A first-principles study of molecular oxygen dissociation at an electrode surface: A comparison of potential variation and coadsorption effects

Influences of coadsorbed sodium and water, aqueous solvent, and electrode potential on the kinetics of O₂ dissociation over Pt(111) are systematically investigated using density functional theory models of vacuum and electrochemical interfaces. Na coadsorption alters the electronic states of Pt to stabilize the reactant (O₂*), transition, and product (2O*) states by facilitating electron donation to oxygen, causing a more exothermic reaction energy (-0.84 eV for Na and O₂, -0.81 eV for isolated O₂) and a decrease in dissociation barrier (0.39 eV for Na and O₂, 0.57 eV for isolated O₂). Solvation decreases the reaction energy (-0.67 eV) due to enhanced hydrogen bond stabilization of O ₂* compared to 2O*. The influence of Na is less pronounced at the solvated interface (barrier decreases by only 0.11 eV) because H₂O screens Na charge-donation. In the electrochemical model system, the dissociation energy becomes more exothermic and the barrier decreases toward more positive potentials. Potential-dependent behavior results from changes in interfacial dipole moment and polarizability between O ₂*, the dissociation transition state, and 2O*; each are influenced by changes in adsorption and hydrogen bonding. Coadsorption of Na in the solvated system dampens the dipole moment change between O ₂* and 2O* and significantly increases the polarizability at the dissociation transition state and for 2O*; the combination causes little change in the reaction energy but reduces the activation barrier by 0.08 eV at 0 V versus NHE. The potential-dependent behavior contrasts that determined at a constant surface charge or from an applied electric field, illustrating the importance of considering the electrochemical potential at the fully-solvated interface in determining reaction energetics, even for non-redox reactions.