Quantifying Confidence in DFT Predicted Surface Pourbaix Diagrams of Transition Metal Electrode-Electrolyte Interfaces

TL;DR

This study introduces an error-estimation approach using BEEF-vdW functional to quantify confidence in DFT-predicted surface Pourbaix diagrams for transition metals, improving reliability of surface phase predictions under electrochemical conditions.

Contribution

It develops a method to incorporate uncertainty quantification into DFT-based surface Pourbaix diagrams, enhancing the accuracy and confidence in predicting catalyst surface states.

Findings

Predicted surface phases agree with experimental cyclic voltammetry data.

Ru binds OH* strongest among studied metals.

Confidence metrics help rationalize surface phase predictions.

Abstract

Density Functional Theory (DFT) calculations have been widely used to predict the activity of catalysts based on the free energies of reaction intermediates. The incorporation of the state of the catalyst surface under the electrochemical operating conditions while constructing the free energy diagram is crucial, without which even trends in activity predictions could be imprecisely captured. Surface Pourbaix diagrams indicate the surface state as a function of the pH and the potential. In this work, we utilize error-estimation capabilities within the BEEF-vdW exchange correlation functional as an ensemble approach to propagate the uncertainty associated with the adsorption energetics in the construction of Pourbaix diagrams. Within this approach, surface-transition phase boundaries are no longer sharp and are therefore associated with a finite width. We determine the surface phase diagram for several transition metals under reaction conditions and electrode potentials relevant for the Oxygen Reduction Reaction (ORR). We observe that our surface phase predictions for most predominant species are in good agreement with cyclic voltammetry experiments and prior DFT studies. We use the OH$^*$ intermediate for comparing adsorption characteristics on Pt(111), Pt(100), Pd(111), Ir(111), Rh(111), and Ru(0001) since it has been shown to have a higher prediction efficiency relative to O$^*$, and find the trend Ru>Rh>Ir>Pt>Pd for (111) metal facets, where Ru binds OH$^*$ the strongest. We robustly predict the likely surface phase as a function of reaction conditions by associating c-values to quantifying the confidence in predictions within the Pourbaix diagram. We define a confidence quantifying metric using which certain experimentally observed surface phases and peak assignments can be better rationalized.