Cobalt-based cubane molecular co-catalysts for photocatalytic water oxidation by polymeric carbon nitrides

In artificial photocatalysis, sluggish kinetics of hole transfer and the high recombination rate of charge have been the Achilles' heel of photocatalytic conversion efficiency. The development of co-catalysts for promoting exciton splitting and charge separation has therefore gained continuous attention. Herein, Co4O4 cubane complex Co4O4(O2CMe)(4)(PY)(4) (1a, py = pyridine derivatives), serves as a homogeneous molecular co-catalyst which is engineered into the framework of pristine polymeric carbon nitride (PCN) for water oxidation with light illumination. This modification strategy maximizes the contact areas between co-catalysts and reactants, reduces the over-potential of oxygen producing and accelerates the interface transfer rate of electron-hole pairs, thus leading to enhanced reaction kinetics for photocatalytic water oxidation. Compared with pristine PCN, the photocatalytic O-2 production rate up to 19-fold-enhanced in the presence of molecular co-catalyst. This work emphasizes the importance of developing effective, stable and earth-abundant molecular co-catalysts for the promotion of water-splitting photocatalysis.