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Self-Assembly of Mn(II)-Amidoximated PAN Polymeric Beads Complex as Reusable Catalysts for Efficient and Stable Heterogeneous Electro-Fenton Oxidation

  • Xiong Li
    Xiong Li
    Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
    More by Xiong Li
  • Lei Qin
    Lei Qin
    Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
    More by Lei Qin
  • Yufan Zhang
    Yufan Zhang
    Department of Mechanical Engineering, College of Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
    More by Yufan Zhang
  • Zehai Xu
    Zehai Xu
    Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
    More by Zehai Xu
  • Lin Tian
    Lin Tian
    Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
    More by Lin Tian
  • Xinwen Guo
    Xinwen Guo
    State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, Dalian University of Technology, Dalian 116012, China
    More by Xinwen Guo
  • , and 
  • Guoliang Zhang*
    Guoliang Zhang
    Institute of Oceanic and Environmental Chemical Engineering, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China
    *E-mail: [email protected]. Phone/Fax: +86-571-8832 0863.
Cite this: ACS Appl. Mater. Interfaces 2019, 11, 4, 3925–3936
Publication Date (Web):January 8, 2019
https://doi.org/10.1021/acsami.8b18704
Copyright © 2019 American Chemical Society
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Abstract

A facile postsynthetic amidoxime modification method was reported on the preparation of transition-metal ions (Mn, Fe, and Co)–polyacrylonitrile (PAN) polymeric beads complex as reusable catalysts for efficient and stable heterogeneous electro-Fenton oxidation. Through one-step phase inversion, low-cost and chemically resistant polymeric PAN beads were fabricated on a large scale with controllable sizes and abundant porous structure. The postfunctionalization strategy led more active sites to be uniformly distributed into modified PAN beads owing to the favorable channel confined effect and chelate coordination. Compared with pure PAN beads, the modified composite catalysts exhibited remarkably higher activity and stability in electro-Fenton oxidation over wide pH range of 3–10 without any addition of H2O2. By analysis, the grafted amidoxime group was extremely beneficial for improving metal loading and binding force between active sites and organic supports, which accelerated the active sites autocatalytic cycle to promote H2O2 activation by means of excited electron transfer from composites’ functional groups. The catalytic activity of Mn–amidoximated PAN evaluated by the turnover frequency was 15 times more than that of traditional iron oxide and very competitive to the reported metal–organic framework-based composites. Moreover, a strong metal and polymeric support interaction significantly enhanced the stabilization of active sites dispersed in porous matrix and solved the ever-present problem of metallic ions leaching to the greatest extent. The scalable introduction of functionalities into sophisticated structures after host framework synthesis will bring valuable insights to develop highly efficient and stable heterogeneous catalysts for green electrochemical oxidation in practical application.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b18704.

  • Electro-Fenton system, SEM images of pure PAN, Fe–AOPAN, and Co–AOPAN beads, photographs of self-assembly PAN beads with different sizes and metal-amidoximated PAN polymeric beads complexes, surface area, and textural data, kinetic parameters for electrochemistry and electro-Fenton oxidation, EDS elemental analysis, adsorption/desorption isotherms, BJH pore size distribution, FTIR, XRD, and XPS spectra of Fe–AOPAN and Co–AOPAN, mass spectra of intermediate products, and reusability and metal leaching of Fe–AOPAN and Co–AOAPAN (PDF)

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