Tailoring *OOH Adsorption Microenvironment for Efficient Hydrogen Peroxide Electrosynthesis

Electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e– ORR) is limited by the trade-off between catalytic activity and H2O2 selectivity. We overcome this by constructing a CeO2-anchored nitrogen–oxygen codoped carbon nanotube hybrid (CeO2/NOCNT) to tailor the *OOH adsorption microenvironment. Operando infrared spectroscopy captures the strongest *OOH absorption and equilibrated *OOH/*HOOH coadsorption on CeO2/NOCNT, signaling dominant 2e– kinetics. Density functional theory uncovers interfacial electron transfer from CeO2 to neighboring carbon atoms, shifting *OOH binding energy toward the volcanic apex and reducing the kinetic barrier. The CeO2/NOCNT catalyst achieves a H2O2 production rate of 6.69 mol gcat–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 H2O2 (84.2% FE) while reducing cell voltage. This interfacial engineering approach provides a scalable route to selective H2O2 generation and coupled production of chemical feedstocks.