Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 13, Pages 5774-5777Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja301212r
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Funding
- NSF [CHE-0950320]
- UNC EFRC: Center for Solar Fuels, an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001011]
- Eastman Chemical Company (Kingsport, TN)
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0950320] Funding Source: National Science Foundation
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Self-assembled monolayers (SAMs) of carboxylated alkanethiolates (-S(CH2)(n-1)CO2-) on flat gold electrode surfaces are used to tether small (ca. 2 nm d.) iridium(IV) oxide nanoparticles ((IrOX)-O-IV NPs) to the electrode. Peak potential separations in cyclic voltammetry (CV) of the nanoparticle Ir-IV/III wave, in pH 13 aqueous base, increase with n, showing that the Ir-IV/III apparent electron transfer kinetics of metal oxide sites in the nanoparticles respond to the imposed SAM electron transfer tunneling barrier. Estimated apparent electron transfer rate constants (k(app)(0)) for n = 12 and 16 are 9.8 and 0.12 s(-1). Owing to uncompensated solution resistance, k(app)(0) for n = 8 was too large to measure in the potential sweep experiment. For the cathodic scans, coulometric charges under the Ir-IV/III voltammetric waves were independent of potential scan rate, suggesting participation of all of the iridium oxide redox sites (ca. 130 per NP) in the NPs. These experiments show that it is possible to control and study electron transfer dynamics of electroactive nanoparticles including, as shown by preliminary experiments, that of the electrocatalysis of water oxidation by iridium oxide nanoparticles.
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