Bridging Catalytic Worlds: A Coassembly Platform for Unified Chemoenzymatic Cascades

The integration of biocatalytic and chemocatalytic cascades offers a promising route toward sustainable and efficient chemical synthesis. However, inherent incompatibilities between these catalytic systems have impeded progress in this area, particularly regarding their efficient coimmobilization within a single carrier. Herein, we report a general Pickering emulsion-driven interfacial coassembly strategy to construct modular micro/nanoreactors that enable the precise spatial integration of metal nanoparticles and multiple enzymes within a porous crystalline framework, including diverse metal–organic frameworks and covalent organic frameworks. These compartmentalized reactors orchestrate efficient chemoenzymatic one-pot reactions, as demonstrated by the dynamic kinetic resolution of racemic amines via synergistic Pd/enzyme catalysis. Furthermore, this architecture drives effective photoenzymatic cascades and exhibits robust utility in degrading pollutants under demanding conditions. By overcoming limitations inherent to conventional strategies, such as restricted carrier compatibility, insufficient active site exposure, and constrained mass transfer, this work provides a universal solution for integrating otherwise incompatible catalytic reactions.