Coupling oxygen reduction and water oxidation for concerted H₂O₂ production: a sustainable paired-electrosynthesis strategy

Abstract

Hydrogen peroxide (H₂O₂) is an important green oxidant for clean energy and environmental technologies, yet its dominant anthraquinone process relies on complex, fossil-based and energy-intensive operations that are incompatible with distributed, low-carbon production. Electrocatalytic synthesis via the two-electron oxygen reduction (2e^- ORR) and water oxidation reactions (2e^- WOR), powered by renewable electricity, offers a sustainable route to on-site H₂O₂ generation from O₂ and/or H₂O. However, conventional electrolyzer setups typically employ only one of these half-reactions for H₂O₂ production, leading to substantial energy losses and limited overall Faradaic efficiency (FE). In this context, coupling 2e^- ORR and 2e^- WOR to produce H₂O₂ simultaneously at the cathode and the anode has emerged as a promising paired-electrosynthesis strategy. Dual-electrode concerted H₂O₂ production could surpass the efficiency ceiling of single-electrode systems by avoiding sacrificial counter reactions, lowering the cell voltage and theoretically pushing the overall FE towards 200%. However, the practical realization is still hampered by 2e^- ORR and 2e^- WOR kinetics mismatch, competitive side reactions, H₂O₂ crossover and degradation, and insufficient catalyst and electrode durability under oxidative operation. This review summarizes recent progress in the paired H₂O₂ electrosynthesis via 2e^- ORR//WOR, covering the thermodynamic and kinetic fundamentals, coupling modes and cell architectures, performance metrics and benchmarking protocols. Finally, we highlight the challenges and opportunities in low-carbon paired-electrosynthesis H₂O₂ manufacturing.

Keywords

Hydrogen peroxide / paired-electrosynthesis / oxygen reduction / water oxidation / electrocatalysis

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