Simulating Linear Sweep Voltammetry from First-Principles: Application to Electrochemical Oxidation of Water on Pt(111) and Pt3Ni(111)

Cyclic voltammetry is a fundamental experimental method for characterizing adsorbates on electrochemical surfaces. We present a model for the electrochemical solid–liquid interface, and we simulate the linear sweep voltammogram of the electrochemical oxidation of H2O on Pt(111) and Pt3Ni(111), based on kinetic and thermodynamic parameters computed by Density Functional Theory (DFT) and the dynamics of the system solved through Monte Carlo-based methods. The model predicts onset of OH and O formation in good agreement with voltammetric and ex situ XPS experiments.