Site-Directed Reduction Engineering within Binary Metal-Organic Frameworks for Efficient Size-Selective Catalysis

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 MOFs compounds. Herein, the reducibility of MOFs clusters first revealed via theoretical calculations from viewpoint of the reduction potential energy (Ereduction), which serves as the basic principle for the site-directed reduction processing of MOFs. The active component with a high Ereduction in binary MOFs is selectively reduced to metal nanostructures, while the other (inert) parts maintain their structural integrity in this process. 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.