Understanding the influence of the electrochemical double-layer on heterogeneous electrochemical reactions

A detailed understanding of the electrical double layer is key to the optimization of heterogeneous electrochemical reactions. In this work, we provide a brief summary of key experimental and computational studies of three key aspects of the double layer: Firstly, potential-dependent structure of the solvent; secondly, reaction-induced concentration gradients; and finally, the potential-dependent behavior of electrolyte cations and their effect on double layer structure, reaction activity, and selectivity. Studies of the double layer in polymer ion exchange membrane devices are also assessed. Finally, we discuss the importance and implications of the previous literature, and provide recommendations for future topics of study and methodological improvements toward a more complete understanding of the effect of various aspects of the electrical double layer on heterogeneous electrochemical reactions.