Novel rapid room temperature synthesis of conjugated microporous polymer for metal-free photocatalytic degradation of fluoroquinolones

J Hazard Mater. 2020 Nov 5:398:122928. doi: 10.1016/j.jhazmat.2020.122928. Epub 2020 May 21.

Abstract

The existence of Fluoroquinolones (FQs), non-biodegradable pharmacophores, in the natural environment possesses a serious threat. We herein report a novel, rapid, room-temperature synthesis of semiconducting conjugated microporous polymer (CMP) for the decontamination of four second-generation FQs, Norfloxacin, Enrofloxacin, Ciprofloxacin, and Ofloxacin. The CMP demonstrated impressive gas uptake and FQ adsorption ability. Decreased HOMO-LUMO bandgap resulted in enhanced exciton pair generation on visible-light-illumination. Additionally, a high degree of photocurrent response and suitable redox potentials of the material conjointly endorsed its almost quantitative FQ-degradation efficiency. Ofloxacin showed the best removal efficiency with 0.061 and 0.207 min-1 adsorption and degradation rate constants, respectively, one of the highest values reported. The CMP exhibited equipotent activity for other FQs as well. On increasing the concentration of the FQs or decreasing the incident photo-intensity, quantitative removal efficiencies are observed. Changing the pH of the medium from acidic to alkaline did not impart any change in catalytic activity as well. The reactive species involved viz. O2-, 1O2, etc. and their roles in the degradation process were determined through control and trapping experiments. A plausible in-depth mechanistic pathway was assessed from the FQ degradation intermediates, and the reactive catalytic species substantiating step-by-step break down of the antibiotic backbone.

Keywords: Conjugated microporous polymer; Fluoroquinolones; Heterogeneous catalysis; Photocatalysis; Wastewater.

MeSH terms

  • Anti-Bacterial Agents
  • Ciprofloxacin
  • Fluoroquinolones*
  • Norfloxacin
  • Polymers*
  • Temperature

Substances

  • Anti-Bacterial Agents
  • Fluoroquinolones
  • Polymers
  • Ciprofloxacin
  • Norfloxacin