New insights into electrocatalytic ozone generation via splitting of water over PbO₂ electrode: A DFT study

The viable mechanisms for O₃ generation via the electrocatalytic splitting of H₂O over β-PbO₂ catalyst were identified through Density Functional Theory calculations. H₂O adsorbed onto the surface was oxidized to form OH then O; the latter reacted with a surface bridging O to form O₂ which in turn reacted with another surface O to form O₃. The final step of the mechanisms occurs via an Eley-Rideal style interaction where surface O₂ desorbs and then attacks the surface bridging oxygen, forming O₃. A different reaction pathway via an O₃H intermediate was found less favoured both thermodynamically and kinetically.