I am measuring an electrode material to be used for photoelectrochemical water splitting and I am obtaining negative photocurrent densities at negative potentials, with an onset potential around 0.3 V vs RHE. P-type materials would give such a response and this also indicates the production of hydrogen in the working electrode. However, I am unsure if the valence and conduction band positions allow it. Any method to confirm it besides Mott-Schotky or measuring the amount of hydrogen produced?
It means that your working electrode is a cathode and you are producing H2 (so, in your counter electrode O2 is being produced), and as you say, it is what you can expect is you are using p-type semiconductors
In case of water splitting, if you have negative potential with negative current you follow the hydrogen evolution reaction(HER) in which yours material or working electrode act as a cathode. If you have positive potential with positive current, you follow the oxygen evolution reaction (OER) and your working electrode act as a cathode.
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