Theoretical Analysis of Electrochemical Formation and Phase Transition of Oxygenated Adsorbates on Pt(111)

The electrochemical oxygenation processes of Pt(111) surface are investigated by combining density functional theory (DFT) calculations and Monto Carlo (MC) simulations. DFT calculations are performed to construct force-field parameters for computing the energy of (√3 × √3)R30°-structured OH*-H2O* hydrogen-bonding networks (differently dissociated water bilayer) on the Pt(111) surface, with which MC simulations are conducted to probe the reversible H2O* ↔ OH* conversion in OH*-H2O* networks. The simulated isotherm (relation between electrode potential and OH* coverage) agrees well with that predicted by the experimental cyclic voltammetry (CV) in the potential region of 0.55-0.85 V (vs RHE). It is suggested that the butterfly shape of CV in this region is due to different variation trends of Pt-H2O* distance in low and high OH* coverages. DFT calculation results indicate that the oxidative voltammetry in the potential region from 0.85 V to ca. 1.07 V is associated with the dissociation of OH* to O*, which yields surface structures consisting of OH*-H2O* networks and (√3 × √3)-structured O* clusters. The high stability of the half-dissociated water bilayer (OH*-H2O* hydrogen-bonding network with equal OH* and H2O* coverages) formed in the butterfly region makes OH* dissociation initially very difficult in energetics, but become facile once starts due to the destabilization of OH* by the formed O* nearby. This explains the experimentally observed nucleation and growth behavior of O* phase formation and the high asymmetry of oxidation-reduction voltammetry in this potential region.