Amorphous Ru-bda MCOF: A Frontier in Heterogeneous Molecular Catalysis for Water Oxidation

Traditional crystalline MCOFs often sacrifice catalytic activity to achieve long-range order, limiting microenvironment tunability. Here, we used the high-performance Ru(bda)(pyCHO)2 complex and ETTA linker to construct two amorphous materials AMCOF-X via coordination and dehydration assembly. Structural characterization and performance tests show that dehydration assembly strategy expands the framework and reduces particle size, greatly improving the accessibility of Ru active sites. In a Ru(bpy)32+ photocatalytic water oxidation system, AMCOF-2 achieves a first-order rate constant of 68.11 μmol g–1 s–1─an exponential enhancement over most COF-based catalysts. The flexible microenvironment and accessible metal sites in the amorphous skeleton promote a water nucleophilic attack pathway, facilitating efficient O═O bond formation. Our modular assembly enables efficient integration of molecular catalysts within metal–organic covalent frameworks, offering a novel design route for combining molecular catalysis with framework materials.