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

Abstract

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^·- and HO^· 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.