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Effective reduction of metronidazole over the cryptomelane-type manganese oxide octahedral molecular sieve (K-OMS-2) catalyst: facile synthesis, experimental design and modeling, statistical analysis, and identification of by-products

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Abstract

High concentrations of antibiotic compounds within pharmaceutical wastewater have hazardous impacts toward environment and human health. Therefore, there is an immediate requirement of efficient treatment method for removal of antibiotics from aquatic environment. In the present study, the cryptomelane catalyst-type manganese oxide octahedral molecular sieve (K-OMS-2) was synthesized in the presence of benzyl alcohol as a reducing agent and cetyltrimethylammonium bromide as a structure-directing agent and then utilized to reduce the metronidazole. The central composite design method was the experimental design adopted. The FESEM analysis revealed that the K-OMS-2 surface contained many uniformly cylindrical aggregates less than about 40 nm in diameter and about 80–100 nm in length. Besides, a high specific surface area of 129 m2/g and average pore size of 45.47 nm were recorded. According to the TGA/DTA analysis, the prepared catalyst revealed high thermal stability. The maximum metronidazole degradation (95.36%) was evident at conditions of pH = 3, catalyst mass = 0.97 g/L, contact time = 200 min, and metronidazole concentration = 20 mg/L. Metronidazole did not form a complex with nitrate, fluoride, sulfate, or hardness. These ions exerted a negligible effect on metronidazole reduction using the K-OMS-2 catalyst, except for hardness, which reduced the removal efficiency of metronidazole by 17%. The FTIR and LC-MS revealed a complex mechanism involved in the metronidazole degradation by the K-OMS-2 involving the formation of an amino group, a hydroxyelated compound via N-denitration, and hydrogenation process on the K-OMS-2 catalyst surface.

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Funding

The authors are grateful to the Alborz University of Medical Sciences for the financial support made available to them for this research.

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Authors and Affiliations

  1. Department of Environmental Health Engineering, Research Center for Health, Safety and Environment, Faculty of Health, Alborz University of Medical Sciences, Karaj, Iran

    Ebrahim Mohammadi Kalhori, Mohammad Noori Sepehr & Mansur Zarrabi

  2. Environmental Health Research Center, Research Institute for Health Development, Kurdistan University of Medical Sciences, Sanandaj, Iran

    Esmaeil Ghahramani

  3. Department of Civil Engineering, Faculty of Engineering, Isra University, Amman, Jordan

    Tariq J. Al-Musawi

  4. Department of Environmental Health Engineering, School of Health, Torbat Heydariyeh University of Medical Sciences, Torbat Heydarieh, Iran

    Hossien Najafi Saleh

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  1. Ebrahim Mohammadi Kalhori
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  2. Esmaeil Ghahramani
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  4. Hossien Najafi Saleh
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Correspondence to Mansur Zarrabi.

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Responsible editor: Philippe Garrigues

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Kalhori, E.M., Ghahramani, E., Al-Musawi, T.J. et al. Effective reduction of metronidazole over the cryptomelane-type manganese oxide octahedral molecular sieve (K-OMS-2) catalyst: facile synthesis, experimental design and modeling, statistical analysis, and identification of by-products. Environ Sci Pollut Res 25, 34164–34180 (2018). https://doi.org/10.1007/s11356-018-3352-9

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