ACS Catalysis· 2026Q1
Entropy–Enthalpy Compensation in Electrocatalytic Rates
- 6citations
- Q1SCImago
- 2026year
Short summary
A new model reveals that entropy-enthalpy compensation, driven by species adsorption/desorption, explains deviations from Butler-Volmer kinetics in electrocatalytic rates, offering distinct kinetic fingerprints for different metal catalysts.
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Key points
- A model for HER kinetics demonstrates how entropy-enthalpy compensation affects Arrhenius parameters with changing potential.
- Deviations from Butler-Volmer kinetics are rationalized by changes in the entropy-dependent prefactor, not solely solvent dynamics.
- Distinct kinetic fingerprints emerge for different metal catalyst groups, correlating with experimental data.
- Species adsorption/desorption is identified as the primary driver for measured changes in the Arrhenius prefactor.
AI-generated from the title and abstract; the full text is not read.
Abstract
Abstract Measuring the temperature dependence of electrocatalytic reaction rates is a powerful, yet underexplored, way of investigating the underlying kinetics. In this study, we develop the understanding behind such kinetic measurements. Through a very simple model of the surface kinetics for the hydrogen evolution reaction (HER), we explore how extracted Arrhenius parameters depend on potential and rationalize a series of entropy-enthalpy correlations in experimental HER rates. We find that the entropy-dependent prefactor can change alongside the apparent activation energy, thus signaling deviations from the established Butler-Volmer kinetics that have so far mostly been attributed to potential-driven solvent dynamics. Distinct kinetic fingerprints emerge for different groups of metal catalysts that are in qualitative agreement with recent experiments. We elucidate these characteristic fingerprints in terms of shifting kinetic regimes and generalize our findings to other electrocatalytic reactions and setups. Our analysis overall suggests the entropy loss/gain due to species’ adsorption/desorption as the main driver behind measured changes in the Arrhenius prefactor.
The authors' abstract, as published at the source. ACS Catalysis, 2026 · DOI ↗
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Field: Renewable Energy, Sustainability and the Environment
Renewable Energy, Sustainability and the EnvironmentEnergy