Fe-based single-atom catalysis for oxidizing contaminants of emerging concern by activating peroxides

Zhe Zhou; Mengqiao Li; Chunguang Kuai; Yuxin Zhang; Virginia F Smith; Feng Lin; Ashlee Aiello; David P Durkin; Hanning Chen; Danmeng Shuai

doi:10.1016/j.jhazmat.2021.126294

Fe-based single-atom catalysis for oxidizing contaminants of emerging concern by activating peroxides

J Hazard Mater. 2021 Sep 15:418:126294. doi: 10.1016/j.jhazmat.2021.126294. Epub 2021 Jun 2.

Authors

Affiliations

¹ Department of Civil and Environmental Engineering, The George Washington University, Washington, DC 20052, USA.
² Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA.
³ Department of Chemistry, United States Naval Academy, Annapolis, MD 21402, USA.
⁴ Department of Chemistry, United States Naval Academy, Annapolis, MD 21402, USA. Electronic address: durkin@usna.edu.
⁵ Department of Chemistry, American University, Washington, DC 20016, USA. Electronic address: hchen@american.edu.
⁶ Department of Civil and Environmental Engineering, The George Washington University, Washington, DC 20052, USA. Electronic address: danmengshuai@gwu.edu.

PMID: 34102366
DOI: 10.1016/j.jhazmat.2021.126294

Abstract

We prepared a single-atom Fe catalyst supported on an oxygen-doped, nitrogen-rich carbon support (SAFe-OCN) for degrading a broad spectrum of contaminants of emerging concern (CECs) by activating peroxides such as peroxymonosulfate (PMS). In the SAFe-OCN/PMS system, most selected CECs were amenable to degradation and high-valent Fe species were present for oxidation. Moreover, SAFe-OCN showed excellent performance for contaminant degradation in complex water matrices and high stability in oxidation. Specifically, SAFe-OCN, with a catalytic center of Fe coordinated with both nitrogen and oxygen (FeN_xO_4-x), showed 5.13-times increased phenol degradation kinetics upon activating PMS compared to the catalyst where Fe was only coordinated with nitrogen (FeN₄). Molecular simulations suggested that FeN_xO_4-x, compared to FeN₄, was an excellent multiple-electron donor and it could potential-readily form high-valent Fe species upon oxidation. In summary, the single-atom Fe catalyst enables efficient, robust, and sustainable water and wastewater treatment, and molecular simulations highlight that the electronic nature of Fe could play a key role in determining the activity of the single-atom catalyst.

Keywords: Contaminants of emerging concern; Electronic structure; High-valent Fe species; Peroxymonosulfate; Single-atom catalysis.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Carbon
Catalysis
Iron*
Oxidation-Reduction
Peroxides*

Substances

Peroxides
Carbon
Iron