Modifiers versus Channels: Creating Shape‐Selective Catalysis of Metal Nanoparticles/Porous Nanomaterials

Shape‐selective catalysis plays a key role in chemical synthesis. Porous nanomaterials with uniform pore structures are ideal supports for metal nanoparticles (MNPs) to generate efficient shape‐selective catalysis. However, many commercial irregular porous nanomaterials face the challenge to realize satisfactory shape selectivity due to the lack of molecular sieving structures. Herein, we report a concept of creating shape selectivity in MNPs/porous nanomaterials through intentionally poisoning certain MNPs using suitable modifiers. The remaining MNPs within the substrates can cooperate with the channels to generate selectivity. Such a strategy not only applies to regular porous nanomaterials (such as MOFs, zeolites) but also extended to irregular porous nanomaterials (such as active carbon, P25). Potentially, the matching among different MNPs, corresponding modifiers, and porous nanomaterials makes our strategy promising in selective catalytic systems. A modifier strategy is utilized to create shape selectivity in metal nanoparticle/porous nanomaterial with regular/irregular pore structures by intentionally poisoning certain MNPs. The strategy of flexibly matching different MNPs and corresponding modifiers could be extended to various catalytic systems such as selective hydrogenation and selective oxidation reactions.