Templating agent-mediated Cobalt oxide encapsulated in mesoporous silica as an efficient oxone activator for elimination of toxic anionic azo dye in water: Mechanistic and DFT-assisted investigations

Ta Cong KHIEM, Po-Hsin MAO, Young-Kwon PARK, Xiaoguang DUAN, Bui Xuan THANH, Chechia HU, Suresh GHOTEKAR, Yiu Fai TSANG, Kun-Yi Andrew LIN

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7 Citations (Scopus)

Abstract

While Azorubin S (AZRS) is extensively used as a reddish anionic azo dye for textiles and an alimentary colorant in food, AZRS is mutagenic/carcinogenic, and it shall be removed from dye-containing wastewaters. In view of advantages of SO₄·⁻-related chemical oxidation technology, oxone (KHSO₅) would an ideal source of SO₄·⁻ for degrading AZRS, and heterogeneous Co₃O₄-based catalysts is required and shall be developed for activating oxone. Herein, a facile protocol is proposed for fabricating mesoporous silica (MS)-confined Co₃O₄ by a templating agent-mediated dry-grinding procedure. As the templating agent retained inside the ordered pores of MS (before calcination) would facilitate insertion and dispersion of Co ions into pores, the resulting Co₃O₄ nanoparticles (NPs) would be grown and confined within the pores of MS after calcination, affording Co@MS. On the contrary, another analogue, Co/MS, is also prepared using the similar protocol without the templating agent-mediated introduction of Co, but Co₃O₄ NPs seriously aggregate as clusters on MS. Therefore, Co@MS outperforms Co/MS for activating oxone to eliminate AZRS. Co@MS shows a noticeably lower activation energy of AZRS elimination than the existing catalysts, revealing its advantage over the reported catalysts. Moreover, the mechanistic investigation of AZRS elimination by Co@MS-activated oxone has been also elucidated for identifying the presence of SO₄·⁻, ·OH, and ¹O₂ in AZRS degradation using scavengers, electron paramagnetic resonance spectroscopy, and semi-quantification. The AZRS decomposition pathway is also investigated and unveiled in details via the DFT calculation. These results validate that Co@MS appears as a superior catalyst of oxone activation for AZRS degradation. Copyright © 2022 Published by Elsevier Ltd.
Original languageEnglish
Article number137309
JournalChemosphere
Volume313
Early online date26 Nov 2022
DOIs
Publication statusPublished - Feb 2023

Citation

Khiem, T. C., Mao, P.-H., Park, Y.-K., Duan, X., Thanh, B. X., Hu, C., . . . Lin, K.-Y. A. (2023). Templating agent-mediated Cobalt oxide encapsulated in mesoporous silica as an efficient oxone activator for elimination of toxic anionic azo dye in water: Mechanistic and DFT-assisted investigations. Chemosphere, 313. Retrieved from https://doi.org/10.1016/j.chemosphere.2022.137309

Keywords

  • Azo dye
  • Sulfate radical
  • Silica
  • SiO₂
  • Cobalt
  • KSO₅

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