以氧化還原置換反應製備Pt和PtIr修飾Pd金屬觸媒及其應用

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研究生：	陳信豪 Hsing-Hao Chen
論文名稱：	以氧化還原置換反應製備Pt和PtIr修飾Pd金屬觸媒及其應用 Pt and PtIr Modified Pd Nanocatalyts Prepared by Redox Transmetallation Reaction and Their Applications
指導教授：	黃炳照 Bing-Joe Hwang
口試委員:	江志強 Jyh-Chiang Jiang 周澤川 Tza-chuan Chou 杜景順 Jing-shuen Du
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：	2008
畢業學年度：	96
語文別：	中文
論文頁數：	111
中文關鍵詞：	氧化還原置換反應、欠電位沉積單層銅、氧氣還原、單層雙金屬觸媒
外文關鍵詞：	Redox transmetallation reaction, Underpotential deposition monolayer copper (UPD), monolayer bimetallic catalysts, Oxygen reduction reaction(ORR)
相關次數：	點閱：360 下載：1
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上一筆

本研究是以氧化還原置換反應製備Pt和PtIr修飾Pd金屬觸媒，並探討其於氧氣還原之催化效能。
於改變UPD ML Cu沉積電位之研究中，Pt(Ⅱ)與UPD ML Cu進行氧化還原置換反應後所得之ML Pt/Pd/C電極，其催化氧氣還原之效能會隨著Pt之負載量增加逐漸提升，而Pt(Ⅱ)與沉積電位為0.3 V之UPD ML Cu進行氧化還原置換反應所得之ML Pt/Pd/C，催化氧氣還原效果達最佳，原因可能為ML Pt覆蓋於Pd表面時，Pd會丟電子給Pt，兩金屬間電子效應有助於降低OH與Pt間之吸引力，進而提高Pt與氧氣之間之作用力，當UPD ML Cu沉積電位更低時，分別為0.28 V與0.27 V，Pt(Ⅱ)與UPD ML Cu進行氧化還原置換反應所製備之ML Pt/Pd/C，其催化氧氣還原效果變差，其原因為第二層Pt沉積於第一層ML Pt表面上或是擴散進入Pd-core內，而導致催化氧氣效能變差。
而於改變UPD ML Cu沉積時間之研究結果中，發現UPD ML Cu沉積時間越短，ML Pt/Pd/C催化氧氣還原效能越差，主要原因為Pt(Ⅱ)與短沉積時間UPD ML Cu進行氧化還原置換反應後，沉積於Pd/C表面之ML Pt不足，亦即過多之Pd裸露於表面，遂而觸媒催化氧氣還原之效能降低。
於單層雙金屬觸媒系統當中，於ML Pt/Pd/C觸媒中添加第三元金屬M ，會提升觸媒催化氧氣還原之效能，其原因為第三元金屬M對於OH基與O基具有強之吸附力，而使OH基於Pt表面之覆蓋率降低，進而提升催化氧氣之效能。於實驗結果中，ML Pt(4)Ir(2)/Pt/Pd/C催化氧氣還原效果為最佳。

Pt and PtIr modified Pd nanocatalysts were prepared by redox transmetallation reaction and studied on the performance of oxygen reduction.
In the case of ML Pt/Pd/C, the redox transmetallation reaction was employed between the Pt(Ⅱ) and the UPD ML Cu on Pd/C with various deposition potential of UPD ML Cu on Pd/C. It was found that the performance of oxygen reduction was gradually improved with the increase of ML Pt loaded on the Pd/C. The highest performance of oxygen reduction was achieved by the ML Pt/Pd/C with UPD ML Cu deposited at the potential of 0.3 V on Pd/C. That may be due to the electronic effects originating from Pt atoms withdrawing electrons from the neighboring Pd atoms, which resulted in the weaker interaction between Pt and OH, and subsequently enhanced the interaction between Pt and O2. The ML Pt/Pd/C by redox transmetallation between Pt(Ⅱ) and UPD ML Cu deposited at the potential of 0.28 V and 0.27 V exhibited the worse perforrmance for oxygen reduction. The enhancement effect was lower, when Pt began to form multilayers on the surface or diffused into the Pd core.
Considering the effect of various deposition time of UPd ML Cu on Pd/C for ML Pt/Pd/C to the performance of oxygen reduction, the catalyst prepared by shorter deposition time behaved the worse performance of oxygen reduction. The main effect was caused by the less amount of ML Pt deposited on the Pd/C, which resulted in the more amount of Pd atoms exposing to the surface, and therefore worse performance of oxygen reduction was shown.
The performance of oxygen reduction was investigated by mixed ML on Pd/C catalysts. The results showed great enhancement for oxygen reduction by the incorporation of ML PtIr with Ir atoms adsorbing OH or O strongly, resulting in the decrease of Pt-OH coverage. The ML Pt(4mM)Ir(2mM)/Pd/C possessed the highest performance of oxygen reduction in the system of mixed monolayer/Pd/C catalysts.

