Advances in the In Situ Synthesis of Hydrogen Peroxide Using Hydrogen Substitutes

ABSTRACT Hydrogen peroxide (H 2 O 2 ), as a prevalently green oxidant in the chemical industry, confronts many bottlenecks in the conventional anthraquinone‐based methods, such as organic solvents dependency, energy‐intensive complex operations and inherent safety risks from centralized production. The direct synthesis route from H 2 coupled with O 2 presents a promising alternative, but remains constrained by the safety requirement and the reaction control demand. This article systematically reviews breakthroughs in non‐hydrogen catalytic systems for in situ synthesis of H 2 O 2 . Through elucidating the mechanism of two‐electron oxygen reduction pathways, renewable hydrogen substitutes with enhanced safety including CO, HCOOH, glucose and alcohols have been highlighted. Their efficient conversion of O 2 to H 2 O 2 and the integration with sustainable processes such as selective oxidation are also discussed. It is expected to provide fundamental insights into the synergistic mechanism in heterogeneous catalysis and offer a new viewpoint for developing a decentralized H 2 O 2 synthesis system for practical applications, moving toward a greener and more economical H 2 O 2 production approach.