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Phenolics-Reengineered Electron Flow in the Electro-Fenton Process for Energy-Conserving Decontamination.

Created on 19 Jun 2026

Authors

Zhipeng Luo, Yue Cheng, Fangkun Lin, Junjie Li, Yilei Fang, Diyong Tang, Xin Yu, Gong Zhang, Huabin Zeng

Published in

Environmental science & technology. Jun 19, 2026. Epub Jun 19, 2026.

Abstract

Electro-Fenton (EF) process suffers from energy and electron inefficiencies arising from residual H2O2 or excess FeII due to the stoichiometric mismatch between the two-electron oxygen reduction reaction (2e- ORR) and ferric ion reduction (FRR) at a shared cathode. Here, we reengineered electron flow in the EF system to achieve on-demand FeII supply synchronized with H2O2 generation. A specific cathode spatially decouples 2e- ORR from FRR, while phenolic coordination modulates the spin state of FeIII to accelerate ferric-peroxide interactions. Quantum-chemical-calculation-assisted in situ spectroscopy reveals a ligand-to-metal charge-transfer chromogenic pathway involving a transient, high-spin phenolics-FeIII-OOH intermediate, which undergoes homolytic Fe-O bond cleavage to yield FeII and HO2·/O2·-. This establishes a directional flow of cathodic electron toward H2O2 and subsequently to FeIII (H2O2 as shuttle), sustaining autonomous ·OH generation until H2O2 is exhausted. The reengineered EF system thereby achieves a 17-fold enhancement in ·OH production at mg-level iron dosage, concomitant with 53.4% reduction in energy consumption relative to conventional EF systems. Finally, pairing this process with anodic hydroxylation of aromatics extends its applicability to the cost-effective treatment of wastewater containing diverse aromatic pollutants. Overall, this work provides a framework for integrating advanced 2e- ORR cathodes into energy-efficient, redox-neutral systems for scalable wastewater decontamination.

PMID:
42318614
Bibliographic data and abstract were imported from PubMed on 19 Jun 2026.

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