摘要	I
ABSTRACT	III
誌謝	V
目錄	VII
圖目錄	XIII
表目錄	XXV
第一章 緒 論	1
1 前言	1
2 直接甲醇燃料電池(DMFC)	6
2.1 DMFC陽極觸媒	8
2.1.1 DMFC陽極觸媒材料	10
2.2 DMFC電解質	12
2.3 DMFC陰極材料	13
3 UPD金屬修飾貴金屬電極	14
4 UPD CU簡介	18
5 研究動機與目的	24
第二章 原理	25
1 XRD分析原理	25
2 電化學原理	27
2.1 循環伏安法	27
2.2 極化曲線	31
2.3 旋轉盤電極(Rotating Disc Electrode, RDE)	32
第三章 實驗設備與方法	37
1 實驗藥品及設備	37
1.1 實驗藥品	37
1.2 儀器設備	38
2實驗方法	38
2.1製備觸媒漿料	38
2.2 製備0.5 M硫酸	39
2.3設備清潔	40
2.4滴觸媒漿料於RDE (Rotating Disk Electrode)表面之程序	40
2.5電化學測試槽之製備	41
2.6電化學量測步驟	42
2.6.1不同Cu之濃度修飾Pd/C/Nafion電極表面	42
2.6.1.1 Pd/C/Nafion之循環伏安	42
2.6.1.2  UPD ML Cu之沉積與脫附	43
2.6.2 Pt(Ⅱ)與不同沉積電位之UPD Cu進行以氧化還原反應置換修飾Pd/C/Nafion電極表面	45
2.6.2.1 Pd/C/Nafion之循環伏安	45
2.6.2.2 UPD Cu之循環伏安及其沉積與脫附	45
2.6.2.3單層鉑修飾Pd/C/Nafion電極	46
2.6.2.4 ML Pt/Pd/C/Nafion之循環伏安	46
2.6.2.5氧氣還原	46
2.6.3. Pt(Ⅱ)與不同沉積時間之UPD Cu進行氧化還原反應置換修飾Pd/C/Nafion電極	48
2.6.3.1 Pd/C/Nafion之循環伏安	48
2.6.3.2 UPD Cu之循環伏安及其沉積與脫附	48
2.6.3.3單層鉑修飾Pd/C/Nafion電極	49
2.6.3.4 ML Pt/Pd/C/Nafion之循環伏安	49
2.6.3.5氧氣還原	49
2.6.4 單層雙金屬( ML PtIr)修飾Pd/C/Nafion電極	51
2.6.4.1 Pd/C/Nafion之循環伏安	51
2.6.4.2 UPD Cu之循環伏安及其沉積與脫附	51
2.6.3.3單層雙金屬(ML PtIr)修飾Pd/C/Nafion電極	52
2.6.4.4 ML PtIr/Pd/C/Nafion之循環伏安	52
2.6.4.5氧氣還原	52
第四章 結果	55
1 XRD 分析結果	56
2 電化學特性分析	57
2.1 不同Cu濃度修飾之Pd/C/Nafion觸媒	57
2.2  Pt(Ⅱ)與不同沉積電位下之UPD ML Cu進行氧化還原置換反應製備ML Pt/Pd/C	63
2.2.1  氧氣還原(Oxygen reduction reaction, ORR)	77
2.3 Pt(Ⅱ)與沉積電位為0.3 V不同沉積時間下之UPD ML Cu進行氧化還原置換反應製備ML Pt/Pd/C	80
2.3.1 氧氣還原反應(ORR)	84
2.3.2 氧氣還原反應(ORR)	92
2.4  Pt(Ⅱ)(4mM)Ir(Ⅲ)(XmM)與UPD ML Cu進行氧化還原置換反應製備ML PtIr/Pd/C	94
2.4.1 氧氣還原反應 (Oxygen reduction reaction)	98
第五章 討論	101
第六章  結論	105
第七章 參考文獻	107
第八章 附錄	113

                                

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