The Pre-exponential Factor in Electrochemistry

Angew Chem Int Ed Engl. 2018 Jul 2;57(27):7948-7956. doi: 10.1002/anie.201800130. Epub 2018 May 14.

Abstract

Like many branches of science, not to mention culture in general, electrochemistry has a number of recurring topics: Areas of research that are popular for a certain time, then fade away as their possibilities seem to have been exhausted, only to return decades later as progress in experimental or theoretical techniques offer new possibilities for their investigation. A prime example are fuel cells, which have undergone five such cycles, but here we discuss a general concept of kinetics-the pre-exponential factor of a rate constant-which has undergone two such cycles. The first cycle was in the 1950-1980s, when the methods of electrochemical kinetics were developed, and the interpretation was based on transition-state theory. The second was triggered by the re-discovery of Kramers theory for reactions in condensed phases. This Minireview will show that the time has come for a third cycle based on recent progress in electrocatalysis.

Keywords: Kramers theory; electrocatalysis; electron transfer; hydrogen evolution; pre-exponential factor.

Publication types

  • Review
  • Research Support, Non-U.S. Gov't