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The Oxygen Evolution Reaction: Water Oxidation Photocatalysis—Photocatalytic Water Oxidation with Suspended alpha-Fe2O3 Particles—Effects of Nanoscaling

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Inorganic Metal Oxide Nanocrystal Photocatalysts for Solar Fuel Generation from Water

Part of the book series: Springer Theses ((Springer Theses))

Abstract

Iron oxide has recently been shown to be active on the nanoscale as a photoanode material and is gaining interest due to the material’s low cost, abundance, and visible light absorption. It has a phonon assisted visible light excited band gap of 2.06 eV which corresponds to the middle of the visible region (600 nm) near the peak intensity of the solar spectrum. This d–d transition is accompanied by a direct band gap of 3.3 eV (375 nm), associated with the ligand to metal charge transfer. In this work, we show for the first time that freely dispersed Fe2O3 nanocrystals are catalytically active for the photo-oxidation of water. Three morphologies of hematite were compared, including bulk-type-α-Fe2O3 (Bulk-Fe2O3, 120 nm), ultrasonicated Bulk-Fe2O3 (Sonic-Fe2O3, 44 nm), and synthetic Fe2O3 (Nano-Fe2O3, 5.4 nm) obtained by hydrolysis of FeCl .3 6H2O. Each material showed similar optical properties, and the water oxidation overpotentials were derived from cyclic voltammetry. Versus NHE at pH = 7, at 1.0 mA cm−2, the extra chemical potential energy required to oxidize water increased with particle size as η = + 0.43 V for Nano-Fe2O3, η = + 0.63 V for Sonic-Fe2O3, and η = + 0.72 V for Bulk- Fe2O3. According to X-ray diffraction, all phases were presented in the alpha structure type, with Nano-Fe2O3 also containing traces of β-FeOOH. When suspended in a sacrificial electron accepting solution of aqueous AgNO3 (20 mM) and irradiated with UV/Vis (λ > 250 nm) or visible (λ > 400 nm) light, all three materials (5.6 mg) evolved O2 from water. The rate of O2 evolution increased with decreasing particle size with 250 mmolh−1g−1 for Bulk-Fe2O3, 381 mmolh−1 g−1 for Sonic-Fe2O3 and 1072 mmolh−1 g−1 for Nano-Fe2O3. While Bulk-Fe2O3 showed turnover numbers (TON = moles O2/moles Fe2O3) less than unity (0.49), the other two nanoscale materials showed catalytic turnovers of 1.10 for Sonic-Fe2O3 and 1.13 for Nano-Fe2O3, showing that the nanoscale morphology was beneficial for catalytic activity.

This chapter appeared as: “T.-K. Townsend, et al., Photocatalytic Water Oxidation with Suspended alpha- Fe 2 O 3 Particles-Effects of Nanoscaling, Energy Environ. Sci. 4, 4270–4275 (2011).”

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Acknowledgments

FEO thanks Research Corporation for Science Advancement for a Scialog award. This work was further supported by the National Science Foundation (NSF, grant 0829142) and by the US Department of Energy (grant FG02–03ER46057). TKT thanks NSF for a Graduate Research Fellowship 2011. N.D.B. thanks the US Department of Energy for support (grant FG02–03ER46057).

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Authors and Affiliations

  1. Department of Chemistry, University of California, One Shields Avenue, 95616, Davis, CA, USA

    Troy K. Townsend, Erwin M. Sabio & Frank E. Osterloh

  2. Department of Chemical Engineering and Materials Science, University of California, One Shields Avenue, 95616, Davis, CA, USA

    Nigel D. Browning

  3. Lawrence Livermore National Laboratory, 7000 East Avenue, 94550, Livermore, CA, USA

    Nigel D. Browning

Authors
  1. Troy K. Townsend
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  2. Erwin M. Sabio
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  3. Nigel D. Browning
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  4. Frank E. Osterloh
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Correspondence to Troy K. Townsend .

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Townsend, T.K., Sabio, E.M., Browning, N.D., Osterloh, F.E. (2014). The Oxygen Evolution Reaction: Water Oxidation Photocatalysis—Photocatalytic Water Oxidation with Suspended alpha-Fe2O3 Particles—Effects of Nanoscaling. In: Inorganic Metal Oxide Nanocrystal Photocatalysts for Solar Fuel Generation from Water. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-319-05242-7_3

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