In this study, we developed a glycerol-mediated safe and facile method to synthesize colored titania nanoparticles (NPs) via solution route. Our method is considerably effective and greener than other options currently available. Colored titania NPs were produced by hydrolyzing TiCl4 precursor in aqueous solution containing different concentrations of glycerol (0.0, 1.163, 3.834, and 5.815 mol/L) and subsequent calcination at 300 °C for 1 h. Our results highlight firstly that glycerol-mediated synthesis is unlikely to affect the anatase crystalline structure of TiO2, and secondly, that it would lead to coloration, band gap narrowing, and a remarkable bathochromic redshift of the optical response of titania. More importantly, the synthesized colored titania have Ti3+ ions, which, at least in terms of our samples, is the major factor responsible for its coloration. These Ti3+ species could induce mid gap states in the band gap, which significantly improve the visible light absorption capability and photocatalytic performance of the colored titania. The photocatalytic experiments showed that the colored TiO2 NPs prepared in 1.163 mol/L aqueous glycerol solution displayed the best photocatalytic performance. Almost 48.17% of phenolic compounds and 62.18% of color were removed from treated palm oil mill effluent (POME) within 180 min of visible light irradiation.
Tuning the characteristics of solvents to fit industrial requirements has currently become a major interest in both academic and industrial communities, notably in the field of room temperature ionic liquids (RTILs), which are considered one of the most promising green alternatives to molecular organic solvents. In this work, several sets of imidazolium-based ionic liquids were synthesized, and their toxicities were assessed towards four human pathogens bacteria to investigate how tunability can affect this characteristic. Additionally, the toxicity of particular RTILs bearing an amino acid anion was introduced in this work. EC50 values (50% effective concentration) were established, and significant variations were observed; although all studied ILs displayed an imidazolium moiety, the toxicity values were found to vary between 0.05 mM for the most toxic to 85.57 mM for the least toxic. Linear quantitative structure activity relationship models were then developed using the charge density distribution (σ-profiles) as molecular descriptors, which can yield accuracies as high as 95%.
The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO2 (both pristine and Ag-decorated), UV-A irradiation and 20 kHz pulsed ultrasound. Sonophotocatalytic tests were compared with photolysis, sonolysis, sonophotolysis, sonocatalysis and photocatalysis data performed in the same conditions. A synergy index of over 2 was determined for tests with pristine TiO2, while values close to 1.3 were observed for Ag-TiO2. Reaction intermediates were studied by HPLC-MS, showing degradation mechanisms activated by hydroxyl radicals. Similar pathways were identified for photocatalytic and sonophotocatalytic tests, although the latter led to more oxidized compounds. Different reactor configurations (static and dynamic set ups) were studied. Sequential and simultaneous application of UV light and ultrasound led to similar performance. The role of water matrix was investigated using ultrapure and drinking water, showing marked detrimental effects of electrolytes on the DC degradation. Overall, the combined treatment proved more efficient than photocatalysis alone especially in demanding working conditions, like in drinking water matrices.