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Issue 21, 2016
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The effect of Rhδ+ dopant in SrTiO3 on the active oxidation state of co-catalytic Pt nanoparticles in overall water splitting

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Abstract

We report on the oxidation state of Pt nanoparticles when deposited on SrTiO3 or Rh-doped SrTiO3 under realistic solar water-splitting conditions. The oxidation state was investigated using state-of-the-art analysis of the reaction in a continuously stirred tank reactor (CSTR) connected to a micro gas chromatograph equipped with a pulsed discharge detector (PDD) detector and ex-situ XPS. We demonstrate an initially large, but transient, peak in the oxygen production rate during the conversion of acidified water using SrTiO3 loaded with Pt nanoparticles prepared by photo-deposition (in the absence of methanol). This was confirmed by XPS analysis to be the result of a change in oxidation state from PtOx to metallic Pt. Remarkably, when PtOx was present on SrTiO3 doped with Rhδ+, the transient peak in the O2 production was of much lower magnitude than when in the absence of Rhδ+. The XPS analysis demonstrates that this can be explained by the incomplete reduction of the Pt nanoparticles in the presence of Rhδ+. The average oxidation state of Pt deposited on SrTiO3 during the water-splitting reaction thus appears very much dependent on the absence or presence of dopants. This effect is often neglected, but is highly relevant for the discussion of composition-activity correlations of (doped) semiconductors functionalized with metal(oxide) nanoparticles in overall water splitting.

Graphical abstract: The effect of Rhδ+ dopant in SrTiO3 on the active oxidation state of co-catalytic Pt nanoparticles in overall water splitting

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Publication details

The article was received on 03 Jul 2016, accepted on 10 Sep 2016 and first published on 12 Sep 2016


Article type: Paper
DOI: 10.1039/C6CY01424K
Citation: Catal. Sci. Technol., 2016,6, 7793-7799
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    The effect of Rhδ+ dopant in SrTiO3 on the active oxidation state of co-catalytic Pt nanoparticles in overall water splitting

    M. G. C. Zoontjes, K. Han, M. Huijben, W. G. van der Wiel and G. Mul, Catal. Sci. Technol., 2016, 6, 7793
    DOI: 10.1039/C6CY01424K

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