A Fully Noble Metal-Free Photosystem Based on Cobalt-Polyoxometalates Immobilized in a Porphyrinic Metal–Organic Framework for Water Oxidation

The sandwich-type polyoxometalate (POM) [(PW₉O₃₄)₂Co₄(H₂O)₂]^10- was immobilized in the hexagonal channels of the Zr(IV) porphyrinic MOF-545 hybrid framework. The resulting composite was fully characterized by a panel of physicochemical techniques. Calculations allowed identifying the localization of the POM in the vicinity of the Zr₆ clusters and porphyrin linkers constituting the MOF. The material exhibits a high photocatalytic activity and good stability for visible-light-driven water oxidation. It thus represents a rare example of an all-in-one fully noble metal-free supramolecular heterogeneous photocatalytic system, with the catalyst and the photosensitizer within the same porous solid material.