Engineering Adaptive Hydrogen Bond Networks in Metal-Organic Frameworks for Bioinspired H2O2 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.