The Efficiency and Mechanism of FeOCl/Ce-Catalyzed Persulfate for the Degradation of Caffeine Under Visible Light

Despite extensive work on FeOCl-based photocatalysts, few studies have explored rare-earth (Ce) doping to simultaneously tune bandgap, suppress charge recombination, and enhance visible light-driven persulfate (PS) activation for the degradation of emerging contaminants. This study synthesized FeOCl/Ce composite photocatalysts via a partial pyrolysis method and systematically characterized their physicochemical properties. The results show that Ce doping significantly lowers the bandgap energy of the photocatalyst, enhances its visible light absorption ability, and effectively suppresses the recombination of photogenerated electron-hole pairs, thereby markedly improving photocatalytic performance under visible light. Analyses including XRD, EDS, XPS, and FT-IR confirm that Ce is incorporated into the FeOCl matrix and modulates the radial growth behavior of FeOCl without altering its intrinsic crystal structure. Morphological observations reveal that FeOCl/Ce exhibits a uniform nanosheet layered structure, with larger particles formed by the aggregation of smaller nanosheets. The nitrogen adsorption-desorption isotherm of FeOCl/Ce shows characteristics of Type IV with a relatively small BET surface area. The broadened optical absorption edge of FeOCl/Ce and the results of PL spectra and I-T curves further confirm its enhanced visible light absorption capacity and reduced electron-hole recombination compared to pure FeOCl. At an initial caffeine (CAF) concentration of 10 μM, FeOCl/Ce dose of 0.5 g/L, PS concentration of 1 mM, and initial pH of 5.06, the FeOCl/Ce-catalyzed PS system under visible light irradiation can degrade 91.2% of CAF within 30 min. An acidic environment is more favorable for CAF degradation, while the presence of SO₄^2-, Cl^-, and NO₃^- inhibits the process performance to varying degrees, possibly due to competitive adsorption on the photocatalyst surface or quenching of reactive species. Cyclic stability tests show that FeOCl/Ce maintains good catalytic performance over multiple runs. Mechanistic analysis indicates that ^•OH and holes are the dominant reactive species for CAF degradation, while PS mainly acts as an electron acceptor to suppress electron-hole recombination. Overall, the FeOCl/Ce photocatalytic system demonstrates high efficiency, good stability, and visible light responsiveness in CAF degradation, with potential applications for removing CAF and other emerging organic pollutants from aquatic environments.