Cobalt-Based Metal-Organic Cages for Visible-Light-Driven Water Oxidation

Water oxidation to molecular oxygen is indispensable but a challenge for splitting H₂O. In this work, a series of Co-based metal-organic cages (MOCs) for photoinduced water oxidation were prepared. MOC-1 with both bis(μ-oxo) bridged dicobalt and Co-O (O from H₂O) displays catalytic activity with an initial oxygen evolution rate of 80.4 mmol/g/h and a TOF of 7.49 × 10^-3 s^-1 in 10 min. In contrast, MOC-2 containing only Co-O (O from H₂O) in the structure results in a lower oxygen evolution rate (40.8 mmol/g/h, 4.78 × 10^-3 s^-1), while the amount of oxygen evolved from the solution of MOC-4 without both active sites is undetectable. Isotope experiments with or without H₂¹⁸O as the reactant successfully demonstrate that the molecular oxygen was produced from water oxidation. Photophysical and electrochemical studies reveal that photoinduced water oxidation initializes via electron transfer from the excited [Ru(bpy)₃]²⁺* to Na₂S₂O₈, and then, the cobalt active sites further donate electrons to the oxidized [Ru(bpy)₃]³⁺ to drive water oxidation. This proof-of-concept study indicates that MOCs can work as potential efficient catalysts for photoinduced water oxidation.