臺灣博碩士論文加值系統

本研究利用微波反應還原方法，於乙二醇之系統中合成Pt-Ag雙合金觸媒，另外，以逐步還原法製備出Pt @ Ag/C及Ag @ Pt/C等奈米級之雙合金觸媒。並利用同步輻射吸收光譜技術，配合本實驗室所發展之原子結構參數對各個雙金屬觸媒材料結構作分析，以探討其結構對ㄧ氧化碳催化氧化反應之影響。
由XRD與TEM圖之結果得知大部份自製Pt-Ag雙金屬合金觸媒之晶粒約為1~3 nm及平均粒徑約為2~3 nm，而自製Ag @ Pt/C觸媒，經XRD分析得到分相的FCC結構，判斷其應非合金相，並且平均粒徑較大且有部分聚集。研究中也藉由程序升溫表面反應，測量CO氧化之效應以電化學方法量測材料之電化學活性，其結果皆以觸媒Pt-Ag/C-R1-1催化性能最好。
本研究嘗試以不同製程與不同原子比例探討觸媒奈米結構的變化，與其氣相與液相中CO氧化催化性能建立關聯性，以尋求對CO氧化之最佳觸媒結構。

In this work, a reduction method based on microwave reaction was used to synthesize Pt-Ag bimetallic catalysts in ethylene glycol solution. A step by step procedure was adopted to prepare Ptcore @ Agshell/C and Agcore @ Ptshell/C nano-sized bimetallic catalysts. By employing the X-ray Absorption Spectroscopy(XAS) and the extracted atomic structure parameters the structure of the bimetallic catalysts was analyzed. The relationship between the structure of the synthesize catalysts and activity toward CO oxidation.
From the XRD analysis, the grain size of synthesized catalysts were about 1~3 nm wich is consistent with TEM observation. From XRD analysis, the Ag @ Pt/C catalysts with larger grain size exhibit a separated fcc structure, it was found that some of Agcore @ Ptshell/C catalysts were aggregated. In this work Temperature Programmed Surface Reaction (TPSR) was employed to evaluate the activity for CO oxidation and the electrochemical activity for CO stripping. The results show that the Pt-Ag/C-R1-1 catalyst shows the bast performance for CO oxidation.
The Pt-Ag bimetallic catalysts were synthesized by changing the sequential procedure and the solution composition. The relationship between their structure and CO oxidation in both gas and liquid phase was established. The best structure of the synthesized catalyst for CO oxidation was found in this studty.

摘要 I
Abstract .II
致謝 ..III
目錄 IV
圖目錄 ...IX
表目錄 XXIX
第一章 緒論 1
1.1前言 1
1.2奈米材料之定義、範疇及特性 3
1.3金屬奈米粒子及核殼型複合奈米粒子 ..6
1.3.1金屬奈米粒子 ..6
1.3.2核殼型複合奈米粒子 ..7
1.4雙合金奈米觸媒 11
1.4.1雙合金奈米粒子之製備 14
1.4.2觸媒奈米結構鑑定 21
1.5 研究動機、目的與方法 25
第二章 原理 27
2.1化學還原法之原理 27
2.2 X-ray吸收光譜之原理 29
2.2.1 EXAFS .29
2.2.2 XANES 35
2.2.3數據分析 37
2.2.3.1以X光吸收光譜分析觸媒結構……………………………..42
2.3 XRD分析原理 46
2.4電化學原理 47
2.4.1循環伏安法 47
2.4.2極化曲線 51
2.5 程序升溫表面反應(TPSR)原理 52
2.6質譜儀(Mass Spectrometer)原理 54
第三章 實驗設備與方法 57
3.1實驗藥品及設備 57
3.1.1實驗藥品 57
3.1.2儀器設備 58
3.2實驗方法 59
3.2.1白金-銀雙金屬奈米觸媒材料製備 59
3.2.1.1碳黑之前處理 59
3.2.1.2微波反應還原方式合成Pt-Ag/C奈米觸媒(1) 59
3.2.1.3微波反應還原方式合成Pt-Ag/C奈米觸媒(2) 61
3.2.1.4微波反應還原方式合成Pt-Ag/C奈米觸媒(3) 62
3.2.2.5 微波反應還原方式合成Pt core @ Ag/C奈米觸媒 64
3.2.1.6 微波反應還原方式合成Ag core @ Pt/C奈米觸媒 66
3.2.2 材料鑑定與分析 69
3.2.2.1 XRD分析 69
3.2.2.2 TEM 分析 69
3.2.2.3 EDS元素分析 70
3.2.2.4 電化學特性測試 70 3.2.2.4.1電極之製備 71
3.2.2.4.2 電化學特性量測 71
3.2.2.4.2.1循環伏安法 72 3.2.2.4.2.2 CO氧化測試 72
3.2.2.5 X光吸收光譜(XAS) 73
3.2.3.5.1 EXAFS之曲線適配 73 3.2.2.6 程序升溫表面反應(TPSR) 74
第四章 結果 75
4.1白金-銀雙金屬奈米觸媒材料之特性分析 75
4.1.1 能譜儀分析(EDX) 78
4.1.2 XRD與TEM分析 81
4.1.3 不同觸媒材料結構之XANES及EXAFS圖譜變化 90
4.1.3.1 X光吸收近邊緣結構 90
4.1.3.2 延伸X光吸收微細結構 97
4.1.4 程序升溫表面反應(TPSR) 132
4.2電化學特性量測結果 .140
4.2.1 循環伏安法 140
4.2.2 CO氧化測試結果 143
第五章 討論 148
5.1白金-銀雙金屬奈米觸媒材料之探討 148
5.1.1 白金-銀雙金屬奈米觸媒材料之XRD及TEM比較 148
5.1.2 白金-銀雙金屬奈米觸媒材料之結構比較 149
5.1.3原子分佈特性及觸媒結構與CO氧化的關係 160
5.1.3.1原子分佈特性及觸媒結構與程序升溫表面反應(TPSR)方
式氧化CO的關係 160
5.1.3.2 原子分佈特性及觸媒結構與電化學方式CO剝除的關係
163
第六章 結論 169
附錄 171
參考文獻 265

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