Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: An electron-transfer dominated and radical/nonradical coupling process

Xiaolin Han; Wei Zhang; Shuai Li; Congyu Cheng; Qi Yu; Qilong Jia; Lei Zhou; Guangli Xiu

doi:10.1016/j.jes.2022.10.026

Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: An electron-transfer dominated and radical/nonradical coupling process

J Environ Sci (China). 2023 Aug:130:197-211. doi: 10.1016/j.jes.2022.10.026. Epub 2022 Oct 25.

Authors

Xiaolin Han¹, Wei Zhang², Shuai Li¹, Congyu Cheng¹, Qi Yu¹, Qilong Jia¹, Lei Zhou³, Guangli Xiu³

Affiliations

¹ State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China; Shanghai Environmental Protection Key Laboratory on Environmental Standard and Risk Management of Chemical Pollutants, East China University of Science and Technology, Shanghai 200237, China.
² State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China; Shanghai Environmental Protection Key Laboratory on Environmental Standard and Risk Management of Chemical Pollutants, East China University of Science and Technology, Shanghai 200237, China; Shanghai Institute of Pollution Control and Ecological Security, Tongji University, Shanghai 200092, China. Electronic address: zhangwei@ecust.edu.cn.
³ State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China; Shanghai Environmental Protection Key Laboratory on Environmental Standard and Risk Management of Chemical Pollutants, East China University of Science and Technology, Shanghai 200237, China; Shanghai Institute of Pollution Control and Ecological Security, Tongji University, Shanghai 200092, China.

PMID: 37032036
DOI: 10.1016/j.jes.2022.10.026

Abstract

Recently, transition metal sulfides have attracted much attention due to their better catalytic capacities as peroxymonosulfate (PMS) activator than their metal oxide counterparts. However, the systematic studies on PMS activation using transition metal sulfides are still lacking. In this work, manganese sulfide (MnS) materials were synthesized via a MOFs-derived method and utilized for PMS activation to degrade levofloxacin (LVF) in water for the first time. As expected, MnS exhibited remarkable LVF degradation efficiency by PMS activation, which was distinctly higher than Mn₂O₃. The results of quenching experiments, electro spin resonance identification and electrochemical tests indicated that electron-transfer progress was the dominant mechanism in α-MnS/PMS system. Meanwhile, the presence of ¹O₂ and radicals further became the removal of LVF by α-MnS/PMS system into a radical/nonradical coupling process. The superior electrical conductivity of α-MnS than α-Mn₂O₃ was revealed by DFT calculations, which resulted in the higher catalytic capacity of α-MnS. The result of XPS also indicated the S species in MnS accelerated the recycle of Mn(IV)/Mn(II) and then promoted the generation of radicals. Furthermore, the influence of various environmental conditions on LVF removal and the reusability of α-MnS were also investigated, which demonstrated the high application potential of α-MnS/PMS system. Finally, six possible pathways of LVF oxidation in the system were proposed based on the identified byproducts and their ecotoxicity was evaluated with ECOSAR method. This work promotes the fundamental understanding of PMS activation by α-MnS and provides useful information for practical application of manganese sulfide in water treatment.

Keywords: Electron-transfer pathway; Levofloxacin; Metal organic frameworks; MnS; PMS.

MeSH terms

Electrons*
Levofloxacin*
Peroxides
Sulfides

Substances

peroxymonosulfate
manganese sulfide
Levofloxacin
Peroxides
Sulfides