本研究工作目的是建立連續式觸媒催化氣相反應系統。在材料合成的部分，我們運用實驗室現有的氣相奈米粒子合成系統。先前結果顯示氣相製成的奈米粒子具有高的分散性，同時藉由改變前驅物溶液之濃度或種類，我們可以改變所製備出產物的組成及粒子大小，並且已經證實在催化甲烷燃燒以及一氧化碳氧化反應方面有很好的活性。然而我們希望更深入控制觸媒材料，目前能控制的是組成及粒子大小，所以此階段的目標是改進合成系統，並透過二次反應還原系統以控制觸媒材料的氧化態，來分析觸媒氧化態是否會影響甲烷燃燒和二氧化碳重組之催化反應。分析技術上實驗室先前之研究階段已建立一套固定床偵測系統來分析奈米粒子的氧化還原能力與觸媒的催化活性，其可利用氣相層析儀來分析反應氣體成分及計算觸媒催化反應的轉化率，並觀察觸媒在催化反應時的起燃溫度，了解氧化反應的放熱情況。除此之外，利用TPR程溫還原反應可以得知奈米粒子的還原能力及還原溫度。本實驗研究方向會透過此反應系統進而做改善，並且藉由更完整實驗結果希望去探討二次反應還原系統所控制之金屬奈米粒子之氧化態對於催化甲烷燃燒反應及二氧化碳重組反應機制所造成的影響。
第一部份我們利用氣相誘導自組裝[gas-phase evaporation-induced self-assembly (EISA)]的方式來製備不同化學組成的單成分CuOx-NP與均質的複合式CuCeOx-NP之奈米觸媒。合成出的結果顯示不論是CuOx-NP或CuCeOx-NP皆可藉由二次反應還原系統來更進一步控制材料性質(氧化程度)，在銅觸媒中添加二氧化鈰我們可以觀察到不論是催化活性還是觸媒的穩定性都有顯著的提升，其原因為氧化鈰的螢石型結構能避免觸媒在反應中燒結，且其所有的氧空洞能有效幫助吸附氧氣從而快速去除積碳。我們也將進一步探討單成分CuOx-NP與複合式CuCeOx-NP經過二次反應還原系統所生成之含有不同氧化態的奈米粒子對於催化甲烷燃燒反應活性的影響。
在第二部分的實驗中，我們一樣利用氣相誘導自組裝以及二次鍛燒合成系統成功製備出不同氧化態的單成分NiOx-NP與複合式NiCeOx-NP，我們使用還原氣體氫氣透過改變第二次鍛燒的溫度來控制樣品的氧化態，並試以不同分析方法佐證我們的結果。實驗上運用上述製備的單成分NiOx-NP與複合式NiCeOx-NP進行二氧化碳重組反應[Dry reforming of methane with carbon dioxide (DRM)]。結果顯示於鎳觸媒中添加氧化鈰之後觸媒的起燃溫度能夠降低約150 ℃且其催化效果在高溫下穩定，沒有失活現象的發生，推測原因為添加CeO2之後(複合式NiCeOx-NP)，雖然和單成分NiOx-NP一樣會產生積碳，不過兩者分別產生的積碳型態不同對於觸媒的催化活性也會造成極大的影響。除了探討觸媒成分對於催化活性之影響，我們也以NiCeOx-NP進行改變進料氣體比例的莫爾比：CO2/CH4 (w) = 1與1.5的催化實驗，其結果顯示積碳量差了18倍之多。
材料分析方面我們使用SEM、XRD、DMA、XPS、HR-TEM來分析奈米粒子的型態與晶格、粒徑分佈以及觸媒的氧化程度，並利用觸媒催化活性測試、觸媒催化穩定性測試(甲烷燃燒與二氧化碳重組反應)、程溫還原反應來進行奈米觸媒催化與還原能力的分析。
此合成方法的最主要的功用在於我們可以有效的合成出經過還原後的銅及鎳系奈米觸媒，對比於之前傳統固定床的還原方法來說，我們可以連續式生產過程來製備金屬態的觸媒，也能避免在傳統之還原過程中發生的燒結現象，並將所生產之觸媒應用於催化甲烷燃燒以及二氧化碳重組反應。這將對以使用甲烷為主的能源發展領域上有所助益，可以提升其效率，並降低對環境的汙染。

