Semiconductor-Metal Composites: The Role of Ion Migration and Alloy Formation on the Stability of Core Shell Cocatalysts for Photoinduced Water Splitting

Nicole S. Hondow, Yi-Hsin Chou, Kasim Sader, Rik Brydson, Richard E. Douthwaite

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Semiconductor-metal nanoparticle composites can mediate the photoinduced reaction of water to H-2 and O-2. High spatial resolution microscopic analysis was used to investigate the structure and composition of nominally NiO/Ni core shell nanoparticles supported on the semiconductors NiTa2O6 and InTaO4, respectively. For NiTa2O6 the metal nanoparticles were confirmed as NiO/Ni core shell structures and photoreaction demonstrated that H-2 and O-2 were evolved from water at 2.75 and 1.00 mu mol g(-1) h(-1), respectively, under ca. 1 W/cm(-2) using an unfiltered 300W Xe lamp. Analysis of the composite after reaction showed evidence of degradation of the NiO/Ni nanoparticles to Ni(OH)(2). For InTaO4 bulk modification of the core shell nanoparticles occurred via diffusion of indium ions from the InTaO4 semiconductor to the nanoparticles to give a new core shell structure best formulated as Ni1.25In0.75O3/Ni3In. Although all other analytical data (PXRD, DRUVS, BET, SEM) is essentially identical to that reported for NiO/Ni:InTaO4, the activity of Ni1.25In0.75O3/Ni3In:InTaO4 for the photoinduced water splitting reaction was significantly less, exhibiting no activity with wavelengths >400 nm and only H-2 under unfiltered illumination. In contrast to NiO/Ni, degradation of Ni1.25In0.75O3/Ni3In core shell nanoparticles was not observed. The data indicate that ion diffusion between the semiconductor and nanoparticle are likely to partly explain why obtaining reproducible photoreactions using these complex systems is often difficult to achieve and that ion diffusion can be detrimental to photoactivity.

Original languageEnglish
Pages (from-to)22758-22762
Number of pages5
JournalJournal of Physical Chemistry C
Issue number51
Publication statusPublished - 30 Dec 2010


  • O-2
  • H-2
  • NB

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