近年來奈米材料在能源領域方面的應用是一個具有潛力的主題，例如應用在改善觸媒效能或是作為燃料的添加物等等。本實驗主要研究為建立一套氣溶膠式鍛燒合成系統，利用此系統於氣相中製備出以氧化銅為基底的複合式奈米粒子，並應用於催化一氧化碳之氧化反應。此合成方法無須受限於溶劑的使用，可搭配即時粒徑分析技術DMA以及後端分析方法鑑定其物理性質，並可進一步推論出粒子在系統中生成與反應的機制。結果顯示，合成之粒子含有高反應性與高穩定度，且可以藉由挑選適合的組成或溫度來控制粒徑大小、晶徑大小和化學組成等性質。氧化銅的晶徑大小對CO還原性及後續的催化能力具有顯著的影響。添加CeO2擔體後，在Cu-Ce-O界面間會誘發形成新的活性部位，進而增強氧化銅的還原能力與催化效果；反之，混摻Al2O3則會因形成尖晶石結構而導致催化能力下降。本實驗所建立之合成系統可以被應用於製造其他類型的功能性奈米觸媒(例如能源和環境奈米觸媒)，且可良好調控其物質性質，進而達到改善觸媒之品質。

We report a systematic study of gas-phase controlled synthesis of copper oxides-based hybrid nanoparticles for catalytic CO oxidation. The complementary physical, spectroscopic and microscopic analyses were conducted to obtain a better understanding of the material properties, including particle size, crystallinity, elemental composition, and oxidation state. Results showed that the synthesized nanoparticles exhibited highly durable catalytic activity and stability, also the particle size, crystallite size, and chemical composition were tunable by choosing suitable chemical compositions of precursors and temperatures. The crystallite size of CuO influenced the reducibility of CuO by CO and the subsequent catalytic activity of CO oxidation. The hybridization process of CeO2 and CuO induces the formation of new active sites at the Cu-Ce-O interface, which enhances reproducibility of CuO and the catalytic activity. However, the reproducibility of CuO and catalytic activity were considerably decreased when CeO2 was replaced with the inert Al2O3. This work describes a prototype method to form highly pure and well-controlled hybrid nanocatalysts, which can be used to establish the correlation of material properties versus reducibility and subsequent catalytic activity for energy and environmental applications.

摘要…………………………………………………………………………………I
目錄…………………………………………………………………………………III
圖目錄………………………………………………………………………………V
表目錄……………………………………………………………………………VII
第一章 緒論………………………………………………………………………1
1.1 功能性奈米材料…………………………………………………………1
1.2 奈米粒子合成方法………………………………………………………6
1.3 氣溶膠合成法…………………………………………………………10
1.4 化學迴圈燃燒技術……………………………………………………15
1.5 氧化銅材料……………………………………………………………17
1.6 研究目的………………………………………………………………19
第二章 實驗方法………………………………………………………………21
2.1 實驗藥品………………………………………………………………21
2.2 氣霧化奈米粒子之合成………………………………………………21
2.3 氣相奈米粒子流動分析儀(DMA)……………………………………26
2.4 熱重量分析儀(TGA)…………………………………………………26
2.5 X光繞射儀(XRD)……………………………………………………27
2.6 X射線光電子能譜儀(XPS)……………………………………………27
2.7 掃描式電子顯微鏡(SEM)……………………………………………27
2.8 穿透式電子顯微鏡(TEM & HRTEM)…………………………………29
2.9 程溫還原(CO-TPR)……………………………………………………29
2.10 催化效果測定……………………………………………………… 30
第三章 結果與討論……………………………………………………………31
3.1 CuxO奈米粒子的物質性質……………………………………………31
3.1.1 操作溫度對CuxO粒子的影響……………………………32
3.1.2 前驅物濃度對CuxO粒子之影響…………………………36
3.2 CuCeOx-NP與CuAlOx-NP的物質性質…………………………… 40
3.3 觸媒性質測試…………………………………………………………49
3.3.1 CO程溫還原與活性測試…………………………………50
3.3.2 觸媒於催化反應之穩定性測試…………………………54
3.3.3 觸媒反應機構……………………………………………55
第四章 結論與未來發展………………………………………………………57
參考文獻……………………………………………………………………………59

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