Single-Atom Fe Catalyst Outperforms Its Homogeneous Counterpart for Activating Peroxymonosulfate to Achieve Effective Degradation of Organic Contaminants

Recently, reactive iron species (RFeS) have shown great potential for the selective degradation of emerging organic contaminants (EOCs). However, the rapid generation of RFeS for the selective and efficient degradation of EOCs over a wide pH range is still challenging. Herein, we constructed FeN4 structures on a carbon nanotube (CNT) to obtain single-atom catalysts (Fe-SA-N-CNT) to generate RFeS in the presence of peroxymonosulfate (PMS). The obtained Fe-SA-N-CNT/PMS system exhibited outstanding and selective reactivity for oxidizing EOCs over a wide pH range (3.0-9.0). Several lines of evidences suggested that RFeS existing as an FeN4=O intermediate was the predominant oxidant, while SO4 center dot- and HO center dot were the secondary oxidants. Density functional theory calculation results revealed that a CNT played a key role in optimizing the distribution of bonding and antibonding states in the Fe 3d orbital, resulting in the outstanding ability of Fe-SA-N-CNT for PMS chemical adsorption and activation. Moreover, CNT could significantly enhance the reactivity of the FeN4=O intermediate by increasing the overlap of electrons of the Fe 3d orbital, O 2p orbital, and bisphenol A near the Fermi level. The results of this study can advance the understanding of RFeS generation in a heterogeneous system over a wide pH range and the application of RFeS in real practice.

Automated summary

In this study, FeN4 structures were constructed on carbon nanotubes to obtain single-atom catalysts, which successfully generated reactive iron species (RFeS) for the selective degradation of emerging organic contaminants (EOCs) over a wide pH range. The results revealed the mechanism of RFeS generation and the important role of carbon nanotubes in enhancing the reactivity of FeN4=O intermediates.