Toward data- and mechanistic-driven volcano plots in electrocatalysis

Abstract

The 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 G_max(U) can be derived by a rigorous thermodynamic analysis of adsorption free energies fed by a data-inspired methodology.