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 V_SCE 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 V_SCE. 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.