Directional processing of metal-organic frameworks (MOFs) into unique hybrid materials with desired structures and properties is a key scientific challenge in exploring the enhanced functionality and potential applications of MOF compounds. Here, the reducibility of MOF clusters is first revealed via theoretical calculations from the viewpoint of the reduction potential energy (E_reduction), which serves as the basic principle for the site-directed reduction processing of MOFs. During this process, the active component with a high E_reduction in bimetallic MOFs is selectively reduced to metal nanostructures, while the other (inert) parts maintain their structural integrity. A series of hierarchical MOFs/metal nanoparticle composites with different structures, including yolk-shell, core-shell, and dispersed, have been successfully customized. More importantly, the as-prepared hybrid materials (Co-B@ZIF-8) exhibit unique size-selective properties in catalyzing ketone hydrogenation, which originate from the combination of the high catalytic performance of the nanoscale metal catalysts and the molecular sieving behavior of the MOFs' well-defined microporous nature.

将金属有机骨架 (MOF) 定向加工成具有所需结构和性能的独特混合材料，是探索 MOF 化合物增强功能和潜在应用的关键科学挑战。在这里，MOF 团簇的还原性首先从还原势能（E_还原）的角度通过理论计算揭示，这是 MOF 定点还原处理的基本原理。在此过程中，具有高E_减少的活性成分双金属 MOF 中的 2 部分被选择性地还原为金属纳米结构，而其他（惰性）部分保持其结构完整性。一系列具有不同结构的分层MOFs/金属纳米颗粒复合材料已成功定制，包括蛋黄-壳、核-壳和分散。更重要的是，所制备的杂化材料（Co-B@ZIF-8）在催化酮加氢过程中表现出独特的尺寸选择特性，这源于纳米级金属催化剂的高催化性能和分子筛行为的结合。 MOF 明确定义的微孔性质。