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Subnano-Fe (Co, Ni) clusters anchored on halloysite nanotubes: an efficient Fenton-like catalyst for the degradation of tetracycline

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Abstract

Iron-based catalysts are environmentally friendly, and iron minerals are abundant in the earth's crust, with great potential advantages for PMS-based advanced oxidation process applications. However, homogeneous Fe2+/PMS systems suffer from side reactions and are challenging to reuse. Therefore, develo** catalysts with improved stability and activity is a long-term goal for practical Fe-based catalyst applications. In this study, we prepared Fe-HNTs nanoreactors by encapsulating a nitrogen-doped carbon layer with one-dimensional halloysite nanotubes (HNTs) using the molten salt-assisted method. Subsequently, Fe (Co, Ni) nanoclusters were anchored onto the nitrogen-doped carbon layer at a relatively low temperature (550℃), resulting in stable and uniform distribution of metal nanoclusters on the surface of HNTs carriers in the form of Fe-Nx coordination. The results showed that the dissolution of the molten salt and leaching of post-treated metal oxides generated numerous mesopores within the Fe-HNTs nanoreactor, leading to a specific surface area more than 10 times that of HNTs. This enhanced mass transfer capability facilitates rapid pollutant removal while exposing more active sites. Remarkably, Fe-HNTs adsorbed up to 97% of tetracycline within 60 min. In the Fe-HNTs/PMS system, the predominant reactive oxygen species has been shown to be 1O2, and the added tetracycline was degraded by more than 98% within 5 min. The removal of tetracycline was maintained above 96% in the presence of interfering factors such as wide pH (3–11) and inorganic anions (5 mM Cl−, HCO3−, NO3−, and SO42−). The investigated mechanism suggests that efficient degradation and interference resistance of the Fe-HNTs/PMS system is attributed to the synergistic effect between the rapid adsorption of porous structure and the non-radical (1O2)-dominated degradation pathway.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

Abbreviations

M–N-C:

Metal-nitrogen-carbon

HNTs:

Halloysite nanotubes

Fe-HNTs:

Fe/N/C@HNTs

Co-HNTs:

Co/N/C@HNTs

Ni-HNTs:

Ni/N/C@HNTs

TC:

Tetracycline

NFA:

Norfloxacin

RhB:

Rhodamine

MB:

Methylene blue

AOPs:

Advanced oxidation processes

PMS:

Peroxymonosulfate

TBA:

Tert-butanol

SEM:

Scanning electron microscopy

XRD:

X-ray diffraction

TEM:

Transmission electron microscope

EDS :

Energy dispersive spectroscopy

XPS:

X-ray photoelectron spectroscopy

BET:

Brunauer–Emmett–Teller

FTIR :

Fourier transform infrared spectrometer

EPR:

Electron paramagnetic resonance

LC-MS:

Liquid chromatography-mass spectrometry

ROS:

Reactive oxygen species

COD :

Chemical oxygen demand

FFA:

Furfuryl alcohol

MeOH:

Methanol

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Funding

The authors acknowledge the financial support provided by the Engineering Research Center of Non-metallic Minerals of Zhejiang Province (ZD2023K04), China Postdoctoral Science Foundation (2022M723394), and Zhejiang Provincial Natural Science Foundation of China (LY24E040002).

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Authors and Affiliations

  1. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, 310014, Zhejiang, China

    Qing Sun, Jiale Yu, Youpu Zhao, Jiajun Tao, Jian Zhang & Jiawei Sheng

  2. School of Environmental Science and Spatial Informatics, China University of Mining and Technology, Xuzhou, 221116, China

    Qing Sun & Hanhu Liu

  3. Zhejiang Institute of Geosciences, Hangzhou, 310007, China

    Chunsheng Li

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  1. Qing Sun
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Contributions

Qing Sun: conceptualization, methodology, data curation, and funding acquisition. Jiale Yu: methodology, writing, and visualization. Youpu Zhao: formal analysis, data curation, visualization, and writing. Hanhu Liu: review and editing and investigation. Chunsheng Li: supervision and resources. Jiajun Tao: visualization and data curation. Jian Zhang: supervision and investigation. Jiawei Sheng: project administration and funding acquisition.

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Correspondence to Jiawei Sheng.

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Sun, Q., Yu, J., Zhao, Y. et al. Subnano-Fe (Co, Ni) clusters anchored on halloysite nanotubes: an efficient Fenton-like catalyst for the degradation of tetracycline. Environ Sci Pollut Res 31, 28210–28224 (2024). https://doi.org/10.1007/s11356-024-32947-1

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