Halogen-Driven Electronic Modulation of Single-Atom Fe Sites for Universal Non-Radical Catalysis.
Rui Lv1, Liying Wang1, Nanyue Xu1
1School of Environment and Geography, Qingdao University, Qingdao, China.
Advanced Materials (Deerfield Beach, Fla.)
|June 5, 2026
Summary
Engineered iodine-polarized Fe-N4 single-atom sites activate peroxymonosulfate (PMS) for ultrafast, non-radical phenol oxidation in real waters. This advanced oxidation process demonstrates high efficiency and matrix tolerance for water purification.
Area of Science:
- Environmental Chemistry
- Materials Science
- Catalysis
Background:
- Advanced oxidation processes (AOPs) are crucial for treating real water matrices.
- Developing selective and matrix-tolerant AOPs remains a significant challenge.
- Peroxymonosulfate (PMS) activation requires efficient catalysts for water purification.
Purpose of the Study:
- To engineer iodine-polarized Fe-N4 single-atom sites (Fe-NI-C) for peroxymonosulfate (PMS) activation.
- To investigate the mechanism of PMS activation for non-radical phenol oxidation.
- To evaluate the performance of Fe-NI-C/PMS in real water matrices under varying conditions.
Main Methods:
- Synthesis of iodine-polarized Fe-N4 single-atom sites in N-doped carbon (Fe-NI-C).
- Utilized electrochemical assays, quenching experiments, and electron paramagnetic resonance (EPR) spectroscopy.
- Employed spin-polarized density functional theory (DFT) calculations to elucidate the reaction mechanism.
Main Results:
- Fe-NI-C/PMS achieved complete phenol removal within 2 minutes with high total organic carbon abatement.
- The catalyst exhibited near-quantitative activity across a wide pH range (3-11) and in various water types (tap, river, seawater).
- Deciphered an electron-transfer-to-singlet-oxygen cascade (ETP → 1O2) as the primary oxidation pathway, suppressing radical formation.
Conclusions:
- Soft-ligand electronic polarization of Fe-N4 sites is a viable strategy for robust PMS activation.
- The Fe-NI-C/PMS system offers a promising, radical-free, and matrix-tolerant approach for advanced water purification.
- Demonstrated the programmability of single-atom catalysts for selective pollutant degradation.
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