Hydrogen Peroxide Electrosynthesis via Selective Oxygen Reduction Reactions Through Interfacial Reaction Microenvironment Engineering

Abstract The electrochemical two‐electron oxygen reduction reaction (2e − ORR) offers a compelling alternative for decentralized and on‐site H 2 O 2 production compared to the conventional anthraquinone process. To advance this electrosynthesis system, there is growing interest in optimizing the interfacial reaction microenvironment to boost electrocatalytic performance. This review consolidates recent advancements in reaction microenvironment engineering for the selective electrocatalytic conversion of O 2 to H 2 O 2 . Starting with fundamental insights into interfacial electrocatalytic mechanisms, an overview of various strategies for constructing the favorable local reaction environment, including adjusting electrode wettability, enhancing mesoscale mass transfer, elevating local pH, incorporating electrolyte additives, and employing pulsed electrocatalysis techniques is provided. Alongside these regulation strategies, the corresponding analyses and technical remarks are also presented. Finally, a summary and outlook on critical challenges, suggesting future research directions to inspire microenvironment engineering and accelerate the practical application of H 2 O 2 electrosynthesis is delivered.