Aqueous and Solid Phase Photocatalytic Degradation of Perfluorooctane Sulfonate by Carbon- and Fe-Modified Bismuth Oxychloride

Abstract

In this study, we prepared and tested a carbon-modified, Fe-loaded bismuth oxychloride (Fe-BiOCl/CS) photocatalyst for photocatalytic degradation of perfluorooctane sulfonate (PFOS). Structural analyses revealed a (110) facet-dominated sheet-type BiOCl crystal structure with uniformly distributed Fe and confirmed carbon modification of the photocatalyst. The presence of D-glucose facilitated the growth control of BiOCl particles and enhanced the adsorption of PFOS via added hydrophobic interaction. Adsorption kinetic and equilibrium tests showed rapid uptake rates of PFOS and high adsorption capacity with a Langmuir Qmax of 1.51 mg/g. When used for directly treating PFOS in solution, Fe-BiOCl/CS was able to mineralize or defluorinate 83% of PFOS (C0 = 100 μgL-1 ) under UV (254 nm, intensity = 21 mW cm-2) in 4 h; and when tested in a two-step mode, i.e., batch adsorption and subsequent photodegradation, Fe-BiOCl/CS mineralized 65.34% of PFOS that was pre-concentrated in the solid phase under otherwise identical conditions; while the total degradation percentages of PFOS were 83.48% and 80.50%, respectively, for the two experimental modes. The photoactivated electrons and/or hydrated electrons and superoxide radicals primarily initiated the desulfonation of PFOS followed by decarboxylation and defluorination, through a stepwise chain-subsiding mechanism. The elevated photocatalytic activity can be attributed to the effective separation of e-/h+ pairs facilitated by the (110) interlayer electrostatic field, Fe- and carbon-facilitated charge transfer, and the presence of oxygen vacancies. This work reveals the potential of carbon-modified and Fe-co-catalyzed BiOCl for concentrating and degrading PFOS and other persistent organic pollutants.

Keywords: Perfluorooctane sulfonate, Catalysis, Carbon-modified catalyst, Photocatalysis, Adsorption and photodegradation, Persistent organic pollutant