Tailoring *OOH Adsorption Microenvironment for Efficient Hydrogen Peroxide Electrosynthesis

Electrosynthesis of H 2 O 2 through the two-electron oxygen reduction reaction (2e – ORR) is limited by the trade-off between catalytic activity and H 2 O 2 selectivity. We overcome this by constructing a CeO 2 -anchored nitrogen–oxygen codoped carbon nanotube hybrid (CeO 2 /NOCNT) to tailor the *OOH adsorption microenvironment. Operando infrared spectroscopy captures the strongest *OOH absorption and equilibrated *OOH/*HOOH coadsorption on CeO 2 /NOCNT, signaling dominant 2e – kinetics. Density functional theory uncovers interfacial electron transfer from CeO 2 to neighboring carbon atoms, shifting *OOH binding energy toward the volcanic apex and reducing the kinetic barrier. The CeO 2 /NOCNT catalyst achieves a H 2 O 2 production rate of 6.69 mol g cat –1 h –1 with 82.9% Faradaic efficiency (FE) and retains performance over 110 h in a flow reactor. Integrating cathodic 2e – ORR with anodic methanol oxidation yields formate (95.6% FE) and H 2 O 2 (84.2% FE) while reducing cell voltage. This interfacial engineering approach provides a scalable route to selective H 2 O 2 generation and coupled production of chemical feedstocks.