Reverse micelle strategy for effective substitutional Fe-doping in small-sized CeO2 nanocrystals: Assessment of adsorption and photodegradation efficiency of ibuprofen under visible light

O. Tammaro, R. Paparo, M. Chianese, I. Ritacco, L. Caporaso, M. Farnesi Camellone, B. Masenelli , A. D. Lamirand, J.M. Bluet, M. Fontana , G. Pinto, A. Illiano, A. Amoresano, M. Di Serio, V. Russo, S. Esposito

Chemical Engineering Journal  479, 2024, 147909 


Reverse micelle nanoreactors were successfully designed to synthesize small-sized ceria nanocrystals (3.5–4.2 nm) with a sizeable amount of substitutional iron. Undoped and doped CeO2 catalysts with an iron content (0.50–10 mol %) compliant with the nominal value were prepared and tested for the first time for the removal of ibuprofen both in the dark and under UV or visible light irradiation.

The effective inclusion and distribution of iron in the ceria lattice were ascertained through in-depth physicochemical characterization. In particular, X-ray diffraction suggested the formation of an F-type crystal structure, ruling out the formation of separate iron-containing crystalline phases. On the other hand, substitutional doping of CeO2 with Fe atoms favoured the formation of Ce3+ defects and vacancy sites (VOs) with a maximum for the sample with 2.5 mol % iron (Fe2.5), as evidenced by X-ray photoelectron spectroscopy (XPS) measurements and Raman spectroscopy. UV–Vis spectroscopy showed that the optical properties were successfully modified by the presence of iron, which causes a gradual decrease in band gap as iron content increases. The experimental evidence was further verified and supported by density functional theory calculations. DFT calculations also revealed that the surface iron and oxygen vacancies are the preferential sites for ibuprofen adsorption. Nevertheless, it was found under dark conditions that adsorption capacity does not monotonically increase with iron content, revealing contrasting roles of surface characteristics. Indeed, catalytic experiments have identified a trade-off between adsorption and photodegradation, identifying Fe2.5 as the best-performing catalyst for ibuprofen removal under visible light irradiation. These results were discussed by considering the key properties of the catalysts as well as their different surface charge determined by ζ potential measurements. The best catalyst was tested through reuse experiments that proved its stability over 4 cycles. Finally, an attempt was made to identify the photodegradation by-products, allowing the detection of 1-ethenyl-4-(2-methylpropyl)benzene as the main by-product.