臺灣博碩士論文加值系統

本論文著眼於鑭系金屬波洛斯凱特觸媒LaBO3(B=錳、鈷和鐵) 與LaMn0.95B’0.05O3 (B’=鈀、鉑和銠) 於甲醇部分氧化(partial oxidation of methanol, POM)之應用。本研究使用不同的物理與化學方法鑑定觸媒的表面和本體。包括比表面積測定(BET)、結晶構造判定(XRD)、表面組成分析(EDS)、表面貴金屬價態分析(XPS)、程溫還原分析(H2-TPR)、程溫氧化分析(TPO)、程溫氧脫附分析(O2-TPD) 和甲醇程溫脫附分析 (CH3OH-TPD)。研究發現，以Mn做為B-site的波洛斯凱特觸媒擁有最好的活性，其主要反應路徑為甲醇燃燒。添加貴金屬的波洛斯凱特觸媒在還原能力和氧的活性相較於LaMnO3有明顯的改變，造成其在甲醇部分氧化反應上的差異，其中又以LaMnPd有最明顯的效果。波洛斯凱特觸媒的氧化還原特性可以促進甲醇部分氧化產生甲醛。因此，本研究也提出LaMnO3系波洛斯凱特觸媒進行甲醇部分氧化的反應機制。

This study investigates methanol partial oxidation over lanthanum transition metal based perovskites, i.e., LaBO3(B = Mn, Fe, and Co) and LaMn0.95 B’0.05O3(B’=Pd, Pt, and Rh). Their bulk and surface properties were characterized by appropriate physiochemical techniques including BET surface area measurement, XRD, EDS, XPS, H2-TPR, TPO, O2-TPD, and CH3OH-TPD. LaMnO3 shows better activity than LaFeO3 and LaCoO3. The major reaction route under oxidative environments is methanol combustion. The characterizations showed significant differences of reducibility and oxygen activity between promoted and un-promoted LaMnO3. Such deviants resulted in diverse catalytic behaviors in methanol partial oxidation. Among them, LaMnPd show the best performance. Perovskite’s redox property was discovered to enhance partial oxidation route to formaldehyde while oxygen activity played a central role in combustion. Accordingly, plausible reaction mechanism of methanol partial oxidation over LaMnO3 based perovskites was thereby proposed.

目錄
摘要 I
Abstract II
目錄 III
表目錄 V
圖目錄 VI
第一章 前言 1
1.1 引言 1
1.2 研究動機 9
第二章 文獻回顧 10
2.1 波洛斯凱特觸媒構造 10
2.2 波洛斯凱特觸媒特性 12
2.3 波洛斯凱特觸媒的製備 15
2.4甲醇部分氧化生成甲醛 16
2.5波洛斯凱特觸媒於甲醇氧化反應 20
第三章 實驗 22
3.1 X光繞射儀 22
3.2 比表面積分析儀 23
3.3 X 射線光電子能譜儀 24
3.4 掃描式電子顯微鏡 25
3.5程溫還原反應 26
3.6程溫氧化反應 27
3.7 氧程溫脫附反應 28
3.8 甲醇程溫脫附反應 29
3.9實驗設備和藥品 31
3.10 觸媒製備 32
3.11 活性測試 33
3.12 產物定性定量分析 34
第四章 結果與討論 40
4.1 不同B-site觸媒物性鑑定 40
4.2 不同B-site觸媒程溫還原分析 43
4.3 不同B-site觸媒進行TPR後之XRD分析 43
4.4 不同B-site觸媒氧程溫脫附分析 46
4.5 不同B-site觸媒活性測試 48
4.6 添加貴金屬之LaMn觸媒物性鑑定 52
4.7 添加貴金屬之LaMn觸媒XPS分析 55
4.8 添加貴金屬之LaMn觸媒程溫還原/氧化分析 58
4.9 添加貴金屬之LaMn觸媒程溫吸/脫附分析 58
4.10 添加貴金屬之LaMn觸媒活性測試 66
第五章 結論 75
第六章 未來方向 76
參考文獻 77
附件-發表文獻 88

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