Journal
CHEMSUSCHEM
Volume 12, Issue 9, Pages 1984-1994Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201802558
Keywords
electrochemistry; kinetics; photochemistry; semiconductors; water splitting
Funding
- Swiss National Science Foundation as part of the SCOUTS project [155876]
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Semiconductor photocorrosion is a major challenge for the stability of photoelectrochemical water-splitting devices. Usually, photocorrosion is studied on the basis of thermodynamic aspects, by comparing the redox potentials of water to the self-decomposition potentials of the semiconductor or analyzing the equilibrium phases at given electrolyte conditions. However, that approach does not allow for a prediction of the decomposition rate of the semiconductor or the branching ratio with the redox reaction. A kinetic model has been developed to describe detailed reaction mechanisms and investigate competition between water-splitting and photocorrosion reactions. It is observed that some thermodynamically unstable semiconductors should photocorrode in a few minutes, whereas others are expected to operate over a period of years as a result of their extremely low photocorrosion current. The photostability of the semiconductor is mainly found to depend on surface chemical properties, catalyst activity, charge carrier density, and electrolyte acidity.
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