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- W2036719045 abstract "We describe the first example of redox catalysis using a dissolved electroactive nanoparticle, based on the oxidation of water by electrogenerated IrOx nanoparticles containing IrVI states, in pH 13 solutions of 1.6 ± 0.6 nm (dia.) IrIVOx nanoparticles capped solely by hydroxide. At potentials (ca. +0.45 V) higher than the mass transport-controlled plateau of the nanoparticle IrV/IV wave, rising large redox catalytic currents reflect electrochemical generation of IrVI states, which by +0.55 V and onward to +1.0 V are shown by rotated ring disk electrode experiments to lead with 100% current efficiency to the oxidation of water to O2. O2 production at +0.55 V corresponds to an overpotential η of only 0.29 V, relative to thermodynamic expectations of the four electron H2O→O2 reaction. The Ir site turnover frequency (TO, mol O2/Ir sites/s) is 8−11 s−1. Controlled potential coulometry shows that all Ir sites in these nanoparticles (average 66 Ir each) are electroactive, meaning that the nanoparticles are small enough to allow the required electron and proton transport throughout. Both the overpotential and TO values are nearly the same as those observed previously for films electroflocculated from similar IrOx nanoparticles, providing the first comparison of electrocatalysis by nanoparticle films with redox catalysis by dissolved, diffusing nanoparticles." @default.
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- W2036719045 date "2009-10-07" @default.
- W2036719045 modified "2023-09-25" @default.
- W2036719045 title "Electrogenerated IrO<sub><i>x</i></sub> Nanoparticles as Dissolved Redox Catalysts for Water Oxidation" @default.
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- W2036719045 doi "https://doi.org/10.1021/ja9063298" @default.
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