RETURN TO ISSUEPREVTreatment and Resour...Treatment and Resource RecoveryNEXT

Nonradical Oxidation of Pollutants with Single-Atom-Fe(III)-Activated Persulfate: Fe(V) Being the Possible Intermediate Oxidant

  • Ning Jiang
    Ning Jiang
    Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
    University of Chinese Academy of Sciences, Beijing 100049, China
    More by Ning Jiang
  • Haodan Xu
    Haodan Xu
    Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
    More by Haodan Xu
  • Lihong Wang
    Lihong Wang
    Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
    More by Lihong Wang
  • Jin Jiang
    Jin Jiang
    Institute of Environmental and Ecological Engineering, Guangdong University of Technology, Guangzhou 510006, China
    More by Jin Jiang
  • , and 
  • Tao Zhang*
    Tao Zhang
    Research Center for Eco-environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
    *Email: [email protected]
    More by Tao Zhang
Cite this: Environ. Sci. Technol. 2020, 54, 21, 14057–14065
Publication Date (Web):October 23, 2020
Copyright © 2020 American Chemical Society
Article Views
Read OnlinePDF (3 MB)
Supporting Info (1)»


When applied for the remediation of polluted water/soil, peroxydisulfate (PDS) usually needs to be effectively activated to generate sulfate radical as the working oxidant. However, a significant part of the oxidation capacity of PDS is lost in this way because sulfate radical unselectively reacts with most of the substances in water/soil. PDS activation without generating radicals is preferred to maximize its oxidation capacity for targeted pollutants. Here, we report that single-atom Fe(III)- and nitrogen-doped carbon (Fe–N–C) can efficiently activate PDS to selectively remove some organic pollutants following an unreported nonradical pathway. The single-atom Fe(III) coordinated with pyridinic N atoms was confirmed to be the active site for the catalytic decomposition of PDS. However, the PDS decomposition did not produce radicals or reactive oxygen species. It is very likely that the coordinated Fe(III) is readily converted to Fe(V) through two-electron abstraction by PDS, and Fe(V) is responsible for the selective degradation of organic pollutants. The PDS/Fe–N–C-coupled process utilizes more oxidation capacity of PDS than both radical oxidation and other reported nonradical oxidation like PDS/CuO under the same experimental conditions. This process provides a new approach to selectively degrade some organic pollutants through PDS activation.

Supporting Information

Jump To

The Supporting Information is available free of charge at

  • Chemicals and materials used in this study; DMPO- and TMP-trapping ESR experiment; electrochemical characterization; molecular structures of the organics used in this study; HPLC conditions for the analysis of the pollutants; Eo values obtained from the XANES spectra; TEM images, SAED, and elemental maps of the as-prepared sample; XPS N 1s, O 1s, and C 1s spectra of Fe-N-C; influence of sulfate on 2,4-DCP degradation during PDS/Fe-N-C-coupled oxidation; oxalate degradation during PDS/Fe-N-C-coupled oxidation; KSCN decomposition (100 μM) and its influence on 2,4-DCP degradation in the PDS/Fe-N-C-coupled oxidation; TEM images of FeNP-N-C; degradation of PMSO by the PDS/FeNP-N-C-coupled oxidation; EPR spectra of PDS, Fe-N-C, and PDS/Fe-N-C; EIS Nyquist plots of N-C and Fe-N-C, current response at the N-C and Fe-N-C-coated working electrode, and LSV curves of Fe-N-C under different conditions, if added, [PDS]o = 2 mM and [2,4-DCP]o = 40 μM; GC/MS chromatograms of 2,4-DCP solution after PDS/Fe-N-C oxidation; influence of pH on 2,4-DCP degradation and Fe ion leaching by PDS/Fe-N-C oxidation; 2,4-DCP degradation by the PDS/Fe3+-coupled system; zeta-potential of Fe-N-C under different pHs; comparison of PDS/Fe-N-C with PDS/CuO for 2,4-DCP degradation; 2,4-DCP concentration in the effluent from a continuous-flow column; and removal of selected pollutants by the PDS/Fe-N-C-coupled oxidation (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 29 publications.

