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研究生： 陳力嘉
Li-Jia Chen
論文名稱： 鈦釕混合氧化物擔載Pt觸媒的製備與其在電化學反應特性研究
Mixed Oxide Supported Pt Catalysts for Electrochemical Characteristic Study
指導教授： 林昇佃
Shawn D. Lin
口試委員: 黃炳照
Bing-Joe Hwang
王丞浩
Chen-Hao Wang,
王冠文
Kuan-Wen Wang
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2015
畢業學年度： 103
語文別： 中文
論文頁數： 150
中文關鍵詞： 混合氧化物載體 、水熱法
外文關鍵詞： mixed oxide support, hydrothermal process
相關次數： 點閱：359  下載：3 
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  •  上一筆

    • 如今燃料電池技術日新月異，在應用端已經有相當成熟的技術，但是目前電極觸媒使用碳當作載體，然而碳載體在高電位下會有碳腐蝕問題發生，並且與白金奈米金屬粒子不具有強力的作用力(SMSI)，最終將導致白金的融解，減少白金的利用率進一步導致燃料電池效率降低，本研究探討非碳載體的在陽極觸媒端運用，利用水熱法來合成雙金屬鈦釕氧化物(TixRu1-xO2) 來作探討，將探討載體經過熱處理及不同的鈦與釕合成比例的變化和結構，瞭解金屬氧化物結構對白金觸媒結構之影響，並將其應用在燃料電池陽極電催化反應上。
    XRD、TEM 結果指出利用乙二醇還原法還原出來的白金粒徑大約在4到6奈米之間比商購觸媒還要略大(3.2 nm)，而在電化學測試方面，而在不同比例雙金屬鈦釕氧化物(TixRu1-xO2)當載體乘載白金觸媒，以40Pt/Ti0.7Ru0.3O2和40Pt/Ti0.3Ru0.7O2 具有最佳的效果反應。

    Nowadays, fuel cell technology is expected to have enormous potential for both mobile and stationary applications. The current electrode catalysts use carbon black at the support. However, the weak interactions between the carbon support and the catalytic metal nanoparticles and the corrosion of carbon eventually leads to Pt dissolution, resulting in decrease in the active surface area with long-term operation. In the study binary metal oxide (TixRu1-xO2) was synthesized by a simple hydrothermal process, a novel functionalised support for Pt.
    The XRD and TEM results show that the Pt particle size of 40 wt% Pt/ TixRu1-xO2 catalyst prepared by EG method was in the range of 4-6 nm, which was slightly larger than that of commercial Pt/C and PtRu/C catalysts. The influences of CO on the electrochemical reaction The results of electrochemical analyses indicate that the prepared 40Pt/Ti0.7Ru0.3O2 and 40Pt/Ti0.3Ru0.7O2 catalysis exhibit higher intrinsic activity and better stability in the presence of CO comparing to commercial PtRu/C.

    摘要 I Abstract II 誌謝 III 目錄 V 圖目錄 VIII 表目錄 XII 第一章、緒論 1 1.1 前言 1 1.2 文獻回顧 5 1.2.1 碳載體觸媒開發 6 1.2.3 金屬氧化物觸媒載體 8 1.3 研究目的與方法 15 第二章、研究設備和方法 16 2.1 藥品與儀器設備 16 2.1.1 藥品部分與氣體 16 2.1.2 儀器部分 17 2.2 觸媒製備 18 2.2.1 H2O2直接氧化法 18 2.2.2 水熱法( hydrothermal method) 19 2.2.3 乙二醇還原法 20 2.2.4 改良式乙二醇還原法 20 2.3 材料鑑定分析方法 21 2.3.1 X光繞射分析(XRD) 21 2.3.2 四點探針量測(Four point probe measurement) 22 2.3.3 表面積與孔隙度測定儀(BET) 22 2.3.4 電子穿透顯微鏡(TEM) 23 2.3.5 掃描式電子顯微鏡-能量散射光譜儀(SEM-EDX) 23 2.3.6 感應耦合電漿原子放射光譜儀(ICP-AES) 24 2.3.7 X光吸收光譜(XANES) 25 2.4 電化學分析方法 26 2.4.1 薄膜電極的製備 26 2.4.2 循環伏安法(Cyclic voltammetry) 26 2.4.3 CO電氧化分析 27 2.4.4 陽極測試條件 27 2.4.5 電化學活性表面積計算 28 2.4.6 塔弗方程式(Tafel equation) 29 2.4.7 迴歸分析最小平方法 29 第三章、結果與討論 30 3.1 H2O2直接氧化法和水熱法製備RuO2 載體 30 3.2 TixRu1-xO2氧化物載體製備 34 3.2.1 材料之晶相與型態分析 35 3.2.2 SEM-EDX和ICP-AES 材料組成分析 38 3.2.3 TixRu1-xO2氧化物載體X光吸收近邊緣結構 40 3.2.4 TixRu1-xO2氧化物載體導電度量測 48 3.2.5 金屬氧化物載體BET比表面積測定 50 3.3 40Pt /TixRu1-xO2觸媒分析 52 3.3.1 材料之晶相與型態分析 52 3.3.2 40Pt /TixRu1-xO2 觸媒TEM-EDX分析 54 3.3.3 感應耦合電漿放射光譜儀(ICP-AES)分析 57 3.3.4 40Pt/TixRu1-xO2觸媒的X光吸收近光譜分析 58 3.4 電化學特性分析結果 67 3.4.1 循環伏安法分析 67 3.4.2 金屬氧化物對Pt 氧化脫附CO 的影響 69 3.4.3 陽極測試 71 3.4.4 不同CO濃度陽極測試 81 3.5 Pt顆粒大小對觸媒影響 89 3.5.1 40Pt/TixRu1-xO2 HI之晶相與型貌分析 89 3.5.2 Pt/TixRu1-xO2 HI觸媒X光吸收近邊緣結構 92 3.6 40Pt/TixRu1-xO2HI 電化學特性分析 100 3.6.1 循環伏安法分析 100 3.6.2 HI系列陽極測試 102 3.6.3 陽極觸媒耐久度測試 118 第四章、 結論 123 第五章、 參考文獻 125 附錄一 Nafion 厚度計算 132 附錄二 40Pt/TixRu1-xO2 Ru K edge 未固定 Ru-Pt fitting結果 132 附錄三 高濃度陽極測試 134 附錄四 陽極觸媒成本考量 136 附錄五 扣除內部質傳的誤差 137

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