Revealing the In Situ Dynamic Regulation of the Interfacial Microenvironment Induced by Pulsed Electrocatalysis in the Oxygen Reduction Reaction

Pulsed electrocatalysis has emerged as a promising technologytoeffectively improve reaction kinetics and tailor product selectivity.While most research focuses on the evolution of electrocatalyst activesites, the dynamic response of the interfacial microenvironment duringpulsed electrocatalysis still remains unknown. Here, we reveal the in situ dynamic regulation of the interfacial microenvironmentinduced by pulsed electrocatalysis in the oxygen reduction reactionprocess, from the interface reactant delivery to intermediate formationdynamics. At the diffusion layer, the coupling of pulsed electrocatalysisand hierarchical pore structure was proven to break the limitationof proton transfer, resulting in favorable H2O2 production kinetics. At the electrode/electrolyte interface, thepulsed electric field would stimulate the cation effect to activateC-*OOH and reduced the reaction energy barrier, giving riseto more favorable *OOH formation thermodynamics. This work providesnew insights into exploring in situ regulation ofthe interfacial microenvironment, which is expected to be extendedto different electrochemical processes.

Automated summary

Pulsed electrocatalysis is a promising technology that can effectively improve reaction kinetics and tailor product selectivity. This study reveals the in situ dynamic regulation of the interfacial microenvironment induced by pulsed electrocatalysis in the oxygen reduction reaction process. The coupling of pulsed electrocatalysis and hierarchical pore structure breaks the limitation of proton transfer, resulting in favorable H2O2 production kinetics. The pulsed electric field stimulates the cation effect to activate C-*OOH and reduces the reaction energy barrier, leading to more favorable *OOH formation thermodynamics.