Quantifying surface diffusion kinetics of Faraday-adsorbed species by classic electrochemical techniques

Surface diffusion of Faraday adsorbed species plays a crucial role in electrocatalysis. Various surface-sensitive techniques, including field ion microscopy, scanning tunneling microscopy, and laser-induced thermal desorption, have provided opportunities to evaluate surface diffusion kinetics. However, the challenge remains in excluding the interference of applied external physical fields on measurements of surface mobility. Classic electrochemical methods offer a compelling approach to studying surface diffusion due to their simplicity and freedom from external field interference. In this review, we discuss the principles for the quantification of surface diffusion kinetics by classical electrochemical techniques, such as cyclic voltammetry and chronoamperometry, in operando electrochemical reaction environment. We also explore recent advances in nano -interface engineering and nanoelectrodes to showcase how they were used to determine the surface diffusion kinetics.