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, H5PWV 2W10O40, 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.
- CO chemistry
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