End-to-End Modeling of Cyclic Voltammograms for Hydrogen Evolution Reaction from First Principles

Hydrogen evolution reaction (HER) is a critical reaction for hydrogen production. In analytical electrochemistry, cyclic voltammetry (CV) has been the practical technique to provide current-potential characteristics based on the Butler-Volmer equation. However, the linkage between the analytical chemistry and first-principles modeling is missing. Herein, we develop an end-to-end electrochemical CV model for HER that is only a function of hydrogen adsorption free energy. At equilibrium conditions, this model reproduces the volcano trend proposed by Nørskov, and significantly improves the discrepancies on exchange currents with experiments owing to a metal-dependent rate-constant. Further, we show that for low-overpotentials, the CV model reproduces experimental cyclic voltammograms with high fidelity. The success of the CV model is justified by the universality of the transfer coefficient and the energy barrier at the equilibrium limit. Our framework for developing the electrochemical model based on fundamental electrochemistry principles and computational quantum-mechanical approaches can be applied to any electrochemical reactions.