臺灣博碩士論文加值系統

本研究以硬脂酸與異硬脂酸合成溶於有機溶劑中之金屬前驅物，以氫氣還原後，即可得分散於有機溶劑中之奈米級金屬粒子。鈀金屬奈米粒子的型態受金屬保護基結構的影響，以直鏈結構之硬脂酸做為保護基，可得三角形的奈米粒子，以多支鏈的異硬脂酸為保護基，奈米粒子則呈現長條狀。此兩種金屬前驅物於二氧化碳膨脹溶液(CO2-expanded liquid, CXL)中進行還原，皆可得球型的鈀金屬奈米粒子，同時可得到較小得鈀金屬奈米粒子粒徑與較窄的粒徑分布。
鈀金屬奈米粒子之活性受到奈米粒子型態的影響，球型奈米粒子之活性最好，其次是三角形奈米粒子，活性最差的是長條形奈米粒子。將此法合成之鈀金屬奈米粒子應用於氫化反應時，可將還原與氫化程序結合為單一步驟進行反應，其活性優於商用觸媒Pd/C與商用金屬前驅物(醋酸鈀與乙醯丙酮鈀)。
於二氧化碳膨脹液體中，亦可合成粒徑約為 3 nm之鈀銀雙金屬奈米粒子，這些粒子具有相當優良的分散性。經由鑑定證實鈀銀雙金屬奈米粒子結構為合金型奈米粒子且其組成具有可調整性。鈀銀雙金屬奈米粒子之粒徑與分散性與氫氣添加量及還原溫度有關，最佳的合成條件為還原氣體氫氣與二氧化碳之壓力分別為200 psi與600 psi，以及40 oC下還原60 min，可得粒徑為2.9 ± 0.7 nm之鈀銀雙金屬奈米粒子。
以鈀銀雙金屬奈米粒子進行Phenylacetylene氫化反應時，加入二氧化碳可提高Styrene選擇率，當以Pd0.3Ag0.7為觸媒時，二氧化碳添加量為20%，於40 oC下反應30 min，轉化率可達100%，Styrene選擇率為91.8%。

摘 要 i
目 錄 iv
表目錄 vii
圖目錄 viii
第一章 緒　論 1
第二章 文獻回顧 3
2.1 奈米粒子之簡介與應用 3
2.2 金屬奈米粒子之製備方法 5
2.2.1鹽類還原法 10
2.2.2 多元醇還原法 14
2.2.3 溶劑熱法 18
2.3 金屬奈米粒子之形成機制 20
2.4 高壓二氧化碳應用於奈米粒子之合成 23
2.5 二氧化碳膨脹液體之應用 25
第三章 實驗方法 29
3.1 實驗藥品 29
3.2 分析儀器 30
3.2.1 穿透式電子顯微鏡(TEM) 30
3.2.2 X-光粉末繞射儀(XRD) 30
3.2.3 X射線能量散佈分析儀(EDX) 31
3.2.4 感應耦合電漿離子源元素組成分析(ICP-Mass) 32
3.2.5 元素分析儀 (EA) 32
3.2.6 紫外線/可見光分光光譜儀(UV/Vis) 32
3.2.7 熱重分析儀(TGA) 33
3.2.8 熱示差掃瞄卡量計(DSC) 33
3.2.9 全反射傅立葉轉換紅外線光譜儀(ATR-FTIR) 34
3.2.10 氣相層析儀(GC-FID) 34
3.3實驗裝置與實驗步驟 36
3.3.1製備異硬脂酸金屬鈀鹽之實驗步驟 36
3.3.2製備異硬脂酸銀鹽之實驗步驟 36
3.3.3 製備雙金屬奈米粒子之裝置圖與實驗步驟 36
3.3.4 以鈀奈米粒子進行Styrene氫化反應之實驗步驟 37
3.3.5 以鈀奈米粒子進行m-CNB氫化反應之實驗步驟 37
3.3.5 以鈀銀雙奈米粒子進行Phenylacetylene氫化反應之實驗步驟 38
第四章 結果與討論 40
4.1 金屬前驅物性質之性質鑑定 40
4.1.1全反射傅立葉轉換紅外線光譜儀(ATR-FTIR) 40
4.1.2 熱分析鑑定(TGA、DSC) 43
4.1.3 前驅物組成鑑定(EA, ICP) 45
4.2 鈀金屬奈米粒子 47
4.2.1 鈀金屬奈米粒子合成 47
4.2.2鈀金屬奈米粒子應用於m-CNB氫化反應 54
4.2.3鈀金屬奈米粒子應用於Styrene氫化反應 59
4.3鈀銀雙金屬奈米粒子 61
4.3.1鈀銀雙金屬奈米粒子合成與鑑定 61
4.3.1.1粒子成分效應 61
4.3.1.2二氧化碳壓力效應 68
4.3.1.3氫氣壓力效應 70
4.3.1.4 溫度效應 72
4.3.2鈀銀雙金屬奈米粒子應用於Phenylacetylene氫化反應 74
第五章 結論 77
參考文獻 79

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