Engineering Adaptive Hydrogen Bond Networks in Metal–Organic Frameworks for Bioinspired H ₂ O ₂ Catalysis Enhancement

Dynamic hydrogen bond networks are integral to enzymatic catalysis, enabling efficient substrate polarization, intermediate stabilization, and rapid active-site turnover. However, translating such adaptive features into synthetic systems at the nanoscale presents a significant challenge. Here, we report a rationally designed Fe-containing metal-organic framework (MOF), 2,5OH-MIL-101(Fe), derived from MIL-101(Fe), that mimics enzyme-like hydrogen-bond dynamics for efficient hydrogen peroxide (H₂O₂) activation. By site-specific hydroxyl functionalization of terephthalate linkers, 2,5OH-MIL-101(Fe) forms a confined hydrogen-bond network around FeO₆ centers that stabilizes H₂O₂-derived intermediates through O-H···O interactions and promotes O-O bond activation. This network subsequently polarizes electrons through directional hydrogen bond interactions and ultimately facilitates H₂O desorption via reversible bond switching. These nanostructured interactions continuously regenerate Fe active sites, leading to a 94.1-fold enhancement in peroxidase-like activity compared to conventional ferroferric oxide nanoparticles. The catalyst demonstrates robust, selective, and sensitive H₂O₂ activation within a physiologically relevant concentration range (10-1000 μM). This work demonstrates hydrogen bond network engineering in MOFs as a promising approach for creating adaptive catalysts that combine the precision of enzymes with the stability of nanomaterials, advancing bioinspired heterogeneous catalysis.