0.1 × 0.1 m2 tin-doped hematite photo-anodes were fabricated on titanium substrates by spray pyrolysis and deployed in a photo-electrochemical reactor for photo-assisted splitting of water into hydrogen and oxygen. Hitherto, photo-electrochemical research focussed largely on the fabrication, properties and behaviour of photo-electrodes, whereas both experimental and modelling results reported here address reactor scale-up issues of minimising inhomogeneities in spatial distributions of potentials, current densities and the resultant hydrogen evolution rates. Such information is essential for optimising the design and photon energy-to-hydrogen conversion efficiencies of photo-electrochemical reactors to progress their industrial deployment. The 2D and 3D reactor models presented here are coupled with a modified micro-kinetic model of oxygen evolution on hematite thin films both in the dark and when illuminated. For the first time, such a model is applied to a scaled-up photo-electrochemical reactor and validated against experimental data.
