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Visible‐Light‐Driven Water Oxidation with a Polyoxometalate‐Complexed Hematite Core of 275 Iron Atoms
Author(s) -
Chakraborty Biswarup,
GanOr Gal,
Duan Yan,
Raula Manoj,
Weinstock Ira A.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201900492
Subject(s) - hematite , polyoxometalate , oxidation state , aqueous solution , water splitting , chemistry , iron oxide , oxide , catalysis , metal , redox , visible spectrum , inorganic chemistry , nanocrystal , chemical engineering , photochemistry , photocatalysis , materials science , nanotechnology , mineralogy , organic chemistry , optoelectronics , engineering
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‐Fe 2 O 3 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.