  1. Mingjie Huang, Yi Han, Wei Xiang, Delai Zhong, Chen Wang, Tao Zhou, Xiaohui Wu, Juan Mao. In Situ-Formed Phenoxyl Radical on the CuO Surface Triggers Efficient Persulfate Activation for Phenol Degradation. Environmental Science & Technology 2021, 55 (22) , 15361-15370.
  2. Banghai Liu, Wanqian Guo, Wenrui Jia, Huazhe Wang, Qishi Si, Qi Zhao, Haichao Luo, Jin Jiang, Nanqi Ren. Novel Nonradical Oxidation of Sulfonamide Antibiotics with Co(II)-Doped g-C3N4-Activated Peracetic Acid: Role of High-Valent Cobalt–Oxo Species. Environmental Science & Technology 2021, 55 (18) , 12640-12651.
  3. Jie Miao, Yuan Zhu, Junyu Lang, Jingzhen Zhang, Shixian Cheng, Baoxue Zhou, Lizhi Zhang, Pedro J. J. Alvarez, Mingce Long. Spin-State-Dependent Peroxymonosulfate Activation of Single-Atom M–N Moieties via a Radical-Free Pathway. ACS Catalysis 2021, 11 (15) , 9569-9577.
  4. Jun Liang, Xiaoguang Duan, Xiaoyun Xu, Kexin Chen, Yue Zhang, Ling Zhao, Hao Qiu, Shaobin Wang, Xinde Cao. Persulfate Oxidation of Sulfamethoxazole by Magnetic Iron-Char Composites via Nonradical Pathways: Fe(IV) Versus Surface-Mediated Electron Transfer. Environmental Science & Technology 2021, 55 (14) , 10077-10086.
  5. Yaowen Gao, Yue Zhu, Tong Li, Zhenhuan Chen, Qike Jiang, Zhiyu Zhao, Xiaoying Liang, Chun Hu. Unraveling the High-Activity Origin of Single-Atom Iron Catalysts for Organic Pollutant Oxidation via Peroxymonosulfate Activation. Environmental Science & Technology 2021, 55 (12) , 8318-8328.
  6. Kun Qian, Hong Chen, Wenlang Li, Zhimin Ao, Yi-nan Wu, Xiaohong Guan. Single-Atom Fe Catalyst Outperforms Its Homogeneous Counterpart for Activating Peroxymonosulfate to Achieve Effective Degradation of Organic Contaminants. Environmental Science & Technology 2021, 55 (10) , 7034-7043.
  7. Yangke Long, Jian Dai, Shiyin Zhao, Yiping Su, Zhongying Wang, Zuotai Zhang. Atomically Dispersed Cobalt Sites on Graphene as Efficient Periodate Activators for Selective Organic Pollutant Degradation. Environmental Science & Technology 2021, 55 (8) , 5357-5370.
  8. Chao He, Wu Xia, Chengyun Zhou, Danlian Huang, Chen Zhang, Biao Song, Yang Yang, Jun Li, Xing Xu, Yanan Shang, Li Du. Rational design to manganese and oxygen co-doped polymeric carbon nitride for efficient nonradical activation of peroxymonosulfate and the mechanism insight. Chemical Engineering Journal 2022, 430 , 132751.
  9. Yangke Long, Jian Dai, Shiyin Zhao, Shixin Huang, Zuotai Zhang. Metal–organic framework-derived magnetic carbon for efficient decontamination of organic pollutants via periodate activation: Surface atomic structure and mechanistic considerations. Journal of Hazardous Materials 2022, 424 , 126786.
  10. Tong Xiao, Yan Wang, Jinquan Wan, Yongwen Ma, Zhicheng Yan, Shuhong Huang, Cheng Zeng. Fe-N-C catalyst with Fe-NX sites anchored nano carboncubes derived from Fe-Zn-MOFs activate peroxymonosulfate for high-effective degradation of ciprofloxacin: Thermal activation and catalytic mechanism. Journal of Hazardous Materials 2022, 424 , 127380.
  11. Xiaoming Peng, Jianqun Wu, Zilong Zhao, Xing Wang, Hongling Dai, Li Xu, Gaoping Xu, Yan Jian, Fengping Hu. Activation of peroxymonosulfate by single-atom Fe-g-C3N4 catalysts for high efficiency degradation of tetracycline via nonradical pathways: Role of high-valent iron-oxo species and Fe–Nx sites. Chemical Engineering Journal 2022, 427 , 130803.
  12. Yunjin Yao, Huanhuan Hu, Hongda Zheng, Hongwei Hu, Yinghao Tang, Xiaoyan Liu, Shaobin Wang. Nonprecious bimetallic Fe, Mo-embedded N-enriched porous biochar for efficient oxidation of aqueous organic contaminants. Journal of Hazardous Materials 2022, 422 , 126776.
  13. Pijun Duan, Jingwen Pan, Weiyan Du, Qinyan Yue, Baoyu Gao, Xing Xu. Activation of peroxymonosulfate via mediated electron transfer mechanism on single-atom Fe catalyst for effective organic pollutants removal. Applied Catalysis B: Environmental 2021, 299 , 120714.
  14. Xiaolei Wang, Tong Yunping, Guodong Fang. Advances of single-atom catalysts for applications in persulfate-based advanced oxidation technologies. Current Opinion in Chemical Engineering 2021, 34 , 100757.
