Simple Approach for Reconciling Cyclic Voltammetry with Hydrogen Adsorption Energy for Hydrogen Evolution Exchange Current.

Cyclic voltammetry (CV) is a standard technique to analyze the current-potential characteristics of the hydrogen evolution reaction (HER). Herein, we develop a computational quantum-scaled CV model for the HER building on the Butler-Volmer relation for a one-step, one-charge transfer process. Owing to a universal and absolute rate constant verified by fitting to experimental cyclic voltammograms of elemental metals, we show that the model quantifies the exchange current─the main analytical descriptor for HER activity─solely using the hydrogen adsorption free energy obtained from density functional theory calculations. Furthermore, the model resolves controversies over analytical studies for HER kinetics.