近年來二氧化碳減量議題受到關注。本研究將針對二氧化碳氫化製備甲醇的二氧化碳再利用途徑進行觸媒材料開發，並運用二階段預還原二氧化碳的想法，將二氧化碳加一氧化碳作為模擬進料，以進行氫化反應來製備甲醇，達到高選擇率之目標。
本研究之第一部份將探討以金屬-有機框架 (Metal-organic framework, MOF)為基礎之混成式奈米材料，作為催化二氧化碳加一氧化碳結合式氫化反應的觸媒。我們利用噴霧乾燥技術進行蒸發誘導自組裝，製備HKUST-1 (Cu-MOF)，並與氧化鋁奈米粉末 (Al2O3 nanopowder) 結合，最後經熱處理以製備Cu-ZnO擔載於Al2O3上的混成式奈米結構，並透過儀器進行相輔式材料分析，探討合成材料之特性。研究結果表明了透過MOF衍生之材料維持優異的金屬分散性質，從而成為具有良好的金屬分散度以及較低的晶體尺寸之Cu-ZnO/Al2O3混成式奈米粒子結構。而透過ZnO (助觸媒) 和Al2O3 (載體) 的添加，提升了 Cu-MOF 衍生材料的活性。結果表明，具較高活性金屬表面積之Cu-ZnO/Al2O3混成式奈米粒子對於二氧化碳加一氧化碳結合式氫化反應顯示出相當高的甲醇空間產率以及選擇率，並以此推測二氧化碳氫化反應之速率決定步驟為氫氣於銅表面之解離性吸附。透過ZnO的添加，觸媒對於催化此反應之甲醇空間產率以及選擇率皆有大幅的提升，顯示出所開發MOF衍生之混成式奈米觸媒的Cu-Zn-O界面對於催化二氧化碳加一氧化碳結合式氫化反應之重要性。而Al2O3的添加能增加金屬分散度及活性金屬表面積，並進而提高催化活性。
而在本研究之第二部份中，我們優化材料合成方法之設計及擴展即時性材料分析之能力。透過第一段噴霧乾燥技術合成MOF材料，並將其分散於水相中與活性成分前驅物均勻分散形成膠體，再運用第二段霧化裝置，進行膠體MOF材料霧化與氣相誘導自組裝，再透過兩段式連續氣相熱處理，以製備出Cu-ZnO擔載於氧化鋁奈米粉末 (Al2O3 nanopowder) 或二氧化鈰奈米粉末 (CeO2 nanopowder) 上之混成式奈米結構，並結合氣相奈米粒子電移動度分析儀 (Differential mobility analyzer, DMA)，通過氣相電泳法之原理，即時分析所製備MOF衍生混成式觸媒之電移動度粒徑分布，藉此對材料製程之參數進行即時調控與優化，不僅如此，我們透過儀器進行相輔式材料分析，研究合成材料之性質。本研究透過製程的改善，成功合成出MOF衍生混成式觸媒，並通過DMA實現即時奈米粒子電移動度粒徑分析，達成了連續式合成與即時性分析之目的。結果顯示由此方法合成之粒子尺寸 (50~500 nm) 會比噴霧乾燥法合成產物之粒子尺寸 (1~5 μm)更小。而相較於Al2O3，以CeO2為載體之樣品具有較高之甲醇選擇率，但由於較低的金屬分散度及活性金屬表面積，因此甲醇時空產率仍低於以Al2O3為載體之樣品。
本研究以氣相蒸發誘導自組裝作為基礎，成功建立一新型MOF衍生之混成式奈米觸媒材料的合成方法，並將其應用於催化二氧化碳加一氧化碳結合式氫化反應，且藉由儀器輔助分析，探討MOF衍生混成式奈米材料在不同的合成條件下，對材料特性及其後續催化活性造成之影響。期許透過此研究之研究結果，優化MOF衍生材料的性能表現，進而開發出應用於碳捕捉再利用領域之高效觸媒，提升二氧化碳之應用價值，在實現減少溫室氣體排放的同時，生產有價值的化學產品之目標。

Reduction of CO2 is the major topic to the environment in recent years. This study aims to develop catalyst for CO2 hydrogenation to methanol. The idea of two-stage hydrogenation of CO2 is employed to achieve a higher selectivity to methanol by design, where a combination of CO2, CO and H2 is used as the simulated feedstock for the second stage hydrogenation to methanol.

In the first part, a spray-drying approach is presented to develop (1) Cu-based metal–organic framework (Cu-MOF) supported on aluminum oxide and (2) its derived Cu-ZnO/Al2O3 hybrid catalyst for combined (CO + CO2) hydrogenation to methanol. The results show superior high space time yield, 23.14 mmol gcat-1h−1, and selectivity to methanol (85%) were achievable under a moderate-pressure (30 bar) and relatively low-temperature (220 °C) operation. Incorporation of ZnO and Al2O3 enhanced the dispersion and the redox ability of Cu in the MOF-derived catalyst, both of which were critical factors to the catalytic activity toward the combined hydrogenation of CO2 and CO to methanol. An optimal performance, in terms of the methanol yield, was achieved by using the catalyst with a Cu/Zn molar ratio of 2 and partially reduction by H2 at a relatively lower temperature (300 °C).

In the second part, we optimized the synthesis method and expanded the capability of real-time material analysis. Firstly, we dispersed the MOF materials, which were synthesized by spray-drying approach, in an aqueous solution to form a colloidal solution uniformly dispersed with the precursor of active components. Based on principle of gas-phase evaporation-induced self-assembly, we atomized the colloidal solution and employed continuous two-stage gas-phase thermal treatment to fabricate MOF-derived Cu-ZnO supported on Al2O3 or CeO2 hybrid nanostructures. Additionally, differential mobility analyzer (DMA), a real-time gas-phase electrophoretic analysis of of the MOF-derived materials in aerosol state was employed for providing the traceability of the particle synthesis. The results demonstrated a successful synthesis in combination with real-time electrophoretic analysis of the synthesized MOF-derived materials. The particle size of MOF-derived materials synthesized by using this method (50~500 nm) will be smaller than using spray-drying (1~5 μm). In terms of material composition, the addition of CeO2 enhanced redox ability of Cu in the MOF-derived catalyst and showed a higher methanol selectivity. The methanol space-time yield was lower in CeO2 supported samples compared to those Al2O3 supported samples, implying that metal surface area was crucial to the performance of the synthesized catalyst.

In summary, this study demonstrated a facile synthesis method for the fabrication of MOF-derived hybrid nanocatalysts based on gas-phase evaporation-induced self-assembly, showing high performance in the combined hydrogenation of (CO2+CO) to methanol. Through the materials analysis, the impacts of different synthesis parameters on the material properties and the corresponding catalytic activity of the MOF-derived hybrid nanomaterials can be elucidated. Overall, this work showed promise for the applications in the field of CO2 capture and utilization via the development of catalyst material.

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