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研究生: 秦宇
Chin Yu
論文名稱: 機理性地探討甲醇及乙醇氧化反應於鉑二元與鉑錫三元 (銀、銅、釕)合金觸媒
Mechanistic investigation of methanol/ethanol oxidation reaction on PtM/PtSnM(M=Ag,Cu,Ru)
指導教授: 王禎翰
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 66
中文關鍵詞: 甲醇及乙醇氧化電化學三元合金XPS
英文關鍵詞: MOR&EOR, Electrochemistry, Platinum, Tin, Trimetallic, XPS
DOI URL: http://doi.org/10.6345/NTNU202001648
論文種類: 學術論文
相關次數: 點閱:47下載:19
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  • 此次研究主要探討甲醇及乙醇氧化反應(MOR/EOR)作用於碳黑XC-72上的金屬觸媒PtM/PtSnM(M = Ag,Cu,Ru)。所有合金觸媒都以含浸法合成,利用能量色散X射線光譜儀 (EDS)、粉末式X光繞射分析儀 (XRD) 及X光光電子光譜儀 (XPS) 來分別鑑定元素組成,晶格結構和各金屬氧化態。電化學實驗以循環伏安法 (CV) 檢測甲醇、乙醇氧化反應 (MOR/EOR) 活性以及合成的催化劑反應活性面積 (ECSA) ,而以計時電流法(CA)檢測合成的催化劑的穩定性。此外,我們採用傅立葉轉換紅外光譜儀 (FTIR) 來研究反應中產生的中間體和產物,以便了解其反應機制。在我們的電化學結果中可以發現Pt3Ag1Sn1具有最佳的MOR活性,但穩定性不佳。Ag的加入改變Pt表面的電子結構,讓甲醇的第一步反應快速進行,但是中間產物CO的脫附反而難以執行;Sn的加入能夠利用其吸附的氧來加速氧化中間產物,釋放活性表面,提升觸媒穩定性。而Pt3Ag1Sn1具有最佳的EOR活性和穩定性,Ag的加入改變Pt表面的電子結構,加強了EOR中的C2路徑反應,不易產生毒化表面的CO吸附,並且產生更強的反應電流;而Sn的加入提高了親氧性,加速了反應的進行,但其對穩定性的正面影響並不明顯。另外利用傅立葉轉換紅外光譜 (FTIR)來判別金屬觸媒的MOR/EOR反應機制,加入不同過渡金屬後產生反應路徑的變化是影響金屬觸媒的MOR/EOR 活性及穩定性的重點。MOR反應中的主要產物為甲醛及甲酸在各觸媒中都有發現;而各觸媒在EOR反應中主要的產物為乙酸,在各觸媒中以C2為主要反應路徑。而不論在MOR或EOR的IR結果中,產物產量最高的觸媒都是Pt3Ag1Sn1。

    The present work mechanistically investigates the methanol and ethanol oxidation reactions (MOR and EOR) on carbon supported Pt3M1 bimetallic and Pt3Sn1M1 trimetallic (M = Ag, Cu and Ru) catalysts. The samples were fabricated by impregnation method and characterized by Energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) for their chemical composition, lattice constants and surface composition/oxidation states, respectively. The electrochemical active surface area (ECSA) and MOR/EOR performance were examined by cyclic voltammetry (CV); their durability were tested by chronoamperometry (CA). Also, the key intermediates during the electrochemical reactions were monitors by Fourier transfer infrared spectroscopy (FTIR) to assist the mechanism study. Pt3Sn1Ag1 has the best electrochemical performance with highest mass and specific activities (MA and SA) as well as the lower onset potential among the bimetallic catalysts, attributable to the enlarged lattice and less oxidized surface Pt upon Ag addition to assist the initial step in the electroxidation reaction. However, the stability is harmed by the retarded CO desorption in MOR. Similarly, Pt3Sn1Ag1 has the best electrochemical performance among the trimetallic catalysts; the addition of oxophilic Sn can further assist the oxidation of poisoning CO to enhance the stability. The FTIR results found that the main products of MOR are formaldehyde and formic acid in the 2 and 4-electron oxidation process; similarly, EOR mainly follows the C2 reaction pathway forming acetaldehyde and acetic acid, which is more abundant. Consistently, Pt3Sn1Ag1 shows the highest yields of those products in both MOR and EOR.

    目錄 iv 圖目錄 vi 表目錄 viii 第一章 緒論 1 1-1 前言 1 1-2 直接酒精燃料電池 2 1-3 直接甲、乙醇燃料電池陽極觸媒 3 1-4 研究動機與目的 7 第二章 實驗設備及流程 8 2-1 含浸法製備金屬觸媒 9 2-2 觸媒鑑定 10 2-2-1 能量色散X光光譜儀 (Energy Dispersive X- Ray Spectrometer; EDS) 10 2-2-2 粉末式X光繞射儀 (Powder X - Ray Diffractometer; XRD) 12 2-2-3 X光光電子光譜儀 (X - Ray Photoelectron Spectroscopy; XPS) 14 2-3 電化學分析 16 2-3-1 工作電極製備 17 2-3-2 循環伏安法 (Cyclic Voltammetry; CV) 17 2-3-3 計時安培法 (Chronoamperometry; CA) 18 2-4 電化學產物分析 19 2-4-1 傅立葉紅外線光譜儀 (Fourier Transfer Infrared Spectrometer; FTIR) 19 第三章 結果與討論 20 3-1 觸媒鑑定 20 3-1-1 能量散射光譜儀 (Energy Dispersive X – Ray Spectrometer; EDS) 20 3-1-2 粉末式X光繞射儀 (Powder X - Ray Diffractometer; XRD) 22 3-1-3 X光光電子光譜儀 (X – Ray photoelectron Spectroscopy; XPS) 25 3-2 電化學分析 32 3-2-1 氫吸脫附 (ECSA) 32 3-2-2 甲醇氧化反應 (Methanol Oxidation Reaction) 35 3-2-3 甲醇電催化穩定度比較 42 3-2-4乙醇氧化反應 (Ethanol Oxidation Reaction) 44 3-2-5 乙醇電催化活性及穩定度比較 50 3-3 傅立葉轉換紅外光譜儀分析 52 3-3-1 甲醇氧化反應紅外光譜分析 52 3-3-2 乙醇氧化反應紅外光譜分析 56 第四章 結論 61 參考資料 64

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