Visible-Light-Driven Water Oxidation with a Polyoxometalate-Complexed Hematite Core of 275 Iron Atoms.

Although metal oxide nanocrystals are often highly active, rapid aggregation (particularly in water) generally precludes detailed solution-state investigations of their catalytic reactions. This is equally true for visible-light-driven water oxidation with hematite α-Fe2 O3 nanocrystals, which bridge a conceptual divide between molecular complexes of iron and solid-state hematite photoanodes. We herein report that the aqueous solubility and remarkable stability of polyoxometalate (POM)-complexed hematite cores with 275 iron atoms enable investigations of visible-light-driven water oxidation at this frontier using the versatile toolbox of solution-state methods typically reserved for molecular catalysis. The use of these methods revealed a unique mechanism, understood as a general consequence of fundamental differences between reactions of solid-state metal oxides and freely diffusing "fragments" of the same material.