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研究生： 黃國晏
Guo-Yan Huang
論文名稱： 鎢釕混合氧化物擔載Pt觸媒製備參數對其氫氣氧化反應的CO耐受性探討
Preparation of Tungsten Ruthenium mixed oxide supported Pt catalysts for CO tolerance in Hydrogen Oxidation Reaction
指導教授： 林昇佃
Shawn D. Lin
口試委員: 林修正
Andrew S. Lin
蘇威年
Wei-Nien Su
黃炳照
Bing-Joe Hwang
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： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 115
中文關鍵詞： 金屬混合氧化物 、陽離子摻雜 、水熱法 、氫氣氧化反應
外文關鍵詞： Metal mixed oxide, cation-doping, hydrothermal process, hydrogen oxidation reaction
相關次數： 點閱：188  下載：4 
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    • 氫能時代的來臨，將對照驗證質子交換薄膜燃料電池(PEMFC)技術的發展成熟度，目前PEMFC電極觸媒主要是以碳當作載體，利用碳載體的高導電性與高比表面積以使Pt可以均勻分散，但在操作過程發生的碳腐蝕現象，會導致Pt觸媒活性下降，並降低PEMFC的效能。本研究目的為探討非碳載體之金屬混合氧化物陽極反應觸媒，以提升觸媒穩定性，並提升觸媒抗CO毒化能力，以實驗室先前水熱法合成的W0.7Ru0.3O2 載體為基礎，進一步測試製備參數對觸媒的影響，所測試的參數包括：不同晶相氧化鎢載體、Ru陽離子摻雜形成不同鎢釕比例載體與不同載體鍛燒溫度，最後進行製作流程優化。
    研究結果顯示以EG法自製40%Pt氧化物擔載觸媒可獲得與商用PtRu/C觸媒相近的Pt粒徑(3-4奈米)，以CO-stripping測試中CO起始氧化電位與峰電位，和氫氣氧化反應(HOR)在純氫、100和250ppm CO環境下的旋轉圓盤電極分析與定電位分析，發現優化流程製得的40Pt/W5Ru5-N12-c300與40Pt/W7Ru3-N12-c300觸媒具有比擬商用20Pt10Ru/C觸媒的良好抗CO能力、氫氣氧化活性與穩定性。

    Proton exchange membrane fuel cells (PEMFCs) are expected to have enormous potential for both mobile and stationary applications. Carbon supports are mainly used in electrocatalysts for fuel cells because of good electron conductivity and high surface area that may leads to good dispersion of active Pt particles. However, carbon corrosion under operating conditions of PEMFCs becomes a concern which can cause deterioration in the performance of Pt catalysts. To enhance the durability and the CO tolerance of anodic catalysts, mixed-oxide supports are examined in this study. A simple hydrothermal process is applied to synthesize mixed W-Ru oxide supports and the influences of preparation parameters are examined, including Tungsten oxide phase, Tungsten Ruthenium ratio, and pretreatment temperature, and subsequently the preparation procedure is optimized.
    Pt loading is prepared by EG method. XRD results show that the prepared 40wt%Pt/W5Ru5-N12-c300 contains Pt particle size of 3-4 nm. CO stripping and hydrogen oxidation reaction (HOR) with 100 and 250 ppm CO are examined. The results indicate that 40Pt/W5Ru5-N12-c300 and 40Pt/W7Ru3-N12-c300 catalysts exhibit improved CO tolerance, intrinsic activity and durability comparing to the other prepared catalysts. The overall performance is comparable with commercial 20Pt10Ru/C catalysts.

    摘要 I Abstract II 誌謝 III 圖目錄 VII 表目錄 X 第1章、 緒論 1 1.1 前言 1 1.2 質子交換薄膜燃料電池 (PEMFC) 3 1.3 直接甲醇燃料電池 (DMFC) 4 第2章、 文獻回顧 5 2.1 陽極觸媒介紹 5 2.2 碳載體觸媒 5 2.3 金屬氧化物載體 6 2.3.1 氧化釕 (Ruthenium oxides、RuOx) 7 2.3.2 鎢氧化物 (Tungsten oxides、WOx) 8 2.3.3 混合金屬氧化物 9 2.4 合金觸媒 10 2.5 研究目的與方法 11 第3章、 研究設備與方法 12 3.1 研究架構 12 3.2 藥品與設備 12 3.3 觸媒製備方法 15 3.3.1 RuOxHy的製備 15 3.3.2 水熱法 15 3.3.3 水熱法製備WOx載體 15 3.3.4 水熱法製備h-WOx載體 16 3.3.5 水熱法製備不同鍛燒溫度之WxRu1-xOy載體 16 3.3.6 水熱法製備WxRu1-xOy-N12載體 17 3.3.7 改良式乙二醇還原法製備40wt%Pt觸媒 18 3.4 材料鑑定方法 19 3.4.1 X光繞射分析(XRD) 19 3.4.2 表面積與孔隙度測定儀 (BET) 20 3.4.3 掃描式電子顯微鏡-能量散射光譜儀 (SEM-EDS) 20 3.5 電化學分析方法 21 3.5.1 可逆氫電極(RHE)的前置作業 22 3.5.2 薄膜電極的製備 22 3.5.3 循環伏安法 (Cyclic voltammetry) 23 3.5.4 CO電催化氧化分析 (CO-stripping) 23 3.5.5 純氫氣中氫氣氧化反應之陽極測試條件 (HOR-pure H2) 24 3.5.6 微量CO下氫氣氧化反應之陽極測試條件 (HOR-100 or 250ppmCO/H2) 24 3.5.7 電化學活性表面積與CO/H比例計算 24 3.5.8 塔弗方程式 (Tafel equation) 25 3.5.9 氫氣氧化之分析方法 25 第4章、 結果與討論 28 4.1 不同晶相氧化鎢載體對40wt%Pt觸媒的影響 28 4.1.1 載體與觸媒特性分析 28 4.1.1.1 XRD分析 28 4.1.1.2 材料形貌與EDS成份分析 32 4.1.2 觸媒之電化學特性分析 34 4.1.2.1 觸媒之循環伏安法分析 34 4.2 混合氧化物載體成份與煅燒溫度對40wt%Pt觸媒的影響 38 4.2.1 載體與觸媒特性分析 38 4.2.1.1 XRD分析 38 4.2.1.2 氮氣等溫吸/脫附分析 47 4.2.1.3 材料形貌與EDS成份分析 50 4.2.2 觸媒之電化學反應分析 52 4.2.2.1 觸媒之循環伏安法分析 52 4.2.2.2 觸媒之氫氣氧化反應分析 57 4.3 釕摻雜效應對40wt%Pt觸媒的影響 67 4.3.1 載體與觸媒特性分析 67 4.3.1.1 XRD分析 67 4.3.1.2 氮氣等溫吸/脫附分析 75 4.3.1.3 材料形貌與EDS成份分析 76 4.3.2 觸媒之電化學反應分析 78 4.3.2.1 觸媒之循環伏安法分析 78 4.3.2.2 觸媒之氫氣氧化反應分析 81 第5章、 結論 86 第6章、 參考文獻 87 附錄一 Nafion 厚度計算 92 附錄二 氫氣氧化動力學數據處理 92 附錄三 合成嘗試經驗 103

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