Photochemical Reduction of CO₂ with Visible Light Using a Polyoxometalate as Photoreductant

The photochemical reduction of CO₂ to CO requires two electrons and two protons that, in the past, have been derived from sacrificial amine donors that are also non-innocent in the catalytic cycle. Towards the realization of a water-splitting reaction as the source of electrons and protons for CO₂ reduction, we have found that a reduced acidic polyoxometalate, H₅ PW^V₂ W₁₀ O₄₀ , is a photoactive electron and proton donor with visible light through excitation of the intervalence charge-transfer band. Upon linking the polyoxometalate to a dirhenium molecular catalyst, a cascade of transformations occurs where the polyoxometalate is electrochemically reduced at a relatively low negative potential of 1.3 V versus Ag/AgNO₃ and visible light, a 60 W tungsten lamp, or a red LED is used to transfer electrons from the polyoxometalate to the dirhenium catalyst active for the selective reduction of CO₂ to CO.