Robust Fe-N<sub>4</sub>-C<sub>6</sub>O<sub>2</sub> single atom sites for efficient PMS activation and enhanced Fe<sup>IV</sup> = O reactivity.
basic_science · Level V
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- Record sourced from PubMed, PMID 40064929.
- Also identified by DOI 10.1038/s41467-025-57643-7 and PMC identifier 11894199.
- Licence recorded as CC BY-NC-ND.
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Abstract
The microenvironment regulation of Fe-N<sub>4</sub> single atom catalysts (SACs) critically governs peroxymonosulfate (PMS) activation. Although conventional heteroatom substitution in primary coordination enhances activity, it disrupts Fe-N<sub>4</sub> symmetry and compromises stability. Herein, we propose oxygen doping in the secondary coordination shell to construct Fe-N<sub>4</sub>-C<sub>6</sub>O<sub>2</sub> SAC, which amplifies the localized electric field while preserving the pristine coordination symmetry, thus trading off its activity and stability. This approach suppresses Fe-N bond structural deformation (bond amplitude reduced from 0.875-3.175 Å to 0.925-2.975 Å) during PMS activation by lowering Fe center electron density to strengthen Fe-N bond, achieving extended catalytic durability (>240 h). Simultaneously, the weakened coordination field lowers the Fe=O σ* orbital energy, promoting electrophilic σ-attack of high-valent iron-oxo towards bisphenol A, and increasing its degradation rate by 41.6-fold. This work demonstrates secondary coordination engineering as a viable strategy to resolve the activity-stability trade-off in SAC design, offering promising perspectives for developing environmental catalysts.