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

Area of Science:

• Materials Science
• Catalysis
• Supramolecular Chemistry

Background:

• Enzymatic catalysis relies on dynamic hydrogen bond networks for efficient reactions.
• Replicating these adaptive nanoscale features in synthetic catalysts is challenging.
• Metal-organic frameworks (MOFs) offer tunable platforms for catalyst design.

Purpose of the Study:

• To design and synthesize a novel iron-containing MOF (2,5OH-MIL-101(Fe)) that mimics enzyme-like hydrogen bond dynamics.
• To investigate the MOF's capability for efficient hydrogen peroxide (H2O2) activation.
• To explore the role of engineered hydrogen bond networks in catalytic performance.

Main Methods:

• Site-specific hydroxyl functionalization of terephthalate linkers in MIL-101(Fe) to create 2,5OH-MIL-101(Fe).
• Characterization of the MOF's structure and hydrogen bond network.
• Evaluation of the MOF's peroxidase-like activity in H2O2 activation.
• Comparison with conventional ferroferric oxide nanoparticles.

Main Results:

• The 2,5OH-MIL-101(Fe) MOF establishes a confined hydrogen bond network around FeO6 centers.
• This network stabilizes H2O2 intermediates and promotes O-O bond activation.
• The catalyst exhibits a 94.1-fold enhancement in peroxidase-like activity compared to ferroferric oxide nanoparticles.
• Robust, selective, and sensitive H2O2 activation was observed in the 10-1000 μM range.

Conclusions:

• Engineered hydrogen bond networks in MOFs can mimic enzymatic adaptability.
• 2,5OH-MIL-101(Fe) represents a promising bioinspired heterogeneous catalyst.
• This approach combines enzymatic precision with nanomaterial stability for advanced catalysis.