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Issue 16, 2013
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A mechanistic study of the electrochemical oxygen reduction on the model semiconductor n-Ge(100) by ATR-IR and DFT

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Abstract

The electrochemical oxygen reduction reaction (ORR) on a n-Ge(100) surface in 0.1 M HClO4 was investigated in situ and operando using a combination of attenuated total reflection infrared (ATR-IR) spectroscopy and density functional (DFT) calculations. The vibrational modes of the detected intermediates were assigned based on DFT calculations of solvated model clusters such as Ge-bound superoxides and peroxides. ATR-IR shows the Ge-bound superoxide with a transition dipole moment oriented at (28 ± 10)° with respect to the surface normal. At slightly negative potentials, the surface-bound peroxide is identified by an OOH bending mode as a further intermediate, oriented at a similar angle. At strongly negative potentials, a surface-bound perchlorate is found. The findings indicate a multistep mechanism of the ORR. The reaction is furthermore coupled with the hydrogen evolution reaction (HER).

Graphical abstract: A mechanistic study of the electrochemical oxygen reduction on the model semiconductor n-Ge(100) by ATR-IR and DFT

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Publication details

The article was received on 04 Nov 2012, accepted on 02 Jan 2013 and first published on 04 Jan 2013


Article type: Paper
DOI: 10.1039/C2CP43909C
Citation: Phys. Chem. Chem. Phys., 2013,15, 5771-5781
  • Open access: Creative Commons BY-NC license
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    A mechanistic study of the electrochemical oxygen reduction on the model semiconductor n-Ge(100) by ATR-IR and DFT

    S. Nayak, P. U. Biedermann, M. Stratmann and A. Erbe, Phys. Chem. Chem. Phys., 2013, 15, 5771
    DOI: 10.1039/C2CP43909C

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