Electrochemical Modification of catalytic activity driven by Pulsed Electrolysis

Abstract

Pulsed electrolysis has emerged as a promising strategy for overcoming the limitations of conventional potentiostatic electrocatalysis and regulating dynamic electrochemical reactions. By dynamically varying the applied potential, pulsed operation introduces additional degrees of freedom for precisely manipulating reaction pathways, catalyst states, and interfacial environments. However, the mechanistic basis of pulsed electrolysis remains insufficiently understood, and the selection of pulse parameters is still largely guided by empirical optimization, with limited mechanistic correlations to the underlying electrochemical processes. Here, we establish a classification framework based on electrochemical modification of catalytic activity, which categorizes the regulatory mechanisms of pulsed electrolysis into two fundamental pathways: Faradaic and non-Faradaic electrochemical modification of catalytic activity. Non-Faradaic modification of catalytic activity does not rely on direct electron transfer but instead regulates the adsorption and desorption of reaction intermediates, catalyst surface states, and interfacial microenvironments, thereby altering surface coverage, catalyst structure, and local reaction conditions. In contrast, Faradaic modification regulates the extent of sequential electron-transfer steps at different potentials, selectively promoting or suppressing specific reaction steps and thereby redirecting complex reaction networks. We systematically review recent advances in two electrochemical modifications of catalytic activity pathways, highlighting how pulsed operation can regulate reaction intermediates, catalyst states, and interfacial environments through distinct mechanisms, and has been applied across diverse electrocatalytic systems, including resource molecular conversion and organic electrosynthesis. Finally, we discuss key challenges and opportunities in this field, highlighting that establishing mechanistic correlations among pulse parameters, electrochemical processes, and reaction performance is expected to advance pulsed electrolysis from empirical parameter screening toward mechanism-guided rational design, enabling precise and predictable control over dynamic electrochemical reactions.