減少溫室氣體排放並將其轉化為高價值燃料和化學品對於緩解氣候變化的影響至關重要。甲烷是一種強效溫室氣體，其全球暖化潛勢遠高於二氧化碳。同時，甲烷也是甲醇和其他化學品生產的寶貴原料。因此，將甲烷催化轉化為甲醇已引起重要的研究關注，成為燃料和大宗化學品來源等。金屬有機骨架材料（MOFs）作為各種化學反應的優良催化劑載體受到廣泛研究，包括甲烷轉化反應。由於其高孔隙度、可調性和空間限制等性能，MOFs提供了獨特的研究方向來設計高效且選擇性的催化劑。近期仿生材料受到顆粒甲烷單加氧酶（pMMO）酶的啟發，利用氧化銅簇作為活性位點，在甲烷轉化中展現了應用潛力。本研究使用密度泛函理論（DFT）計算研究了以MIL-53(Al)作為載體支撐的銅氧化物簇（Cu2On，Cu3On，n=1~3）對甲烷氧化的反應性。首先，我們考慮使用O2和N2O這兩種氧化劑形成氧化銅簇。在甲烷轉化的過程中，Cu2O2/MIL-53(Al)和Cu3O2/MIL-53(Al)催化劑上的初始C-H鍵活化能非常低，表明CumO2(m=2,3)/MIL-53(Al)催化劑可以有效活化甲烷分子，這是甲烷轉化為甲醇反應的速率決定步驟。此外，研究結果表明由於甲醛生成的能障皆極高，所以CumO2(m=2,3)/MIL-53(Al)對甲醇的生成具有高度的選擇性。甲醇在CumO(m=2,3)/MIL-53(Al)催化劑上的脫附能皆小於0.75 eV，表明甲醇可以輕易地從催化劑表面脫附。同時，我們探索了不同的方法來再活化氧化銅簇，並提出了多種反應途徑來完成反應循環。此外，我們進行了電子分析以瞭解氧化銅簇對甲烷活化的影響，並使用微觀動力學模擬來預測室溫下的反應可行性。總的來說，我們的研究結果顯示以MOF載體支撐的銅氧化物簇具有潛力成為高效且可重複使用的甲烷轉化催化劑，並同時具有高甲醇選擇性。

Reducing greenhouse gas emissions and converting them into high-value fuels and chemicals is crucial for mitigating the effects of climate change. Methane is a potent greenhouse gas with a much higher global warming potential than carbon dioxide. It is also a valuable feedstock for the production of methanol and other chemicals. Therefore, the catalytic conversion of methane to methanol has attracted significant research interest as a sustainable source of vehicle fuels and bulk chemicals. Metal-organic frameworks (MOFs) have emerged as promising catalyst supports for various chemical reactions, including methane conversion. They provide a unique platform for designing highly efficient and selective catalysts because of their high porosity, tuneability, and confinement properties. The particulate methane monooxygenase (pMMO) enzyme, which utilizes copper oxide clusters as active sites, has inspired the development of biomimetic materials for methane conversion. In this study, we study the reactivity of copper oxide clusters (Cu2On, Cu3On, n=1~3) supported by the well-known MIL-53(Al) MOF towards methane oxidation using density functional theory (DFT) calculations. Initially, two oxidizing agents, O2 and N2O, are considered to form the copper oxide clusters. In the CH4 conversion, the initial C-H bond activation barriers on Cu2O2/MIL-53(Al) and Cu3O2/MIL-53(Al) catalysts are low, indicating that the CumO2(m=2,3)/MIL-53(Al) catalyst can effectively activate methane molecules, which is a rate-determining step in overall methane conversion to methanol. Furthermore, our results show that CumO2(m=2,3)/MIL-53(Al) has a high selectivity towards methanol formation, with an extremely high energy barrier for formaldehyde formation. The desorption energy of methanol over the CumO (m=2,3)/MIL-53(Al) catalyst is less than 0.75 eV, indicating that methanol can be easily detached from the catalyst surface. We also explore different methods for regenerating the active copper oxide clusters and propose various reaction pathways to complete the reaction cycle. In addition, we performed an electronic analysis to understand the influence of the copper oxide clusters on methane activation and used microkinetic simulations to predict the reaction of viability at room temperature. Overall, our findings show that MOF-supported copper oxide clusters have the potential to be highly efficient and reusable methane conversion catalysts with high methanol selectivity.

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