本研究目的為以氣溶膠法開發觸媒材料來催化甲烷雙重組反應，以降低其反應溫度，並生成可調控H2/CO比例之合成氣，同時達到穩定產氫之目標。
第一部分實驗中，我們以氣溶膠法合成出MOF材料(Ni/ZIF-8@Al2O3)，並經由空氣鍛燒及氫氣還原形成Ni-ZnO-Al2O3衍生材料來催化甲烷雙重組反應。以甲烷雙重組反應的係數比進行程溫活性測試，並在650℃下調控不同進料比進行10小時的穩定度測試。結果顯示我們所開發的Ni-ZnO-Al2O3觸媒具有低起始反應溫度(450℃)，並且在10小時內具有相當穩定的催化性能。此外在反應中添加水蒸氣也證實可以抑制積碳的產生，防止觸媒失活。同時藉由調整反應物進料比及反應溫度也能控制產物H2/CO比在1.4至6.5之間。然而觸媒中的鋅具備低沸點特性，不適合於高溫下催化反應，且其在低溫區(300~500℃)無法抑制副反應水氣反應的發生，故該區間其二氧化碳轉化率為負值。
第二部分實驗中，我們以氣溶膠法合成出NiPd@Al2O3觸媒催化甲烷雙重組反應，並以工業二氧化碳回流概念設計甲烷雙重組產氫系統，利用過量二氧化碳作為反應物以讓甲烷轉化率在600℃達100%，未反應的二氧化碳及副產物一氧化碳則可回流以作為下次反應時的反應物。結果顯示適量的一氧化碳作為反應物時有助於促進水氣反應發生以產出更多氫氣。然而過量的一氧化碳會阻礙甲烷雙重組產氫，因此隨著循環次數增加，過多的一氧化碳必須從產物中分離出來。藉由添加貴金屬Pd可降低甲烷雙重組反應溫度，並在30小時的穩定性測試中具有穩定的催化性能，且在CO2及CO回流的系統中可穩定產氫持續4個循環，並在第5個循環時排除CO有助於維持更多次循環。
以上研究顯示我們可以氣溶膠法合成MOF，並以其衍生材料來催化甲烷雙重組反應，為CO2再利用提供另一有效途徑。或者利用CO2及CO回流系統達到甲烷雙重組穩定產氫之目的。

The objective of this research is to develop catalysts by aerosol method to catalyze the methane bi-reforming reaction, reduce the reaction temperature, and generate syngas with adjustable H2/CO ratio, and achieve the goal of stable hydrogen production.
In the first part of the work, we synthesized MOF materials (Ni/ZIF-8@Al2O3) using aerosol method. The MOF-derived Ni-ZnO-Al2O3 catalyst was synthesized through air and hydrogen calcination. Temperature-programmed activity test based on the stoichiometric feed ratio of BRM and 10-hour stability test at 650℃ are performed at different feed ratio to see the performance of the developed hybrid catalysts for bi-reforming of methane. The results show that the Ni-ZnO-Al2O3 catalyst we developed has low onset temperature (450°C) and has stable catalytic performance within 10 hours. In addition, the presence of the steam in the reaction has shown to inhibit the coke formation and prevent catalyst deactivation. Tunable H2/CO ratio (1.4~6.5) can be controlled by adjusting the feed ratio and reaction temperature. However, Zn in the catalyst has a low boiling point and is not suitable for catalytic reactions at high temperatures. Moreover, it cannot inhibit the water gas shift reaction at the low-temperature range (300~500°C), so the CO2 conversion is negative at this temperature range.
In the second part of this work, we synthesized the NiPd@Al2O3 catalyst to catalyze methane bi-reforming reaction by aerosol method, and designed the reaction system with the concept of industrial carbon dioxide reflux, using excess carbon dioxide as a reactant to achieve a methane conversion rate of 100% at 600°C, while the unreacted CO2 and by-product CO can be refluxed as the reactant in the next cycle. The results showed that an appropriate amount of CO as a reactant can promote the water-gas shift reaction to produce more hydrogen. However, excess CO will hinder hydrogen production, so as the number of cycles increases, excess CO must be separated from the system. The addition of precious metal Pd could reduce the temperature of methane bi-reforming reaction, and had stable catalytic performance in the stability test for 30 hours, and the hydrogen production could be stably produced in the CO2 and CO reflux system for 4 cycles, and the CO removal in the 5th cycle was helpful to maintain more cycles.
The above research shows that we can synthesize MOF by aerosol method and use its derived materials to catalyze the methane bi-reforming reaction, which provides another effective way for CO2 utilization. Besides, we can use CO2 and CO reflux system to achieve the goal of stable hydrogen production through methane bi-reforming reaction.

摘要Ⅱ
AbstractⅢ
致謝Ⅴ
目錄Ⅵ
圖目錄Ⅷ
表目錄XI
第一章 緒論1
1.1 二氧化碳再利用：甲烷重組反應1
1.2 混成式觸媒材料於甲烷重組反應之應用6
1.3 金屬有機框架及其衍生材料7
1.4 氣溶膠合成方法9
1.5 研究目的11
第二章 實驗方法及儀器13
2.1 實驗藥品13
2.2 觸媒之製備：金屬有機框架及其衍生材料之合成14
2.2.1 Ni/ZIF-8@Al2O3及其衍生物之合成14
2.2.2 NiPd@Al2O3材料之合成16
2.3 觸媒材料分析之儀器18
1. X光繞射儀 (X-ray Diffraction Analyzer)18
2. 掃描式電子顯微鏡 (Scanning Electron Microscopy)19
3. 化學吸附分析儀20
4. 比表面積與孔隙度分析儀(Brunauer-Emmett-Teller Method)23
5. 熱重量分析儀 (Thermogravimetric Analyzer)24
6. 高解析度X光電子能譜儀(High resolution X-ray Photoelectron Spectrometer)25
7. X光螢光光譜儀(X-ray fluorescence spectrometer)26
2.4 甲烷雙重組反應之熱力學分析27
2.5 甲烷雙重組反應之活性測試及穩定性測試29
2.6 反應參數對於平衡轉化率、產率與選擇性之探討32
2.7 二氧化碳進料量對工業二氧化碳回流系統的影響34
第三章 實驗結果與分析37
3.1 以Ni/ZIF-8@Al2O3之MOF衍生材料催化甲烷雙重組反應37
3.1.1 材料性質分析37
3.1.2 觸媒活性測試54
3.1.3 定溫650℃觸媒穩定性測試60
3.2 以NiPd@Al2O3材料催化甲烷雙重組反應69
3.2.1 材料性質分析69
3.2.2 觸媒活性測試82
3.2.3 定溫600℃觸媒穩定性測試87
3.2.4 甲烷雙重組8次循環測試92
第四章 結論103
第五章 未來工作104
第六章 參考文獻105

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