Abstract
PHOTODECOMPOSITION of water using semiconducting electrodes is being widely investigated. Using a combination of theoretical methods and experimental results we have analysed the sequential processes involved in this (phenomenon and show here that several steps are irreversible. Some of the consequences of these irreversibilities are discussed. A theory of electronic charge transfer between electrodes and aqueous electrolytes, based on an equilibrium approximation by Marcus1, seems to be valid for metal electrodes. Gerischer2 has considered both metal and semiconductor electrodes and concluded that in general the electron is isoenergetically injected (tunnels) from the occupied band state of the electrode into an unoccupied state of the electrolyte. Rearrangement of the molecular environment then occurs, irreversibly changing the energy of the electronic state of the electrolyte. Finally, reverse tunnelling from the relaxed state back into the electrode may occur.
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WILLIAMS, F., NOZIK, A. Irreversibilities in the mechanism of photoelectrolysis. Nature 271, 137–139 (1978). https://doi.org/10.1038/271137b0
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DOI: https://doi.org/10.1038/271137b0
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