Regulating electronic structure of Fe single-atom site by S/N dual-coordination for efficient Fenton-like catalysis

Huiwang Dai; Zhendong Zhao; Kun Wang; Fanxu Meng; Daohui Lin; Wenjun Zhou; Dingjiang Chen; Ming Zhang; Dongye Yang

doi:10.1016/j.jhazmat.2023.133399

Regulating electronic structure of Fe single-atom site by S/N dual-coordination for efficient Fenton-like catalysis

J Hazard Mater. 2024 Mar 5:465:133399. doi: 10.1016/j.jhazmat.2023.133399. Epub 2023 Dec 28.

Authors

Huiwang Dai¹, Zhendong Zhao², Kun Wang², Fanxu Meng², Daohui Lin¹, Wenjun Zhou³, Dingjiang Chen⁴, Ming Zhang⁵, Dongye Yang⁶

Affiliations

¹ Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China; Zhejiang Ecological Civilization Academy, Anji, Zhejiang 310058, China.
² Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China.
³ Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China; Zhejiang Ecological Civilization Academy, Anji, Zhejiang 310058, China. Electronic address: wenjunzhou@zju.edu.cn.
⁴ Zhejiang Ecological Civilization Academy, Anji, Zhejiang 310058, China; Institute of Soil and Water Resources and Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China.
⁵ Department of Environment Engineering, China Jiliang University, Hangzhou 310018, China.
⁶ Zhejiang Huanneng Environmental Technology Co. Ltd., Hangzhou, Zhejiang 310012, China.

PMID: 38163411
DOI: 10.1016/j.jhazmat.2023.133399

Abstract

The activity of single-atom catalysts in peroxymonosulfate activation process is bound up with the local electronic state of metal center. However, the large electronegativity of N atoms in Metal-N₄ restricts the electron transfer between center metal atom and peroxymonosulfate. Herein, we constructed Fe-SN-C catalyst by incorporating S atom in the first coordination sphere of Fe single-atom site (Fe-S₁N₃) for Fenton-like catalysis. The Fe-SN-C with a low valent Fe is found to exhibit excellent catalytic activity for bisphenol A degradation, and the corresponding rate constant reaches 0.405 min^-1, 11.9-fold higher than the original Fe-N-C. Besides, the Fe-SN-C/PMS system exhibits ideal catalytic stability under the effect of wide pH range and background substrates by the fast generation of high-valent Fe species. Experimental results and theoretical calculations reveal that the dual coordination of S and N atoms notably increases the local electron density of Fe atoms and electron filling in e_g orbital, causing a d band center shifting close to the fermi level and thereby optimizes the activation energy for peroxymonosulfate decomposition via Fe 3d-O 2p orbital interaction. This work provides further development of promising SACs for the efficient activation of peroxymonosulfate based on direct regulation of the coordination environment of active center metal atoms.

Keywords: Electronic structure; Fenton-like catalysis; Peroxymonosulfate; Single-atom catalyst; Sulfur doping.