Modelling and development of photoelectrochemical reactor for H2 production

Photoelectrolysis of aqueous solutions, using one or more semiconducting electrodes in a photoelectrochemical reactor, is a potentially attractive process for hydrogen production because of its prospectively high energy efficiency, simplicity and potentially low cost. The design requirements and preliminary results of modelling a photoelectrochemical (PEC) reactor are described. Potential and current density distributions, due to ohmic potential losses in thin (non-photo) anodes on poorly conducting fluoride-doped tin oxide coated glass substrates, were modelled. The predicted current densities decayed rapidly from the terminals at the edges, towards the centre of a 0.1 × 0.1 m2 anode, so limiting scale-up with such substrates. Spatial distributions of dissolved oxygen concentrations were also modelled, aiming to define operating conditions that would avoid forming bubbles, which reflect light specularly decreasing photon absorption efficiencies of photoelectrodes. The implications for the future optimization of the reactor are discussed.

► A voltage balance has been derived for a photoelectrochemical cell.
► Design requirements for a practical photoelectrochemical reactor have been defined.
► Mathematical modelling of the design was used to analyse and optimise operation.
► Bubble formation cannot be prevented by manipulating normal reactor operation.
► On low conductivity transparent substrates ohmic potential losses may cause significant fractions of photoanode area to become inactive to oxygen evolution.