Graphene Mediates Charge Transfer between Lead Chromate and a Cobalt Cubane Cocatalyst for Photocatalytic Water Oxidation.

The interfacial barrier of charge transfer from semiconductors to cocatalysts means that the photogenerated charges cannot be fully utilized, especially for the challenging water oxidation reaction. Using cobalt cubane molecules (Co O ) as water oxidation cocatalysts, we rationally assembled partially oxidized graphene (pGO), acting as a charge-transfer mediator, on the hole-accumulating {-101} facets of lead chromate (PbCrO ) crystal. The assembled pGO enables preferable immobilization of Co O molecules on the {-101} facets of the PbCrO crystal, which is favorable for the photogenerated holes transferring from PbCrO to Co O molecules. The surface charge-transfer efficiency of PbCrO was boosted by selective assembly of pGO between PbCrO and Co O molecules. An apparent quantum efficiency for photocatalytic water oxidation on the Co O /pGO/PbCrO photocatalyst exceeded 10 % at 500 nm. This strategy of rationally assembling charge-transfer mediator provides a feasible method for acceleration of charge transfer and utilization in semiconductor photocatalysis.