  We introduce an approach to calculate the thermodynamic oxidation and
reduction potentials of semiconductors in aqueous solution. By combining a
newly-developed ab initio calculation for compound formation energy and band
alignment with electrochemistry experimental data, this approach can be used to
predict the stability of almost any compound semiconductor in aqueous solution.
30 photocatalytic semiconductors have been studied, and a graph (a simplified
Pourbaix diagram) showing their valence/conduction band levels and
oxidation/reduction potentials is produced. Based on this graph, we have
studied the stabilities and trends against the oxidative and reductive
photocorrosion for compound semiconductors. We found that, only metal oxides
can be thermodynamically stable when used as the n-type photoanodes. All the
non-oxides are unstable due to easy oxidation by the photogenerated holes, but
they can be resistant to the reduction by electrons, thus stable as the p-type
photocathodes.
