Nitrogen-Fluorine co-doped TiO2/SiO2 nanoparticles for the photocatalytic degradation of acrylonitrile: Deactivation and regeneration

Abstract

In this study, we investigated the deactivation kinetics and mechanism of N-F-TiO₂/SiO₂ nanopowder as a model photocatalyst for the purpose of facilitating the photocatalytic degradation of acrylonitrile (AN) in aqueous environment. Prior research has already displayed the proficient degradation of AN through the utilization of N-F-TiO₂/SiO₂ catalysts, revealing a degradation efficiency of 81.2% within a span of 6 min at an initial AN concentration of 10 mg/L. Multiple variables including the initial AN concentration, illumination intensity, and initial pH value were extensively analyzed during the degradation process. The kinetics of photocatalytic degradation of AN, facilitated by the N-F-TiO₂/SiO₂ photocatalyst, were modeled by fitting the pseudo first-order reaction kinetics to each individual factor. Furthermore, the adverse effect of catalyst poisoning during the photocatalytic breakdown of AN using the N-F-TiO₂/SiO₂ photocatalyst was analyzed through a range of different techniques including SEM, XPS, BET, XRD, TG, and NH₃-TPD. The incorporation of findings from these diverse techniques revealed that, the primary factors contributing to the photocatalyst's poisoning were as follows: (i) During the degradation process, the build-up of intermediate molecules on active sites hindered their functionality, leading to a decrease in the efficiency of the photocatalytic reaction, (ii) Carbonaceous deposits formed when the catalyst's pore structure was obstructed by pollutants or intermediate products that had not undergone timely photocatalytic breakdown and (iii) The persistent erosion of active sites due to hydraulic forces resulted in inadequate performance of the N-F-TiO₂/SiO₂ photocatalyst in aqueous solutions. A comprehensive analysis of the deactivation kinetics was conducted, deciding in the formulation of a detailed poisoning mechanism for the N-F-TiO₂/SiO₂ photocatalyst. Additionally, we explored the catalysts regeneration, involving thermal treatment, ultrasonic irradiation, and catalyst reloading. This study not only advances our insight into the waning performance of catalysts in aqueous media but also establishes a conceptual framework for extrapolating analogous deactivation dynamics in other catalysts, grounded in precedent experimental knowledge. This research contributes to the development of a deactivation model for catalysts in the aqueous environment, based on existing experimental research, providing a theoretical framework for understanding the deactivation process of photocatalysts.

Keywords: Acrylonitrile; Deactivation mechanism; N–F–TiO(2)/SiO(2); Photocatalytic degradation; Regeneration.