Breaking the Concentration Barrier: MOF‐Stabilized Metal Ion‐Enzyme Systems for Enhanced Catalytic Efficiency

Metal ion‐enzyme tandem systems hold immense potential for biocatalysis, environmental remediation, and medical therapy, yet their development is hindered by inherent incompatibility, low ion concentration, and spatial distance barriers between metal ions and enzyme, limiting the maximization of metal ion catalytic potential. Here, we developed a convenient one‐step doping strategy to achieve spatial separation of high concentration metal ions and enzymes within single metal‐organic frameworks (MOFs). Catalytically active metal ions partially replace MOF sites through ligand coordination, while enzymes are in‐situ encapsulated (enzyme@M‐MOFs), maintaining structural integrity and enhancing stability. This design enables efficient chem‐bio tandem reactions by preventing mutual inactivation and accelerating reaction rates due to distance shortening between metal ions and enzymes. The enzyme@M‐MOFs exhibit good therapeutic effect in diabetic wound healing, establishing a new paradigm for catalytic medicine applications. The strategy's versatility is demonstrated by its successful application with a range of metal ions (Fe²⁺, Mg²⁺, Cd²⁺ …) as catalysts or enzyme promoters. By transforming incompatible systems into compatible tandem platforms, this work offers a universal approach for efficient chemical‐enzyme tandem catalysis, unlocking novel possibilities in biocatalysis and beyond.