Peer-Reviewed Journal Details
Mandatory Fields
Hidalgo-Acosta, Jonnathan C.; Méndez, Manuel A.; Scanlon, Micheál D.; Vrubel, Heron; Amstutz, Véronique; Adamiak, Wojciech; Opallo, Marcin and Girault, Hubert H.
Chemical Science
Catalysis of water oxidation in acetonitrile by iridium oxide nanoparticles
Optional Fields
Water oxidation Water/acetonitrile mixtures IrO2 nanoparticles
Water oxidation catalysed by iridium oxide nanoparticles (IrO2 NPs) in water/acetonitrile mixtures using [RuIII(bpy)3]3+ as oxidant was studied as a function of the water content, the acidity of the reaction media and the catalyst concentration. It was observed that under acidic conditions (HClO4) and at high water contents (80% (v/v)) the reaction is slow, but its rate increases as the water content decreases, reaching a maximum at approximately equimolar proportions (≈25% H2O (v/v)). The results can be rationalized based on the structure of water in water/acetonitrile mixtures. At high water fractions, water is present in highly hydrogen-bonded arrangements and is less reactive. As the water content decreases, water clustering gives rise to the formation of water-rich micro-domains, and the number of bonded water molecules decreases monotonically. The results presented herein indicate that non-bonded water present in the water micro-domains is considerably more reactive towards oxygen production. Finally, long term electrolysis of water/acetonitrile mixtures containing [RuII(bpy)3]2+ and IrO2 NPs in solution show that the amount of oxygen produced is constant with time demonstrating that the redox mediator is stable under these experimental conditions. doi=10.1039/C4SC02196G
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