Rational Synthesis of Amorphous Iron‐Nickel Phosphonates for Highly Efficient Photocatalytic Water Oxidation with Almost 100 % Yield

A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe(OH)(O₃P(CH₂)₂CO₂H)]?H₂O (MIL‐37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of ?OH group, which provides the corner‐sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe³⁺ is partially replaced by Ni²⁺, the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using Ru(bpy)₃]²⁺ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.