Tuning Two-Electron Oxygen-Reduction Pathways for H₂ O₂ Electrosynthesis via Engineering Atomically Dispersed Single...

The hydrogen peroxide (H₂ O₂ ) generation via the electrochemical oxygen reduction reaction (ORR) under ambient conditions is emerging as an alternative and green strategy to the traditional energy-intensive anthraquinone process and unsafe direct synthesis using H₂ and O₂ . It enables on-site and decentralized H₂ O₂ production using air and renewable electricity for various applications. Currently, atomically dispersed single metal site catalysts have emerged as the most promising platinum group metal (PGM)-free electrocatalysts for the ORR. Further tuning their central metal sites, coordination environments, and local structures can be highly active and selective for H₂ O₂ production via the 2e^- ORR. Herein, recent methodologies and achievements on developing single metal site catalysts for selective O₂ to H₂ O₂ reduction are summarized. Combined with theoretical computation and advanced characterization, a structure-property correlation to guide rational catalyst design with a favorable 2e^- ORR process is aimed to provide. Due to the oxidative nature of H₂ O₂ and the derived free radicals, catalyst stability and effective solutions to improve catalyst tolerance to H₂ O₂ are emphasized. Transferring intrinsic catalyst properties to electrode performance for viable applications always remains a grand challenge. The key performance metrics and knowledge during the electrolyzer development are, therefore, highlighted.