Gas-phase errors in computational electrocatalysis: a review

Abstract

Currently, computational models based on density functional theory (DFT) are intensively used for the analysis of electrocatalytic reactions and the design of enhanced catalysts. As the accuracy of these models is subjected to the quality of the input data, knowing the intrinsic limitations of DFT is crucial to improve computational predictions. A common pitfall of DFT is the estimation of the total energies of molecules, particularly those containing double and triple bonds. In this review, we show how gas-phase errors permeate thermodynamic and kinetic models of customary use in electrocatalysis, potentially compromising their predictiveness. First, we illustrate how these errors can be identified and provide a list of corrections for common molecules and functional groups. Subsequently, we explain how the errors spread from simple reaction energy calculations to adsorption energies, scaling relations, equilibrium potentials, overpotentials, and Sabatier-type activity plots. Finally, we list the remaining challenges toward an improved assessment of energetics at solid–gas–liquid interfaces.