4.7 Article

Iron porphyrin-TiO2 modulated peroxymonosulfate activation for efficient degradation of 2,4,6-trichlorophenol with high-valent iron-oxo species

Journal

CHEMOSPHERE
Volume 309, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.chemosphere.2022.136744

Keywords

Ball milling; Peroxymonosulfate; Hemin; High-valent iron-oxo; Biomimetic catalyst

Funding

  1. National Key Research and Development Program of China [2018YFC1900105]
  2. Natural Science Foundation of Hubei Province [2020CFA042]
  3. National Natural Science Foundation of China [51508213, 52170134, 52070083]
  4. Fundamental Research Funds for Central Universities [2017KFYXJJ217]
  5. Innovative Interdisciplinary Team at HUST [0118261077]

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In this study, a new catalyst TiO2-hemin was prepared and demonstrated high catalytic degradation efficiency in the PMS activation system. The strong interaction between TiO2 and hemin was found to be the key factor for the high activity, and high-valent iron-oxo species were identified as the primary active species.
Developing efficient catalysts with low cost and environmental friendliness for peroxymonosulfate (PMS) activation attracts broad interest. In this study, TiO2-hemin was prepared by immobilizing hemin on TiO2 using a ball milling method, demonstrating 126.9-fold enhanced catalytic degradation efficiency compared with unsupported hemin in the PMS activation system, with 92.9% of 2,4,6-trichlorophenol (2,4,6-TCP) removed in 10 min. The superior performance is attributed to the strong interaction between TiO2 and hemin, which induces the redistribution of the electron density of hemin molecules. In the TiO2-hemin/PMS system, sulfate radicals (SO4 center dot-), hydroxyl radicals (center dot OH), singlet oxygen (1O2), and superoxide radicals (O2 center dot-) were identified, which only played a minor role in the elimination of 2,4,6-TCP. Instead, high-valent iron-oxo species were proposed and identified as the primary active species. This study provides a facile strategy to enhance the activity of the biomimetic catalyst and offers insight into the catalytic mechanism of iron porphyrin with PMS activation.

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