Pulsed electrocatalysis enables the stabilization and activation of carbon-based catalysts towards H2O2 production

Hydrogen peroxide (H2O2) electrosynthesis through oxygen reduction reaction (ORR) provides an environmentally-friendly alternative to the traditional anthraquinone process. While most studies focus on the original construction of active sites in electrocatalysts, it is also necessary to optimize the microenvironment in the dynamic catalytic process. Here, we proposed a pulse-induced strategy to achieve the in-situ regulation of active sites and interface microenvironment in ORR process, enabling a 210 % leap in H2O2 yield and a 74 % increase in Faraday efficiency. A series of operando measurements revealed the stabilization effect on the catalyst morphology and oxygen-containing functional groups distribution, and the activation effect on the basal defect sites to strengthen the interaction with *O2 and *OOH. Density functional theory calculations were further employed to reveal a unique ORR reaction pathway which decoupled the proton transfer and electron transfer process in pulsed electrocatalysis, providing new insights into the origin of ORR activity and selectivity.