Macro‐/mesoporous Metal–Organic Frameworks Templated by Amphiphilic Block Copolymers Enable Enhanced Uptake of Large Molecules

Abstract The first synthesis of hierarchical porous metal–organic frameworks (HP‐MOFs) is reported through a solvent evaporation‐induced co‐assembly of polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) and MOF building blocks. The growth of MOFs is restricted to confined spaces formed by self‐assembled PS‐b‐PEO, and mesopores and/or macropores are created after removing PS‐b‐PEO by solvent rinsing. This approach avoids phase separation and competitive interactions between templates and MOF building blocks. Both amorphous and crystalline HP‐MOFs can be synthesized by finely controlling MOF growth conditions. Additionally, HP‐MOFs (ZIF‐L sheets) with honeycomb‐like channels show significantly enhanced incorporation of large guest molecules compared to microporous MOFs. This study establishes an efficient synthetic strategy for preparing HP‐MOFs with highly accessible mesopores and macropores for applications involving large molecules.