Simple Approach for Reconciling Cyclic Voltammetry with Hydrogen Adsorption Energy for Hydrogen Evolution Exchange Current
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Updated: Aug 1, 2025

Electrochemical Roughening of Thin-Film Platinum Macro and Microelectrodes
Published on: June 30, 2019
Timothy T Yang1, Wissam A Saidi1
1Department of Materials Science and Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
Abstract:
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.
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