在本研究中，我們改良前人所開發的可調控共沉澱法，在無界面活性劑的條件下，以偏矽酸鈉作為矽源，乙酸乙酯作為酸鹼調控劑，製備由二氧化矽顆粒鬆散交聯所形成具高比表面積以及高孔體積的奈米孔洞二氧化矽材料，並進一步在合成溶液中加入不同鋅銅比的氨錯離子作為金屬前驅物，以製備出不同鋅銅比的高分散銅基觸媒，以應用於催化丙烯選擇性氧化反應。藉由氫氣程溫還原以及臨場X光吸收光譜，我們發現銅可被還原為零價，銅鋅之間存在的強作用力會使部分氧化鋅逐漸覆蓋於銅表面。催化實驗結果顯示，觸媒的活性與鋅含量多寡呈先升後降的趨勢，在260 oC的反應溫度下，具最佳鋅銅氨錯離子比(0.2)的觸媒，丙烯轉化率可達20.62 %，丙烯醛產率可達12.06 %，產率約為純銅觸媒的三倍。我們進一步藉由臨場X光吸收光譜以及臨場漫反射紅外光譜，我們發現在反應條件下銅的價態主要為一價，表面仍覆蓋部分氧化鋅。一氧化碳吸附實驗顯示一價銅表面的氧化鋅可扮演電子予體，我們認為此現象可提升銅觸媒的本質活性。

In this study, the controlled coprecipitation method we developed, utilizing sodium silicate as silica source and ethyl acetate as pH modifier, was optimized and applied to fabricate nanoporous silica materials with high surface area and pore volume in the absence of surfactants, comprising loosely packed silica nanoparticles. Zinc/copper ammonia complexes with different molar ratio were further added as metal precursor to prepare highly dispersed copper-based catalysts with different zinc/copper ratio. With H2 TPR and in-situ XAS, we found that copper species could be reduced into Cu0, partially covered with zinc oxide due to the strong interaction between them. The prepared catalysts were further conducted in catalytic selective oxidation of propylene to acrolein; With different zinc/copper ratio, the activity of catalysts rise first and then descend. With an optimized zinc/copper ratio in ammonia complex of 0.2, the activity was about three times higher than that of the copper catalyst. The promotional effect was further investigated by in-situ XAS and CO chemisorption, revealing that the copper species were in Cu+ state after catalytic reactions, partially covered with zinc oxide acting as electron donors, enhancing the intrinsic activity of copper-based catalysts.

謝誌 I
摘要 II
Abstract III
目錄 IV
圖目錄 VII
表目錄 XI
第一章 緒論 - 1 -
1.1 異相催化觸媒原理 - 1 -
1.2 丙烯選擇性氧化反應 - 6 -
1.3 丙烯選擇性氧化催化機制 - 9 -
1.4 有序及無序奈米孔洞二氧化矽材料簡介 - 19 -
1.5 二氧化矽的溶膠-凝膠化學 - 23 -
1.6 可調控共沉澱法 - 27 -
1.7 研究動機 - 31 -
第二章 實驗部分 - 33 -
2.1 實驗藥品 - 33 -
2.2 樣品製備 - 34 -
2.2.1 以可調控共沉澱法合成純奈米孔洞二氧化矽材料 - 34 -
2.2.2 以可調控共沉澱法製備銅鋅觸媒 - 34 -
2.2.3 以可調控共沉澱法合成對照組純鋅觸媒 - 36 -
2.2.4 樣品命名 - 37 -
2.3 催化研究 - 38 -
2.3.1 丙烯選擇性氧化反應 - 38 -
2.3.2 氫氣程溫還原研究 - 40 -
2.3.3 臨場漫反射式紅外光譜儀 - 42 -
2.3.4 臨場X光吸收光譜實驗 - 46 -
2.4 材料分析簡介 - 52 -
2.4.1 粉末X光繞射 - 52 -
2.4.2 氮氣物理吸脫附 - 53 -
2.4.3 掃描式電子顯微鏡 - 58 -
2.4.4 能量散射光譜 - 59 -
2.4.5 穿透式電子顯微鏡 - 60 -
2.4.6 感應耦合電漿質譜 - 61 -
2.4.7 紫外光/可見光光譜 - 62 -
第三章 結果與討論 - 64 -
3.1 奈米孔洞二氧化矽材料的最佳化 - 66 -
3.2 以可調控共沉澱法製備銅鋅觸媒及其鑑定 - 69 -
3.2.1 銅鋅觸媒鑑定 - 70 -
3.3 丙烯選擇性氧化 - 93 -
3.3.1 丙烯選擇性氧化反應 - 93 -
3.3.2 觸媒穩定性測試 - 96 -
3.3.3 催化反應條件下觸媒金屬價數分析 - 98 -
3.3.4 反應氣體之化學吸附 - 102 -
3.3.5 催化反應條件下觸媒臨場一氧化碳吸附紅外光譜 - 104 -
3.4 綜合討論 - 108 -
第四章 結論與展望 - 110 -
第五章 參考文獻 - 112 -

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