Physical and photoelectrochemical studies for hydrogen photo-evolution over the spinel ZnCr2O4

The present work deals with the photoelectrochemical hydrogen production over the spinel ZnCr2O4. The photoactivity is dependent on the synthesis conditions and the oxide has been prepared by nitrate way in order to produce homogeneous powder with large active surface. The transport properties indicate p-type conductivity with activation energy of 0.21 eV. A corrosion potential of 0.404 VSCE and an exchange current density of 50 μA cm−2 have been determined from the semi logarithm plot. The photocurrent onset potential, assimilated to the flat band potential, was found to be −0.39 VSCE. ZnCr2O4/S2O32− is a self driven system where absorption of light promotes electrons into the conduction band with a potential (−1 V) sufficient to reduce water into hydrogen. The activity shows a tendency toward saturation whose deceleration is the result of the competitive reductions of end products namely S2O62− and S2O42− with water. A comparative study with CuCr2O4 is reported.