  15. Yunjin Yao, Xiaoyan Liu, Huanhuan Hu, Yinghao Tang, Hongwei Hu, Zhenshan Ma, Shaobin Wang. Synthesis and Characterization of Iron–Nitrogen-Doped Biochar Catalysts for Organic Pollutant Removal and Hexavalent Chromium Reduction. Journal of Colloid and Interface Science 2021, 248
  16. Yu Li, Yong Feng, Bin Yang, Zequn Yang, Kaimin Shih. Activation of peroxymonosulfate by molybdenum disulfide-mediated traces of Fe(III) for sulfadiazine degradation. Chemosphere 2021, 283 , 131212.
  17. Wei Miao, Ying Liu, Dandan Wang, Ningjie Du, Ziwei Ye, Yang Hou, Shun Mao, Kostya (Ken) Ostrikov. The role of Fe-Nx single-atom catalytic sites in peroxymonosulfate activation: Formation of surface-activated complex and non-radical pathways. Chemical Engineering Journal 2021, 423 , 130250.
  18. Youyou Hu, Siyu Sun, Mengshan Xu, Jialin Guo, Zhengkui Li. Efficient degradation of aqueous organic contaminants in manganese(II)/peroxymonosulfate system assisted by pyridine organic ligands. Science of The Total Environment 2021, 24 , 151441.
  19. Jun Wang, Bin Li, Yang Li, Xiaobin Fan, Fengbao Zhang, Guoliang Zhang, Wenchao Peng. Facile Synthesis of Atomic Fe‐N‐C Materials and Dual Roles Investigation of Fe‐N 4 Sites in Fenton‐Like Reactions. Advanced Science 2021, 8 (22) , 2101824.
  20. Lin-Qian Yu, Yi-Heng Zhao, Hao Wang, Feng Jin, Shu-La Chen, Te-Er Wen, Chuan-Shu He, Bao-Cheng Huang, Ren-Cun Jin. Surface oxygen vacancies formation on Zn2SnO4 for bisphenol-A degradation under visible light: The tuning effect by peroxymonosulfate. Journal of Hazardous Materials 2021, 11 , 127828.
  21. Huiwang Dai, Wenjun Zhou, Wei Wang, Zhiqi Liu. Unveiling the role of cobalt species in the Co/N-C catalysts-induced peroxymonosulfate activation process. Journal of Hazardous Materials 2021, 38 , 127784.
  22. Jie Dong, Weihua Xu, Shaobo Liu, Li Du, Qiang Chen, Ting Yang, Youzi Gong, Meifang Li, Xiaofei Tan, Yunguo Liu. Recent advances in applications of nonradical oxidation in water treatment: Mechanisms, catalysts and environmental effects. Journal of Cleaner Production 2021, 321 , 128781.
  23. Liang Wang, Yangyang Wang, Lili Zhang, Tong Li, Min Yang, Chun Hu. CoO anchored on boron nitride nanobelts for efficient removal of water contaminants by peroxymonosulfate activation. Chemical Engineering Journal 2021, 12 , 132915.
  24. Qihui Xu, Hong Zhang, Haoran Leng, Hong You, Yuhong Jia, Shutao Wang. Ultrasonic role to activate persulfate/chlorite with foamed zero-valent-iron: Sonochemical applications and induced mechanisms. Ultrasonics Sonochemistry 2021, 78 , 105750.
  25. Lihong Wang, Haodan Xu, Ning Jiang, Suyan Pang, Jin Jiang, Tao Zhang. Effective activation of peroxymonosulfate with natural manganese-containing minerals through a nonradical pathway and the application for the removal of bisphenols. Journal of Hazardous Materials 2021, 417 , 126152.
  26. Zhe Zhou, Mengqiao Li, Chunguang Kuai, Yuxin Zhang, Virginia F. Smith, Feng Lin, Ashlee Aiello, David P. Durkin, Hanning Chen, Danmeng Shuai. Fe-based single-atom catalysis for oxidizing contaminants of emerging concern by activating peroxides. Journal of Hazardous Materials 2021, 418 , 126294.
  27. Abdellah Ait El Fakir, Zakaria Anfar, Abdallah Amedlous, Asma Amjlef, Salaheddine Farsad, Amane Jada, Noureddine El Alem. Synergistic effect for efficient catalytic persulfate activation in conducting polymers-hematite sand composites: Enhancement of chemical stability. Applied Catalysis A: General 2021, 623 , 118246.
  28. Bingkun Huang, Zelin Wu, Hongyu Zhou, Jiayi Li, Chenying Zhou, Zhaokun Xiong, Zhicheng Pan, Gang Yao, Bo Lai. Recent advances in single-atom catalysts for advanced oxidation processes in water purification. Journal of Hazardous Materials 2021, 412 , 125253.
  29. Yanan Shang, Xing Xu, Baoyu Gao, Shaobin Wang, Xiaoguang Duan. Single-atom catalysis in advanced oxidation processes for environmental remediation. Chemical Society Reviews 2021, 50 (8) , 5281-5322.