Electrosynthesis of hydrogen peroxide (HO) via two-electron oxygen reduction reaction (2e ORR) is a promising alternative to the anthraquinone oxidation process. To improve the overall energy efficiency and economic viability of this catalytic process, one pathway is to develop advanced catalysts to decrease the overpotential at the cathode, and the other is to couple 2e ORR with certain anodic reactions to decrease the full cell voltage while producing valuable chemicals on both electrodes. The catalytic performance of a 2e ORR catalyst depends not only on the material itself but also on the environmental factors. Developing promising electrocatalysts with high 2e ORR selectivity and activity is a prerequisite for efficient HO electrosynthesis, while coupling appropriate anodic reactions with 2e ORR would further enhance the overall reaction efficiency. Considering this, here a comprehensive review is presented on the latest progress of the state-of-the-art catalysts of 2e ORR in different media, the microenvironmental modulation mechanisms beyond catalyst design, as well as electrocatalytic system coupling 2e ORR with various anodic oxidation reactions. This review also presents new insights regarding the existing challenges and opportunities within this rapidly advancing field, along with viewpoints on the future development of HO electrosynthesis and the construction of green energy roadmaps.
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