The synergistic effect of Cu-Ce-O hybrid nanostructure has shown the promise for catalytic methane combustion. In this study, we develop an aerosol-based two-stage thermal treatment method to (1) synthesize the Cu-Ce-O hybrid nanoparticle (NP) with a tunable oxidation state directly in gas phase, and (2) provide a mechanistic understanding of surface reduction of the Cu-Ce-O hybrid NP for catalysis of methane combustion. After evaporation-induced self-assembly followed by a thermal decomposition (i.e., 1st stage) to form metal oxide NP at the 1st stage thermal treatment, a temperature-programmed, aerosol-based hydrogen reduction process was employed for direct tuning the oxidation state of the NP in the gas phase (the 2nd stage thermal treatment). Differential mobility analysis, x-ray diffractomery, x-ray photoelectron spectroscopy, and scanning electron microscopy were employed complementarily for characterization of particle size, morphology, crystallinity, elemental composition, and oxidation state of the NPs. The results show a successful surface reduction of Cu for both Cu-only NP and Cu-Ce-O hybrid NP by the aerosol-based two-stage thermal treatment method. Using the Cu-Ce-O hybrid nanoparticle as catalyst, our results show a successfully catalysis on methane combustion over various initial oxidation states of Cu. The results show a high activity with a low light-off temperature, a high light-off stability and operation stability toward catalytic methane combustion. The prototype method proposed in this study provides the mechanistic understanding of the synergistic catalysis of the surface-reduced Cu-Ce-O hybrid nanoparticle with different oxidation states. The method can be especially useful to fabricate a variety of nanocatalysts with different oxidation states of active metals by design for the study of methane-based energy and environmental applications (e.g., CO2 dry reforming by methane).
The second part of the work is targeted on the catalysis of dry reforming of methane with carbon dioxide (DRM). DRM is highly attractive for simultaneously reducing greenhouse gases and producing syngas. Here, we develop a new NiCeOx hybrid nanoparticle as a high-performance catalyst for DRM. The crystallites of Ni and CeO2 were homogenously self-assembled in gas phase, creating a large amount of Ni-Ce-O interface for a strong metal-support interfacial interaction. Chemical composition, particle size, and oxidation state of the hybrid nanostructure were tunable directly in aerosol state. The results show that the starting catalytic temperature of Ni-based catalysts reduced by around 150 ˚C through the hybridization with CeO2 followed by a direct gas-phase H2-reduction. The Ni-CeOx hybrid nanoparticle showed stable and high conversion of CH4 and CO2 with a remarkably turnover frequency at low temperature (0.1 s-1 at 450 °C). The amount of coke formation greatly reduced by 18×, whereas the H2/CO ratio was constant at around 0.8 after increasing the CO2/CH4 by 1.5×. The work demonstrated a facile route for controlled gas-phase synthesis of NiCeOx hybrid nanoparticles with a very high catalytic activity and stability for DRM. The findings of this study can shed a light on the mechanism of Ni-Ce-O synergistic catalysis, which can be especially useful for methane-based energy applications.

摘要 I
Abstract III
誌謝辭 VI
第一章 緒論 7
1.1 金屬/金屬氧化物的觸媒特性 7
1.2 金屬/金屬氧化物奈米粒子作為觸媒催化的應用 9
1.3 奈米觸媒對甲烷燃燒反應機制之影響 11
1.4 氣溶膠合成技術 12
1.5 催化甲烷燃燒實驗之目的及方法 16
1.6 先前實驗結果(催化甲烷燃燒反應) 18
1.6.1 以氧化銅為基底之觸媒材料性質分析 18
1.6.2 添加不同莫耳比例的鈰對甲烷燃燒催化活性之影響 20
1.6.3 單成分/複合式奈米觸媒之穩定性分析與催化機制的探討 22
1.7單成分/複合式奈米觸媒對二氧化碳重組反應催化之影響 26
第二章 實驗方法及儀器 27
2.1 實驗藥品 27
2.2 氣相奈米粒子之合成 28
2.4 掃描式電子顯微鏡(Scanning Electron Microscopy) 33
2.5 X射線光電子能譜儀(X-ray photoelectron spectroscopy) 34
2.6 X光繞射儀(X-ray diffraction) 35
2.7 氣相奈米粒子流動分析儀(DMA) 36
2.8 熱重量分析儀(TGA) 37
2.9 觸媒催化甲烷燃燒反應之活性測試 38
2.10 觸媒催化二氧化碳重組反應之活性測試 40
2.11 TPR程溫還原反應 42
第三章 實驗結果與分析 44
3.1 甲烷燃燒催化反應 44
3.1.1 二次鍛燒系統製備氧化銅基底之奈米觸媒其材料性質分析 44
3.1.2 CuOx-NP/CuCeOx-NP觸媒對甲烷催化之活性影響 53
3.1.2.1 不同二次鍛燒溫度(Td2)對甲烷燃燒催化活性之影響 53
3.1.2.2二次鍛燒對於單成分/複合式奈米觸媒穩定性與催化機制之影響探討 61
3.2 二氧化碳重組(DRM)催化反應 67
3.2.1 以二次鍛燒還原系統製備之鎳系奈米觸媒其材料性質分析 67
3.2.2 Ni-only-NP/NiCeOx-NP觸媒對二氧化碳重組反應催化活性之影響 74
3.2.2.1 不同二次鍛燒溫度(Td2)對二氧化碳重組反應催化活性之影響 74
3.2.2.2 不同二氧化碳相對濃度對於催化DRM反應8-h穩定性之影響 83
第四章 結論 92
第五章 未來展望 93
5.1 以NiO/MOF混成奈米材料催化二氧化碳重組反應 93
5.2 甲烷蒸氣重組催化反應 95
5.3 以氣溶膠鎳系奈米觸媒催化還原胺化法製備聚醚胺 96
第六章 參考文獻 99

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