈米管擔體鉑觸媒在室溫即可促進乙醇分解並且產生大量的氫氣，與商用二氧化鈰擔體鉑觸媒比較，其活性與氫氣產生量均有良好的表現。

    Shape-controlled synthesis of CeO2 has drawn lots of attention in the decade. Especially tubular nanostructures have received significant interest since the unique physical and chemical properties. In the present work, CeO2 nanotubes (CeNT) have been fabricated via a hydrothermal method through controlling reaction time, acid washing conditions, reaction temperature, concentration of alkaline solution, and temperature of calcination. The properties of the CeO2 nanotubes were characterized by N2-isotherm sorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM).
    Three kinds of methods are chosen to prepare ceria-nanotubes supported platinum (Pt/CeNT) catalysts: incipient wetness impregnation, impregnation, and sodium borohydride reduction method. Application of catalysis over Pt/CeNT catalysts focus on the CO oxidation (evaluation in the micro flow-reaction) and ethanol reforming (studies with the in-situ spectra) reactions. In the CO oxidation reaction, the residual chlorine on the Pt/CeNT catalyst plays an important role in determining the catalytic activity.
    Combination of in-situ FTIR and TPD-MS techniques to investigate the catalytic performance and mechanisms of ethanol reforming reactions (including decomposition, steam reforming, and partial oxidation of ethanol). The results show the activities of ethanol reforming over Pt/CeNT catalyst is better than the Pt/CeO2(C) catalyst.

    致謝 i 摘要 ii Abstract iii 目錄 iv 表目錄 vii 圖目錄 viii 1. 緒論 1 1.1前言 1 1.2二氧化鈰特性與應用 1 1.2.1特性與應用 1 1.2.2二氧化鈰奈米管的文獻回顧 3 1.3 一氧化碳氧化反應 8 1.3.1 一氧化碳之來源與與毒害 8 1.3.2 一氧化碳氧化於二氧化鈰擔體鉑觸媒文獻回顧 14 1.4乙醇重組製氫 16 1.4.1 原位光譜介紹 19 1.4.2 乙醇重組製氫於二氧化鈰擔體鉑觸媒的文獻回顧 20 1.5 研究動機與目標 22 2. 實驗 23 2.1實驗藥品與儀器 23 2.2 觸媒製備 25 2.2.1 CeOHCO3的合成 25 2.2.2 二氧化鈰奈米管觸媒的合成 27 2.2.2.1 改變水熱時間 28 2.2.2.2 改變水洗條件 29 2.2.2.3 改變水熱溫度 29 2.2.2.4 改變鹼液濃度 29 2.2.2.5 改變煅燒溫度 30 2.2.3 二氧化鈰奈米管擔體鉑觸媒的合成 30 2.2.3.1 改變製備方法 31 2.2.3.2 改變前處理條件 34 2.3特性鑑定與原理 34 2.3.1 粉末X光繞射光譜(XRD 34 2.3.2 氮氣等溫吸附/脫附(N2 adsorption-desorption isothermal) 35 2.3.3 誘導偶極電漿原子發射光譜(ICP-AES) 36 2.3.4 程溫還原(TPR) 37 2.3.5場發射掃描式電子顯微鏡(FESEM) 38 2.3.6掃瞄式電子顯微鏡–X射線能量散佈分析(SEM-EDS) 38 2.3.7穿透式電子顯微鏡(TEM) 38 2.3.8 X射線光電子光譜(XPS) 38 2.4 一氧化碳氧氧反應之流式微反應系統測試(flow-micro reactor) 39 2.5 乙醇重組製氫反應 41 2.5.1原位紅外線光譜儀(In-Situ FTIR) 41 2.5.2程溫脫附質譜(TPD-MS) 41 3. 結果與討論 45 3.1 CeOHCO3 45 3.2 二氧化鈰奈米管 47 3.2.1 水熱時間的影響 47 3.2.2 水洗條件的影響 53 3.2.3 水熱溫度的影響 58 3.2.4 鹼液濃度的影響 64 3.2.5煅燒溫度的影響 70 3.3 二氧化鈰奈米管擔體鉑觸媒 76 3.3.1鉑觸媒特性鑑定 76 3.3.1.1 不同前處理條件的影響 76 3.3.1.2 不同製備方法的影響 80 3.3.2一氧化碳氧化之催化活性探討 83 3.3.3乙醇重組反應之探討 86 3.3.3.1 原位紅外線光譜分析 86 3.3.3.2 程溫脫附質譜分析 90 3.3.3.3 乙醇重組反應機制探討 102 4. 結論 104 5. 參考文獻 106

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