Toward data‐ and mechanistic‐driven volcano plots in electrocatalysis

Abstract

AbstractThe present application note summarizes an advanced methodology that allows for deriving potential‐dependent volcano curves for energy storage and conversion processes. The conventional approach relies on the combination of density functional theory calculations and scaling relations for a single mechanistic pathway as well as a discussion of electrocatalytic activity by means of the potential‐determining step, determined at the equilibrium potential of the reaction. Herein, it is illustrated how several reaction mechanisms can be factored into the volcano curve and how the rate‐determining step based on the descriptor Gmax(U) can be derived by a rigorous thermodynamic analysis of adsorption free energies fed by a data‐inspired methodology.