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Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods
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Using TiO2 as a conductive protective layer for photocathodic H2 evolution.

Brian Seger1, Thomas Pedersen, Anders B Laursen

  • 1Department of Physics, CINF, Technical University of Denmark, DK-2800, Kongens Lyngby, Denmark.

Journal of the American Chemical Society
|January 8, 2013
PubMed
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A titanium dioxide (TiO2) layer protects silicon photocathodes from surface passivation during hydrogen evolution. This TiO2 layer conducts electrons, enhancing performance and stability for efficient photocatalytic water splitting.

Area of Science:

  • Materials Science
  • Electrochemistry
  • Photocatalysis

Background:

  • Surface passivation hinders electron conduction in Si-based photoelectrodes at the semiconductor/electrolyte interface.
  • Protecting Si photocathodes is crucial for efficient photocatalytic hydrogen evolution.

Purpose of the Study:

  • To investigate TiO2 as a protective and conductive layer for n(+)p Si photocathodes.
  • To analyze the behavior of TiO2 under photocathodic conditions for hydrogen evolution.
  • To optimize the performance and stability of Si-based photocathodes.

Main Methods:

  • Sputtering a 100 nm TiO2 layer onto a thin Ti metal layer on an n(+)p Si photocathode.
  • Utilizing a Pt catalyst for hydrogen evolution.
  • Illumination with the red part (λ > 635 nm) of the AM 1.5 spectrum.

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  • Employing an Fe(2+)/Fe(3+) redox couple to study the band diagram.

    • Main Results:

    • The TiO2 layer effectively protected the Si photocathode from surface passivation.
    • TiO2 exhibited metallic conductor-like behavior due to favorable band alignment, facilitating electron transfer.
    • The electrode achieved an H2 evolution onset of 520 mV vs NHE and a Tafel slope of 30 mV.
    • Antireflective properties of TiO2 enhanced saturation photocurrent, and electrodes showed stability for 72 hours after annealing.

    Conclusions:

    • A sputtered TiO2 layer on Ti metal is an effective strategy to prevent surface passivation in Si photocathodes.
    • The unique electronic properties of TiO2 under photocathodic conditions enable efficient electron conduction and protection.
    • This approach significantly enhances hydrogen evolution performance and long-term stability for Si-based photoelectrodes.