本研究工作的目的為開發以連續式氣溶膠合成法製備的雙功能奈米觸媒，應用於甲烷裂解產氫與結合二氧化碳再利用相關的製氫－減碳技術。此程序包含了兩個步驟：(1) 透過甲烷裂解反應(CH4 → C + 2H2)將甲烷分解為氫氣與碳，達成無碳排製氫目標；(2) 利用逆Boudouard反應(C + CO2 → 2CO)，將二氧化碳引入並與甲烷裂解中產生的積碳進行反應，以生成一氧化碳，可作為燃料和化學品生產的原料，如甲醇、氨和合成柴油，達到減碳永續化製程的目標。
在材料合成的部分，我們使用實驗室所架設之連續式氣相奈米粒子合成系統以製備所需之混成式奈米粒子觸媒，此種合成方式結合了氣相蒸發誘導自組裝的原理與膠體懸浮液的穩定化(stabilization)原理，並且可以透過改變前驅物溶液的種類與濃度來控制所合成之觸媒的組成、大小以及形貌。在第一部分中，我們利用Ni-CeO2-Al2O3觸媒材料恆溫於600 °C下促進此化學迴圈製程，可以實現穩定的高產氫效率(TOFCH4 = 39.62 h-1)，並達到成功的觸媒再生(TOFCO2 = 36.09 h-1)。實驗結果顯示，以含有CeO2的樣品進行甲烷裂解後產生之絲狀積碳對於逆Boudouard反應表現出更好的催化活性。
第二部分中，我們期望透過更快速的逆Boudouard反應來加速觸媒的再生程序，因此我們將具有增強氧化還原能力的成分融入雙功能奈米觸媒材料中(Ni-Fe-Al2O3)，以期能實現更迅速的逆Boudouard反應。同時，我們也針對逆Boudouard反應的參數進行修改：(1) 將反應溫度提高到700 ℃ (2) 引入氧氣以促進碳的氣化。結果顯示，我們透過上述方法皆能夠將逆Boudouard反應程序的所需時間縮減至原來的一半(20 → 10分鐘)，實現更快速的觸媒再生。與相關文獻相比，本研究系統的特點在於我們可以在相對較低的溫度下促成反應進行，同時透過氫氣與一氧化碳的直接氣體分離實現純產氫。這項研究工作提供了一種利用連續式氣溶膠合成法開發高性能之混成式奈米觸媒的新路徑，並將其應用於製氫－減碳的化學迴圈程序，以實現有效的負化學碳排製氫之雙效目標。

A two-stage chemical looping approach is demonstrated for sustainable carbon-free hydrogen production through methane decomposition (CH4 → C + 2H2) combined with cyclic catalyst regeneration via the reverse Boudouard reaction (C + CO2 → 2CO). Ni-based spherical nanoparticle cluster, fabricated using a continuous aerosol-based synthetic approach, is developed for an effective cyclic catalysis of the above two chemical reactions.
In the first part, we utilized Ni-CeO2-Al2O3 catalyst materials to facilitate isothermal chemical looping reactions, maintaining a temperature of 600 °C throughout the process. Sufficiently high CO2 conversion rate for catalyst regeneration (in terms of TOFCO2, 36.09 h-1) and a stably high yield of hydrogen (in terms of CH4 conversion; TOFCH4, 39.62 h-1) are achievable. CeO2-incorporated samples generating whisker carbon after methane pyrolysis demonstrate a better activity for cyclic catalyst regeneration.
In the second part, we utilized Ni-Fe-Al2O3 catalyst material and modified the reaction parameters of the reverse Boudouard reaction as follows: (1) raised the reaction temperature to 700 ℃ (2) introduced oxygen to facilitate the gasification of carbon. These adjustments are anticipated to expedite the catalyst regeneration process effectively. Experimental results show that using the above methods, we can reduce the time required for the reverse Boudouard reaction (from 20 minutes to 10 minutes), achieving faster catalyst regeneration. The novelty of the work stands on developing high-performance dual functional catalyst material, by which the two-stage reactions can be promoted under a remarkably lower temperature (e.g., 600 °C). The proposed dual functional catalyst material and catalytic pathway in this study demonstrate significant advances for the chemical looping process of effective hydrogen production combined with cyclic catalyst regeneration via CO2 utilization, offering eco-friendly pathway for industrial applications.

摘要...I
Abstract...II
誌謝...IV
目錄...V
圖目錄...VII
表目錄...XII
第一章 緒論...1
1.1 前言...1
1.2 氫氣能源技術...3
1.3 氫氣能源分類...5
1.4 甲烷裂解反應產氫...7
1.5 透過逆Boudouard反應進行二氧化碳再利用...9
1.6 同步減碳製氫之化學迴圈製程...11
1.7 以連續式氣溶膠合成法製備雙功能奈米觸媒材料...12
1.8 研究目的...14
第二章 實驗方法及儀器...16
2.1 實驗藥品...16
2.2 以連續式氣溶膠合成法製備鎳系雙功能奈米觸媒材料...17
2.3 分析儀器介紹...19
2.3.1 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)...19
2.3.2 高解析穿透式電子顯微鏡 (High-resolution Transmission Electron Microscope, HR-TEM)...20
2.3.3 X光繞射儀 (X-ray Diffraction Analyzer, XRD)...21
2.3.4 比表面積與孔隙度分析儀 (Brunauer-Emmett-Teller Method, BET)...22
2.3.5 熱重分析儀 (Thermogravimetric Analysis, TGA)...23
2.3.6 化學吸附分析儀 (Chemisorption Analyzer)...24
2.3.7 氣相奈米粒子流動分析儀 (Differential Mobility Analyzer, DMA)...26
2.3.8 靜電式氣溶膠粒子收集器 (Electrostatic Aerosol Sampler)...27
2.3.9 高解析X光電子能譜儀 (High resolution X-ray Photoelectron Spectrometer, HR-XPS)...28
2.3.10 電子順磁共振光譜儀 (Electron Paramagnetic Resonance Spectrometer, EPR)...29
2.4 鎳系雙功能奈米觸媒材料之活性與穩定性測試...30
2.4.1 甲烷裂解反應與逆Boudouard反應之測試系統...30
2.4.2 催化性能與活化能之分析與計算...32
第三章 結果與討論...34
3.1 以鎳系雙功能奈米觸媒材料催化甲烷裂解與逆Boudouard反應...35
3.1.1 鎳系雙功能奈米觸媒材料之材料性質分析...35
3.1.2 甲烷裂解反應之活性與穩定性測試...42
3.1.3 逆Boudouard反應之活性與穩定性測試...52
3.1.4 循環穩定性測試...60
3.2 透過優化觸媒材料與反應參數以加速催化逆Boudouard反應並實現觸媒材料的快速再生...68
3.2.1 以Ni-Fe-Al2O3觸媒進行反應...68
3.2.1.1 Ni-Fe-Al2O3奈米觸媒之材料性質分析...68
3.2.1.2 Ni-Fe-Al2O3奈米觸媒之催化性能測試...73
3.2.2 以700 ℃進行觸媒之快速再生程序...81
3.2.2.1 恆溫於450 ℃下進行甲烷裂解...81
3.2.2.2 恆溫於700 ℃下進行逆Boudouard反應...86
3.2.3 加入氧氣進行逆Boudouard反應...90
第四章 結論...95
第五章 未來展望...96
參考文獻...i

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