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研究生: 蔡博凱
Tsai, Po-Kai
論文名稱: 鈀鉑與鈀鉑合金觸媒對於甲乙醇氧化反應表現與機構之探討
Mechanistic Investigation of Methanol/Ethanol Oxidation Reactions (MOR/EOR) on Platinum, and Palladium Their Alloys
指導教授: 王禎翰
Wang, Jeng-Han
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2017
畢業學年度: 105
語文別: 中文
論文頁數: 56
中文關鍵詞: 乙醇氧化反應甲醇氧化反應非即時性傅立葉紅外線光譜儀鈀鉑合金觸媒比例效應
英文關鍵詞: ratio effect, MOR, PtPd alloy catalyst, ex situ FT-IR, CO-stripping
DOI URL: https://doi.org/10.6345/NTNU202202013
論文種類: 學術論文
相關次數: 點閱:130下載:16
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  • 本研究主要探討在碳黑(XC-72)上Pt、Pd、PtPd不同比例分別為3:1, 1:1, 1:3(以下寫作Pt3Pd1,Pt1Pd1,Pt3Pd1)觸媒對於直接甲醇(乙醇)燃料電池中的甲醇(乙醇)氧化反應中的陽極反應,在實驗中所用到的合金觸媒皆為含浸法合成,並且使用XRD、SEM、EDS去鑑定物理性質,接著將觸媒放在1M KOH中曝氮氣再使用電化學CV測量ECSA,再分別利用CV及CA測量1M甲醇和乙醇的電催化活性和穩定度。結果顯示合金的活性和穩定度都優於純Pt與Pd其中Pt3Pd1有著最高的MA(1279 mA/ugPt)及SA65(mA/cm2)而Pt1Pd1有著最好的穩定性(經過90分鐘CA測試後仍有原本51%的電流)。進一步利用ex-FTIR來偵測溶液中的2,4,6電子產物(HCHO, HCOOH, CO32-)隨著CV圈數的變化來推測觸媒在MOR的機制,圖譜顯示所有的合金都有些微的差異,其差異趨勢與CA的結果相同。

    The present study mechanistic investigates methanol/ethanol oxidation reactions (MOR/EOR), the anodic reactions for direct methanol/ethanol fuel cells (DMFC/DEFC), on Pt, Pd and their alloys with the ratios of Pt/Pd = 3:1, 1:1, 1:3 (denoted as Pt3Pd1, Pt1Pd1 and Pt1Pd3) on carbon black XC-72. All the metallic electrodes were fabricated by the impregnation method and characterized by X-ray diffraction (XRD), Secondary electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The fabricated electrodes were examining by cyclic voltammetry (CV) in 1 M KOH purged with N2 to determine their electrochemical surface area (ECSA). The MOR/EOR activity and stability of the electrodes were investigated by CV and chronoamperometry (CA), respectively, in 1 M methanol/ethanol in alkaline solution of 1 M KOH. The electrochemical tests showed that all the alloys has better both activity and stability than pure Pt and Pd; among them Pt3Pd1 has the best activity with mass activity (MA) =1279 (mA/ugPt)and surface activity (SA) = 65(mA/cm2), and Pt1Pd1 has the best stability (51% decay in 90 minutes CA). The MOR performance was further examined by ex-situ FT-IR to determine the variations of products of HCHO, HCOOH and CO32-(in two, four and-six electron reactions) with CV cycles. The spectroscopic results show that all the alloys have smaller variations, indicating the better stability and agreeing with the CA results.

    目錄 IV 圖目錄 V 表目錄 VI Section 1 緒論 1 1-1前言 1 1-2燃料電池 1 1-3直接酒精燃料電池 6 1-4 研究目的與動機 10 Section 2 實驗設備以及流程 12 2-1含浸法金屬觸媒製備 14 2-2觸媒鑑定 15 2-2-1粉末式X光繞射儀(powder X-Ray Diffractometer; XRD) 15 2-2-2掃描式電子顯微鏡(Scanning Electron Microscope; SEM) 16 2-2-3能量散射光譜儀(Energy Dispersive X-ray Spectrometer; EDS) 17 2-3電化學分析 17 2-3-1工作電極製備 17 2-3-2循環伏安法(Cyclic Voltammetry; CV ) 18 2-3-3計時安培法 20 2--4電化學產物分析 20 2-4-1傅立葉紅外線光譜儀 20 Section 3 結果與討論 21 3-1 觸媒鑑定 21 3-2電化學分析 27 3-2-1氫氣吸脫附 27 3-2-2 一氧化碳脫附 28 3-2-3甲醇氧化反應 31 3-2-4乙醇氧化反應 36 3-2-5 甲醇乙醇電催化活性比較 42 3-2-6傅立業轉換紅外光譜儀 43 Section 4 結論 51 Section 5未來展望 53 Reference 54

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