Abstract
AbstractAlthough 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‐Fe2O3 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.
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