Abstract
In the analysis of electrocatalysis mechanisms and the design of catalysts, the effect of electrochemistry-induced surface coverage is a critical consideration that should not be overlooked. The surface Pourbaix diagram emerges as a fundamental tool in this context, providing essential insights into the surface coverage of adsorbates generated via electrochemical potential-driven water activation. A classic surface Pourbaix diagram considers the pH effects by correcting the free energy of H(+) ions by the concentration-dependent term: -k(B)T ln(10) × pH, which is independent of the reversible hydrogen electrode (RHE) scale. However, this is sometimes inconsistent with the experimentally observed potential-dependent surface coverage at an RHE scale, especially under high-pH conditions. Here, we derived the pH-dependent surface Pourbaix diagram at an RHE scale by considering the energetics computed by density functional theory with the Bayesian Error Estimation Functional with van der Waals corrections (BEEF-vdW), the electric field effects, the derived adsorption-induced dipole moment and polarizability, and the potential of zero-charge. Using Pt(111) as the typical example, we found that the surface coverage predicted by the proposed RHE-dependent surface Pourbaix diagram can significantly minimize the discrepancy between theory and experimental observations, especially under neutral-alkaline, moderate-potential conditions. This work provides a new methodology and establishes guidelines for the precise analysis of the surface coverage prior to the evaluation of the activity of an electrocatalyst.