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Overall Photocatalytic Water Splitting with Suspended NiO-SrTiO3 Nanocrystals

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Inorganic Metal Oxide Nanocrystal Photocatalysts for Solar Fuel Generation from Water

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Abstract

In the presence of NiO cocatalyst, large band gap (3.2 eV) SrTiO3 (STO) semiconductor catalyzes the overall water splitting reaction under UV light irradiation. As our results show, this reactivity persists at the nanoscale, although the process is less effective. Here, we compared the reactivity of Bulk STO, 30 ± 5 nm STO and 6.5 ± 1 nm STO. These materials were synthesized by three different methods and were all found to be crystalline with XRD, and were imaged with HRTEM before and after NiO deposition. When NiO is present on the surface of STO, each sample showed photocatalytic activity for overall water splitting from water into stoichiometric mixtures of H2 and O2 gas. The highest rates were observed for Bulk-STO (30 μmol g−1 h−1) followed by 30 nm STO (19.4 μmol g−1 h−1) and 6.5 nm STO (3.0 μmol g−1 h−1). We attribute this trend to reduced light absorption due to a quantum size effect, an increase of water oxidation overpotentials for the smaller particles, and a shift of the conduction band edge towards more oxidizing values. Traditionally, NiO-STO is viewed as a two-photon catalyst material; however, we present arguments in favor of a z-scheme four-photon mechanism for electron transport during the water splitting reactions.

This chapter appeared as: “T.-K. Townsend, et al., Overall Photocatalytic Water Splitting with NiOx-SrTiO 3 —A Revised Mechanism, Energy Environ. Sci. 5, 9543–9550 (2012).”

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Acknowledgments

Financial support was provided by Research Corporation for Science Advancement (Scialog award), by the National Science Foundation (NSF, Grants 0829142 and 1133099) and by the U.S. 70 Department of Energy under Grant FG02-03ER46057. TKT thanks NSFGRFP for fellowship 2012.

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Authors and Affiliations

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

    Troy K. Townsend & Frank E. Osterloh

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

    Nigel Browning

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

    Nigel Browning

Authors
  1. Troy K. Townsend
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  2. Nigel Browning
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  3. Frank E. Osterloh
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Correspondence to Frank E. Osterloh .

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Townsend, T.K., Browning, N., Osterloh, F.E. (2014). Overall Photocatalytic Water Splitting with Suspended NiO-SrTiO3 Nanocrystals. 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_4

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