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Highly efficient degradation of tetracycline in groundwater by nanoscale zero-valent iron-copper bimetallic biochar: active [H] attack and direct electron transfer mechanism

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Abstract

Development of carbon materials with high activity was important for rapid degradation of emerging pollutants. In this paper, a novel nanoscale zero-valent iron-copper bimetallic biochar (nZVIC-BC) was synthesized by carbothermal reduction of waste pine wood and copper-iron layered double hydroxides (LDHs). Characterization and analysis of its structural, elemental, crystalline, and compositional aspects using XRD, FT-IR, SEM, and TEM confirmed the successful preparation of nZVIC-BC and the high dispersion of Fe-Cu nanoparticles in an ordered carbon matrix. The experimental results showed that the catalytic activity of nZVIC-BC (Kobs of 0.0219 min−1) in the degradation of tetracycline (TC) in anoxic water environment was much higher than that of Fe-BC and Cu-BC; the effective degradation rate reached 85%. It was worth noting that the negative effects of Ca2+, Mg2+, and H2PO4− on TC degradation at ionic strengths greater than 15 mg/L were due to competition for active sites. Good stability and reusability were demonstrated in five consecutive cycle tests for low leaching of iron and copper. Combined with free radical quenching experiments and XPS analyses, the degradation of TC under air conditions was only 62%, with hydroxyl radicals (·OH) playing a dominant role. The synergistic interaction between Fe2+/Fe3+ and Cu0/Cu+/Cu2+ under nitrogen atmosphere enhances the redox cycling process; π-π adsorption, electron transfer processes, and active [H] were crucial for the degradation of TC; and possible degradation pathways of TC were deduced by LC-MS, which identified seven major aromatic degradation by-products. This study will provide new ideas and materials for the treatment of TC.

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Funding

This work was supported by the National Natural Science Foundation of China (52270079), Hunan Province Science and Technology Talents (2020TJ-N09), Chenzhou National Sustainable Development Agenda Innovation Demonstration Zone Innovation (2019sfq37), and Key Project of Hunan Provincial Education Department (21A0112).

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Authors and Affiliations

  1. Department of Environment, College of Environment and Resources, **angtan University, **angtan, Hunan, 411105, P. R. China

    Lingling Zhang, Yujiao Wang & Yin Xu

  2. Hunan Key Lab for Environmental Behavior of New Pollutants and Control Principle, Hunan, 411105, P. R. China

    Yujiao Wang & Yin Xu

Authors
  1. Lingling Zhang
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  2. Yujiao Wang
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Contributions

Lingling Zhang (**angtan, Hunan 411105, P. R. China): investigation, data curation, formal analysis, writing — original draft. Yujiao Wang (**angtan, Hunan 411105, P. R. China): formal analysis; writing — original draft; writing — review and editing; validation. Yin Xu (**angtan, Hunan 411105, P. R. China): conceptualization; methodology; writing — review and editing; funding acquisition.

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Correspondence to Yin Xu.

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Zhang, ., Wang, Y. & Xu, Y. Highly efficient degradation of tetracycline in groundwater by nanoscale zero-valent iron-copper bimetallic biochar: active [H] attack and direct electron transfer mechanism. Environ Sci Pollut Res (2024). https://doi.org/10.1007/s11356-024-33976-6

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