A multivariate modeling and experimental realization of photocatalytic system of engineered S-C3N4/ZnO hybrid for ciprofloxacin removal: Influencing factors and degradation pathways.

Ciprofloxacin, a pharmaceutically active compound, is present as a micropollutant in wastewater, which cannot be removed by conventional techniques due to its recalcitrant nature. Therefore, in the present study, the photocatalytic degradation of this bio-toxic compound was demonstrated using a three-dimensional sulfur-doped graphitic-carbon nitride/zinc oxide hybrid, with enriched oxygen vacancies. The influence of various water matrices and experimental conditions on the ciprofloxacin degradation was optimized. The hybrid material showed 98.8% and 75.8% degradation efficiency under optimum experimental conditions (i.e., catalyst dose: 1 g/L; pH: 5; initial ciprofloxacin concentration: 20 mg/L; temperature: 27 °C) under ultraviolet (UV) and visible light, respectively. A neural-network-based multivariate approach was used to predict a significant model considering the experimental conditions that showed adequate statistical significance (R2: 0.992 and F-value: 8707.1). The relative significance of the experimental conditions was assessed, suggesting that the initial ciprofloxacin concentration has a more significant effect on the degradation efficiency than the other factors. The rate kinetics and reaction mechanisms for ciprofloxacin degradation were demonstrated, and the driving radicals involved were identified. A higher rate of reaction was found under UV irradiation (0.01702 min-1) than under visible light (0.00802 min-1). Superoxide radicals were identified as the main driving radicals, which caused substantial photocatalytic reactions among the hybrid and ciprofloxacin molecules. Microscopic and macroscopic analyses of the used hybrid were conducted, which confirmed the presence of higher defect concentrations, crystallinity, and interlinked stacked structure in the hybrid. Hence, the 3D hybrid can be efficiently used and reused for ciprofloxacin degradation. This advanced photocatalytic system can be widely used to remediate emerging contaminants in wastewater treatment.