Computational Insights into Water Oxidation Mechanisms on Rutile SnO2(110) that Form Ozone

Electrochemical ozone production (EOP) is intriguing as a sustainable route for gen- erating powerful chemical oxidants and disinfectants, but atomic scale details of EOP mechanisms on nickel and antimony doped SnO2 (NATO) electrocatalysts have been unclear. We used computational quantum chemistry to evaluate the thermodynamic feasibility of six-electron water oxidation steps based on 1) the adsorbate evolving mech- anism (AEM) and the lattice oxygen mechanism (LOM). This work provides atomic scale insights into the atomic scale nature of tin oxide-based electrocatalysts under highly oxidizing potentials and how and why dopants would influence EOP catalysis on NATO. Importantly, we identify that EOP adsorbates are significantly stabilized by explicit hydrogen bonding networks that arise from H* and OH* intermediates that form from dissociated water molecules, likely over the entire SnO2 surface. The disso- ciated water network is essential to developing computational catalysis model for EOP that is qualitatively consistent with experimental observations.