ArticleFaraday discussions2026
Compensation effects between the apparent activation energy and pre-exponential factor in simple models of electrocatalytic hydrogen evolution.
Article in Faraday discussions, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 2 papers.
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Who cites it
2 citing papers in PubMed.
- The Interplay between Interfacial Solvation and Surface Kinetics Tunes the Selectivity between Hydrogen Evolution and Zinc Electrodeposition.Journal of the American Chemical Society · 2026Article
- The role of interfacial excess charge in the reversibility of proton and hydroxide solvation in electrocatalysis and bipolar membranes.Proceedings of the National Academy of Sciences of the United States of America · 2026Article
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Authors and funding
6 authors.
Funding
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Abstract
Understanding how activation energies and entropies vary with electrode potential is central to interpreting electrocatalytic kinetics, yet temperature-dependent analyses often yield apparent "compensation effects" whose physical origin remains debated. Here, we model the hydrogen evolution reaction (HER) through both Volmer-Heyrovsky and Volmer-Tafel mechanisms to determine under which conditions compensation effects emerge-even when the entropic contribution to the activation barriers of the individual reaction steps is, by assumption, potential-independent. By simulating steady state currents across realistic potential and temperature ranges and extracting apparent Arrhenius parameters, we identify two general origins of compensation-like behavior: (i) shifts in the effective rate law arising from changes in coverage or in the rate-determining step, and (ii) the presence of multiple active sites with different equilibrium potentials of reaction steps. Both phenomena generate non-constant Tafel slopes and curvature in Arrhenius plots, producing Constable-plot (log
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