RETURN TO ISSUEPREVResearch ArticleNEXT

Spin-State-Dependent Peroxymonosulfate Activation of Single-Atom M–N Moieties via a Radical-Free Pathway

  • Jie Miao
    Jie Miao
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
    More by Jie Miao
  • Yuan Zhu
    Yuan Zhu
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
    More by Yuan Zhu
  • Junyu Lang
    Junyu Lang
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
    More by Junyu Lang
  • Jingzhen Zhang
    Jingzhen Zhang
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
  • Shixian Cheng
    Shixian Cheng
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
  • Baoxue Zhou
    Baoxue Zhou
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
    More by Baoxue Zhou
  • Lizhi Zhang
    Lizhi Zhang
    Key Laboratory of Pesticide & Chemical Biology of the Ministry of Education, Institute of Environmental and Applied Chemistry, Central China Normal University, Wuhan 430079, P. R. China
    More by Lizhi Zhang
  • Pedro J. J. Alvarez
    Pedro J. J. Alvarez
    Department of Civil and Environmental Engineering, Rice University, Houston, Texas 77005, United States
  • , and 
  • Mingce Long*
    Mingce Long
    School of Environmental Science and Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University, Shanghai 200240, China
    *Email: [email protected]
    More by Mingce Long
Cite this: ACS Catal. 2021, 11, 15, 9569–9577
Publication Date (Web):July 16, 2021
https://doi.org/10.1021/acscatal.1c02031
Copyright © 2021 American Chemical Society
Article Views
1838
Altmetric
-
Citations
LEARN ABOUT THESE METRICS
Read OnlinePDF (5 MB)
Supporting Info (1)»

Abstract

Transition metal catalysts are known to activate persulfate, but the properties that govern the intrinsic activity of these catalysts are still unknown. Here, we developed a series of catalysts with transition metals anchored on carbon nanotubes (denoted M–N–CNTs, where M = Co, Fe, Mn, or Ni) containing single-atom M–N moieties, to activate peroxymonosulfate for the efficient nonradical oxidation of sulfamethoxazole. The spin state of M–N–CNTs strongly determined their catalytic activity. A large effective magnetic moment with a high spin state (e.g., Co–N) favored the overlap of d orbitals with oxygen-containing adsorbates (such as peroxo species) on metal active sites and promoted electron transfer, which facilitated peroxymonosulfate adsorption and enhanced the oxidation capacity of the reactive species. These findings advance the mechanistic understanding of transition metal-mediated persulfate activation and inform the development of efficient spintronic catalysts for environmental applications.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.1c02031.

  • Material synthesis, characterization, evaluation of catalytic performance, electrochemical test, theoretical calculations, effects of pH, kobs of SMX oxidation in different PMS systems, quenching tests, GC-MS spectra of DMSO degradation, PMS adsorption in different systems, open-circuit potential curves, PMS* potentials, and spin states and μeff values of M–N–CNTs (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: http://pubs.acs.org/page/copyright/permissions.html.

Cited By


This article is cited by 1 publications.

  1. 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. https://doi.org/10.1021/acs.est.1c04091