Visible Light-Driven Water Oxidation by Ir Oxide Clusters Coupled to Single Cr Centers in Mesoporous Silica

Visible light-induced water oxidation has been demonstrated at an Ir oxide nanocluster coupled to a single CrVI site on the pore surface of MCM-41 mesoporous silica. The photocatalytic unit was assembled by the reaction of surface Cr=O groups with Ir(acac)3 precursor followed by calcination at 300 degrees C and bond formation monitored by FT-Raman and FT-IR spectroscopy. High-resolution Z-contrast electron micrographs of the calcined material combined with energy-dispersive X-ray spot analysis confirmed the occlusion of Ir oxide nanoparticles inside the mesopores. Oxygen evolution of an aqueous suspension of the IrxOy-CrMCM-41 upon visible light irradiation of the CrVI-O ligand-to-metal charge-transfer absorption was monitored mass-spectrometrically. Comparison of the product yields for samples with low Cr content (Cr/Si </= 0.02) and high Cr content (Cr/Si = 0.05) indicates that only isolated Cr centers are capable of extracting electrons from Ir oxide clusters, while di- or polychromate species are not. Water oxidation at a multielectron-transfer catalyst coupled to a single metal center has not been demonstrated before. The ability to drive water oxidation with a single metal center as electron pump offers opportunities for coupling the oxygen-evolving photocatalytic unit to reducing sites in the nanoporous scaffold.