Visible light-induced degradation of antibiotic ciprofloxacin over Fe–N–TiO2 mesoporous photocatalyst with anatase/rutile/brookite nanocrystal mixture

Abstract

Titanium dioxide photocatalysts co-modified with iron and nitrogen (Fe–N–TiO2) were produced via hydrothermal method using iron(III) nitrate nonahydrate and urea as iron and nitrogen sources, respectively. The effects of different dopant concentrations were investigated. The modified TiO2 catalysts were characterized for phase composition, surface morphology, specific surface area, degree of doping, charge states and bandgap energy combining various techniques. The results showed that controlled iron and nitrogen concentrations significantly altered the physicochemical properties of the catalysts. The photocatalysts displayed the anatase/rutile/brookite crystal phase mixture. The rutile and brookite phase contents increased with increasing iron content. On the other hand, increasing nitrogen content inhibited the formation of rutile and brookite phases and the catalysts displayed predominantly the anatase phase. High iron and low nitrogen contents led to the highest BET surface areas. The surface morphology changed from nanorice to spherical shape with increasing iron content. The bandgap energy of all Fe–N–TiO2 samples was in the range 2.7–3.1 eV, being lower than that of undoped TiO2 and pure anatase phase. Nitrogen was incorporated into the TiO2 lattice on interstitial positions (Ti–O–N). The iron, substituting some Ti4+ in the lattice was presented in Fe2+ and Fe3+ oxidation state, as confirmed by XANES measurements. The photocatalytic degradation of antibiotic ciprofloxacin was performed under visible light using a LED illumination source and nearly 70 % of the antibiotic was removed in 6 h by using the most active sample (2.5 %N–1.5 %Fe). As verified by photoluminescence results, the iron and nitrogen dopants synergistically enhanced the charge separation, since they promoted the formation of the different TiO2 phases.