Department of Chemistry and Catalysis Research Institute, Technische Universität München , 85748 Garching, Germany.
Institute for Integrated Catalysis, and Fundamental and Computational Science Directorate, Pacific Northwest National Laboratory , Richland, Washington 99352, United States.
J Am Chem Soc. 2017 Aug 2;139(30):10294-10301. doi: 10.1021/jacs.7b02936. Epub 2017 Jul 17.
Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu and ∼85% Cu. The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu to Cu. The products, methanol, dimethyl ether, and CO, were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.
通过原子层沉积在金属有机骨架（MOF）NU-1000 的节点上合成的氧化铜团簇在温和的反应条件下可用于甲烷氧化为甲醇。通过化学反应性分析、原位 X 射线吸收光谱和密度泛函理论计算，确定了 Cu-NU-1000 催化体系中的结构/活性关系。负载 Cu 的 MOF 含有少量 Cu 原子的 Cu-氧簇。在环境条件下，Cu 以 ∼15%Cu 和 ∼85%Cu 的混合物形式存在。在 Cu-NU-1000 上进行的甲烷氧化伴随着催化剂中 9%的 Cu 从 Cu 还原为 Cu。在 135°C 下用 10%水/He 通过时，产物甲醇、二甲醚和 CO 解吸，甲烷到甲醇的碳选择性为 45-60%。稳定在 NU-1000 中的 Cu 氧簇提供了一种活性的、第一代基于 MOF 的、选择性的甲烷氧化催化剂。
