Abstract
Rutile IrO(2) is known as being among the best electrocatalysts for water oxidation. Here we report on the unexpected photocatalytic water oxidation activity of 1.98 nm ± 0.11 nm succinic acid-stabilized IrO(2) nanocrystals. From aqueous persulfate and silver nitrate solution the nonsensitized particles evolve oxygen with initial rates up to 0.96 μmol min(-1), and with a quantum efficiency of at least 0.19% (measured at 530 nm). The catalytic process is driven by visible excitations from the Ir-d(t(2g)) to the Ir-d(e(g)) band (1.5-2.75 eV) and by ultraviolet excitations from the O-p band to the Ir-d(e(g)) (>3.0 eV) band. The formation of the photogenerated charge carriers can be directly observed with surface photovoltage spectroscopy. The results shed new light on the role of IrO(2) in dye- and semiconductor-sensitized water splitting systems.
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