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I am looking into the mechanism of different electrocatalytic reaction in acidic media on metal-oxide electrodes.

Reduction of on such electrodes generally happens with the help of electrons from the conducting band of the electrode, which is mainly d bands of the metal. That made me wonder about the mechanism of hydrogen formation: I assumed hydrogen is formed from protons chemisorbed on the surface. However, protons are likely to attach to surface oxygen ions, not metal ions, therefore it seems difficult to receive electrons from the conducting band.

Different of water-related electrocatalysis seems very extensively studied, including many atomistic simulations, however, I haven't found much on hydrogen evolution on oxide electrodes. Is there an established mechanism for hydrogen formation?

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  • $\begingroup$ I don't think there's established mechanism, there may be postulated one, but heterogenic reactions are notoriously difficult as far as finding mechanism is concerned. $\endgroup$ – Mithoron Dec 16 '17 at 16:58

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