隨著溫室效應的日漸嚴重，對於溫室氣體中的主要成分二氧化碳之減量問題也愈加受到重視，而二氧化碳再利用主要可分為碳捕捉與儲存後使用以及碳捕捉後直接反應兩大面向，本研究選用碳捕捉後直接反應方式，探討二氧化碳於直接氫化反應之應用。
第一部分的研究為金屬-有機骨架衍生之混成式奈米材料在逆水氣反應上之催化。逆水氣反應(Reverse water-gas shift, RWGS)是以大氣中的二氧化碳作為原料來選擇性氫化，從而獲得之一氧化碳將進一步生產出各種具有高附加價值之化學品，因此十分具有發展的潛力。在這部分的研究工作中，我們開發了一種透過氣溶膠技術蒸發誘導來自組裝生成金屬-有機骨架(Metal-Organic Frameworks, MOFs)，並利用衍生之Cu@CeO2混成式奈米觸媒作為RWGS反應之催化劑。我們透過X-ray diffraction、Brunauer-Emmett-Teller表面積分析、氫氣程溫還原、二氧化碳程溫脫附、N2O化學吸附分析和掃描式電子顯微鏡技術交互分析所開發出之奈米觸媒特性，以及探討不同金屬比例下MOF衍生之Cu@CeO2混成式奈米觸媒於RWGS反應的活性和穩定性。我們發現隨著觸媒之Cu/Ce原子比降低，金屬分散度和比表面積均得到提升。具有低Cu含量的MOF衍生Cu@CeO2奈米觸媒在低溫下時對RWGS反應顯示出高選擇率、足夠的操作穩定性以及優異的催化活性(i.e., TOFCO2 = 0.1635 s-1 at 400 °C)，顯示CeO2奈米粒子團簇的加入增強了MOF衍生之混成式奈米觸媒的活性以及穩定性。
在本研究的第二部份中，沿用第一部分之合成方法，研究金屬-有機骨架衍生之混成式奈米材料在二氧化碳/一氧化碳加氫甲醇化反應上之催化。甲醇作為高價值的C1化學品，因此期望可透過二氧化碳來高效率地轉化為甲醇，且透過加入一氧化碳與二氧化碳一同與氫氣反應，探討二段式反應：逆水氣反應(二氧化碳先行部分轉化成一氧化碳)-加氫甲醇化的潛力。本研究利用氣溶膠技術蒸發誘導自組裝來生成銅鋅雙金屬之金屬-有機骨架，結合了氧化鋁奈米粒子團簇，透過熱處理形成Cu-ZnO擔載於Al2O3之雜化奈米結構。我們透過X-ray diffraction、Brunauer-Emmett-Teller表面積分析、氫氣程溫還原、二氧化碳程溫脫附、N2O化學吸附分析和掃描式電子顯微鏡技術交互分析所開發出之奈米觸媒特性。結果顯示加入Al2O3有助於增加活性金屬表面積以及增加表面金屬的分散度，形成Cu、ZnO奈米微晶分散良好的CuZn@Al2O3混成式奈米粒子，其中Cu作為活性物質，ZnO則提供鹼性位點來吸附二氧化碳。我們發現銅晶徑小且具有高活性金屬表面積之CuZn@Al2O3混成式奈米粒子對於二氧化碳/一氧化碳加氫甲醇化反應顯示出相當高的甲醇選擇性以及甲醇空間產率，顯示Cu-Zn-O界面增強了MOF衍生之混成式奈米觸媒對於二氧化碳/一氧化碳加氫甲醇化反應的活性。
此研究為氣溶膠蒸發誘導自組裝開發MOF衍生之奈米結構材料應用於碳捕捉後直接反應之催化劑設計開闢了新的視野，希望開發出新型的材料製備技術用以生成金屬-有機骨架之衍生觸媒應用在二氧化碳相關之能源科技，並提升二氧化碳之應用價值。

As the greenhouse effect becomes more and more serious, more attention has been paid to the reduction of carbon dioxide in the atmosphere, which is one of the main components of greenhouse gases. The utilization of emitted carbon dioxide can be divided into two major aspects: carbon capture & storage and carbon capture & utilization. In this research work, we aim to develop a new type of material synthesis approach to obtain metal-organic frameworks and its derived catalysts, which can be used for the application of catalytic carbon dioxide hydrogenation, a carbon dioxide capture & utilization technology.
In first part, an aerosol spray-drying method followed by a powder-form thermal treatment is employed as an effective route to preparing metal-organic framework (MOF)-derived Cu/CeO2 nanostructured materials. X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, H2-temperature programmed reduction, CO2-temperature programmed desorption, N2O chemisorption and scanning electron microscopy are employed complementarily for the characterization of material properties of the developed nanocatalysts. The results show both metal surface area and metal dispersion were enhanced by decreasing Cu/Ce atomic ratio of the hybrid material. Incorporation of CeO2 nanoparticle cluster enhanced both activity and stability of the MOF-derived nanostructured catalysts. In addition to high selectivity and sufficient operation stability toward RWGS, a superior high catalytic activity under a relatively low-temperature operation was achievable (i.e., TOFCO2 = 0.1635 s-1 at 400 °C).
On the basis of the development of the synthesis method, the catalysis of hybrid nanomaterials derived from metal-organic frameworks in combined (CO2 + CO) hydrogenation to methanol is studied in the second part of the article. Bimetallic CuZn metal-organic framework and its derived nanostructured materials are synthesized by aerosol-assisted method followed by a powder-form thermal treatment. X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, H2-temperature programmed reduction, CO2-temperature programmed desorption, N2O chemisorption analysis and scanning electron microscopy are employed complementarily for the characterization of material properties of the developed nanocatalysts. The result shows both metal surface area and metal dispersion were enhanced with the presence of Al2O3 nanoparticle cluster support. CuZn@Al2O3 hybrid nanoparticles with low copper crystal size and high active metal surface area show high selectivity and space time yield of methanol toward combined (CO2 + CO) hydrogenation to methanol. The result imply that the Cu-Zn-O interface enhanced the activity of MOF-derived hybrid nanocatalysts for the reaction.
The present development for MOF-derived nanostructured materials produced by using an aerosol-based evaporation-induced self-assembly method opens up opportunities for the design of nanostructured catalysts useful for a variety of applications in CO2 capture and utilization.

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