臺灣博碩士論文加值系統

將波洛斯凱特結晶構造之LaMnO3與LaFeO3觸媒擔載於二氧化矽後不僅造成觸媒結晶顆粒變小，也可以藉此調整觸媒本身的酸鹼性值。未擔載的LaMnO3與LaFeO3於觸媒本質上呈現較強的鹼性特質，將二者分別擔載於二氧化矽後，由於四價錳陽離子以及四價鐵陽離子的比例增加導致其路易斯酸性點數量及強度因而增加，擔載後的觸媒因此呈現酸性的觸媒特質。而需要酸鹼催化的乙醇轉化可以用來反應LaMnO3與LaFeO3擔載於二氧化矽前後鹼酸特質的改變。
在低轉化率的反應條件下，乙醇於未擔載之LaMnO3與LaFeO3上的主要轉化產物為鹼性觸媒催化的反向醇醛縮合反應 (Reverse-aldolization) 與 Tishchenko反應，而乙醇於二氧化矽擔載的LaMnO3與LaFeO3上的主要轉化產物為需要酸鹼性點共同催化的醇醛縮合反應(Aldolization) 與酸性催化的脫水反應 (Dehydration)。
　LaMnO3/SiO2 在醇醛縮合反應的活性優於LaFeO3/SiO2的主要的原因為存在於LaMnO3/SiO2表面的正四價錳離子與非晶格氧(nonstoichiometric oxygen) 形成對醇醛縮合反應具有催化活性的路易斯酸 (正四價錳離子) - 鹼 (非晶格氧) 對，而這樣的酸鹼對幾乎不存在於LaFeO3/SiO2，原因為LaFeO3/SiO2富含氧空缺的特性而造成表面非晶格氧的缺乏，因此我們推測除了正四價陽離子之外，非晶格氧的存在與否為另一個影響醇醛縮合反應活性的關鍵因素。

This study reports that the Lewis acid-base properties of peroskite-type LaMnO3 and LaFeO3 can be adjusted by immobilizing them on silica. Bulk LaMnO3 and LaFeO3 were strong base catalyst due to unsaturated-coordinated oxygen on the surface, While, after supported them on silica, the basic properties of bulk materials were diluted and simultaneously acidities improved due to the increased amounts of tetravalent B-site cations. Ethanol reactivity was performed to reflect the different acid-base properties of bulk and silica-supported LaMnO3 and LaFeO3. Under differential analysis conditions, bulk perovskites were active in base-catalyzed reactions such as reverse aldolization and Tishchenko reaction, while silica-supported perovskites were active in aldolization and dehydration. We also notice the higher aldolization activity over LaMnO3/SiO2 than that of LaFeO3/SiO2, the different activity was attributed to existence of excess mobile oxygen on the surface of LaMnO3/SiO2, forming aldolization-active Lewis acid (Mn4+)-base (nonstoichiometric oxygen) pair sites while these sites were absent in LaFeO3/SiO2 which was enriched with oxygen vacancies.

摘要 i
英文延伸摘要 ii
誌謝 xi
目錄 xii
表目錄 xv
圖目錄 xv
第一章 前言 1
1.1引言 1
1.2研究動機 3
第二章 文獻回顧 4
2.1 乙醇轉化反應路徑 4
2.2 乙醇於異相觸媒轉化之探討 8
2.3 波洛斯凱特結構介紹及酸鹼性質 14
2.4 波洛斯凱特於乙醇轉化之研究 19
第三章 實驗儀器與實驗方法 21
3.1 X光繞射儀 21
3.2 比表面積與孔隙分佈分析儀 23
3.3 穿透式電子顯微鏡 25
3.4 感應耦合電將放射光譜儀 26
3.5 X線光電子能譜移 27
3.6 高性能全自動化學吸附儀 28
3.6.1 二氧化碳及氨氣程溫脫附 29
3.6.2 氫氣程溫還原 29
3.6.3 氧氣程溫脫附 30
3.6.4 乙醇程序升溫表面反應 30
3.7 傅立葉轉換紅外光譜儀 32
3.7.1 布朗斯特酸鑑定 33
3.7.2吡啶及二氧化碳吸附實驗 33
3.8 氣相層析儀 35
3.8.1 氣相產物定性與定量 38
3.9 實驗藥品與實驗設備 44
3.10 觸媒製備與合成 46
3.10.1 二氧化矽載體預處理 46
3.10.2 Bulk 波洛斯凱特合成 46
3.10.3 二氧化矽擔載波洛斯凱特合成 46
3.11 觸媒反應性測試 47
第四章 實驗結果與討論 48
4.1 觸媒物理性質鑑定 48
4.1.1 觸媒組成與命名 48
4.1.2 X-光繞射圖樣 48
4.1.3 比表面積與元素組成 49
4.1.4 高解析穿透式電子顯微影像 51
4.1.5 X-光光電子能譜分析 54
4.1.6 氫氣程溫還原測試 58
4.2 觸媒酸鹼性質鑑定 60
4.2.1 氨氣程溫脫附測試 60
4.2.2二氧化碳程溫脫附測試 61
4.2.3吡啶吸附紅外光譜分析 61
4.2.4二氧化碳吸附紅外光譜分析 63
4.2.5 異丙醇轉化測試 64
4.3 乙醇轉化之反應性測試 67
4.3.1乙醇程序升溫表面反應分析 68
4.3.2 觸媒乙醇轉化反應性分析 71
4.3.3 LaFe/SiO2缺氧之於醇醛縮合反應 79
第五章 結論 83
參考文獻 84

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