Compensation effects between the apparent activation energy and pre-exponential factor in simple models of electrocatalytic hydrogen evolution

Faraday Discussions, vol. 267, pp. 100–117

Abstract

) relations that mimic intrinsic entropy-enthalpy compensation. Our results demonstrate that compensation effects in electrocatalysis can arise purely from kinetic coupling and site heterogeneity rather than from fundamental thermodynamic scaling, underscoring the need for caution when interpreting temperature-dependent kinetic data. We propose that meaningful mechanistic insight requires measurements on well-defined single-crystal electrodes within potential regions where Tafel slopes remain constant.

Authors 6

1. Jan Fingerhut Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

2. Rifael Z. Snitkoff‐Sol Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

3. M. Albers Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands

4. Rafaël E. Vos

   Eindhoven University of Technology

   Affiliation as printed

   Department of Chemical Engineering and Chemistry, Technical University of Eindhoven, 5600 MB, Eindhoven, The Netherlands

5. Onno van der Heijden

   Eindhoven University of Technology

   Affiliation as printed

   Department of Chemical Engineering and Chemistry, Technical University of Eindhoven, 5600 MB, Eindhoven, The Netherlands

6. Marc T. M. Koper Aachen

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands