Li Yi-Ming, Shi Dongxia, Yuan Jian, Zuo Rui-Min, Yang Hui, Hu Jinhui, Hu Shu-Xian, Sheng Hongting, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University, Hefei, Anhui, 230601, P. R. China.
School of Chemistry and Materials Engineering and Anhui Provincial Key Laboratory of Green Carbon Chemistry, Fuyang Normal University, Fuyang, Anhui, 236041, P. R. China.
Adv Mater. 2025 Jan;37(1):e2412768. doi: 10.1002/adma.202412768. Epub 2024 Oct 30.
The combination of atomically precise nanoclusters (APNCs) and reticular frameworks is promising for generating component-specific nanocomposites with emergent properties. However, traditional liquid-phase synthesis often hampers this potential by damaging APNCs and limiting combination diversity. Here, mechanochemical synthesis to explore the encapsulation of diverse oil- and water-soluble APNCs within various reticular frameworks is employed, establishing a database of 21 unique APNC-framework combinations, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and multivariate MOFs. These framework coatings not only spatially immobilize APNCs but also secure their structures, preventing aggregation and degradation while enhancing stability and activity. Encapsulating Au in HOFs resulted in a remarkable 315-fold increase in catalytic activity compared to Au homogeneous catalyst, highlighting the framework's crucial role in catalytic enhancement. The mechanochemical synthesis strategy facilitates tailored support screening, catering to specific needs, and shows promise for developing multifunctional systems, including enzyme-APNC@frameworks material for cascade reactions.
原子精确的纳米团簇（APNCs）与网状框架的结合有望生成具有新兴特性的特定成分纳米复合材料。然而，传统的液相合成常常通过破坏APNCs和限制组合多样性来阻碍这种潜力。在此，采用机械化学合成方法来探索将各种油溶性和水溶性APNCs封装在各种网状框架内，建立了一个包含21种独特APNC-框架组合的数据库，包括金属有机框架（MOFs）、共价有机框架（COFs）、氢键有机框架（HOFs）和多元MOFs。这些框架涂层不仅在空间上固定了APNCs，还保护了它们的结构，防止聚集和降解，同时提高了稳定性和活性。与金均相催化剂相比，将金封装在HOFs中导致催化活性显著提高了315倍，突出了框架在催化增强中的关键作用。机械化学合成策略有助于进行定制的载体筛选，满足特定需求，并显示出开发多功能系统的前景，包括用于级联反应的酶-APNC@框架材料。
