Degradation study of malachite green on chitosan films containing heterojunctions of melon/TiO2 absorbing visible-light in solid-gas interfaces

Abstract

Urea modified TiO2 nanoparticles were synthesized at different TiO2: urea ratios (10, 30 and 60 (%wt) named UTiO2-10, 30 and 60) by sol-gel method and annealing at 400 °C during 1 h. Characterization revealed the presence of TiO2 nanoparticles with visible light absorption (between 400 and 500 nm) probably due by the formation of thermolysis urea byproducts such as melon, which may induce a TiO2/melon heterojunction. Then, modified nanoparticles were immobilized on chitosan films by adding 30% (70QS/30UTiO2) and 50% 50QS/50UTiO2) of UTiO2 nanoparticles. Functionalized films were characterized by SEM-EDS, DRS and AFM. Photo-induced degradation of malachite green stains was evaluated on these films under different wavelengths. Upon UV-A + visible light irradiation, films showed good activity even slightly better than those containing Evonik P-25 (70QS/30P-25). Upon visible light between 450 and 800 nm, films evidenced a satisfactory performance but slower than under UV-A + visible light irradiation whereas the photobleaching activity of 70QS/30P-25 was very poor. When visible light irradiation with wavelengths higher than 590 nm was used, a slight photobleaching was also observed. DRS spectra taken at different irradiation times showed that dye underwent N-demethylated oxidative reactions either upon UV–vis or visible light irradiation. ATR-FTIR measurements revealed the generation of benzophenones after 6 h of irradiation probably suggesting the formation of singlet oxygen under visible light. 70QS/30UTiO2-10 films showed a good photo-bleaching activity after 18 h of continuous UV-A + visible light irradiation.