Photodegradation kinetics and halogens release of the emerging concern pollutants dexamethasone and S-metolachlor on TiO2/rGO composites.

This work studies the photocatalytic degradation of solutions containing 0.11 mM of a glucocorticoid (dexamethasone, DEX) and 0.11 mM of an herbicide (S-metolachlor, MTLC), organohalogenated compounds containing fluorine and chlorine atoms in their molecules, respectively. To treat 1 L volume, a mass of 0.5 g of TiO2/rGO composite in suspension has been used as photocatalyst, irradiated with UV-A LEDs with 200 W m-2 of irradiance. MTLC is partially adsorbed on the surface of the catalyst, while DEX is not adsorbed, showing different degradation kinetics. The halogen ions released into the solution from the breakage of the parent molecules, F- and Cl- respectively, were analysed. In the case of MTLC, the released Cl- followed two different kinetic trends, being faster, and with a rate that matched the rate of MTLC disappearance, the part corresponding to non-adsorbed MTLC. In the experiments with DEX solutions a different behaviour was observed; the released F- in the photocatalytic degradation was partially adsorbed on the catalyst surface, but the adsorption capacity decreased with the use of the photocatalyst in consecutive cycles until the solubilised F- matched the degraded concentration of DEX. Furthermore, the mass balance between the degraded contaminant and the solubilised halogen anion, for both contaminants, allowed to conclude the absence of halogenated intermediates under the final operating conditions, that is a remarkable outcome in water remediation processes.

Performance of TiO2-Based Tubular Membranes in the Photocatalytic Degradation of Organic Compounds.

This work presents the photocatalytic degradation of organic pollutants in water with TiO2 and TiO2/Ag membranes prepared by immobilising photocatalysts on ceramic porous tubular supports. The permeation capacity of TiO2 and TiO2/Ag membranes was checked before the photocatalytic application, showing high water fluxes (≈758 and 690 L m-2 h-1 bar-1, respectively) and <2% rejection against the model pollutants sodium dodecylbenzene sulfonate (DBS) and dichloroacetic acid (DCA). When the membranes were submerged in the aqueous solutions and irradiated with UV-A LEDs, the photocatalytic performance factors for the degradation of DCA were similar to those obtained with suspended TiO2 particles (1.1-fold and 1.2-fold increase, respectively). However, when the aqueous solution permeated through the pores of the photocatalytic membrane, the performance factors and kinetics were two-fold higher than for the submerged membranes, mostly due to the enhanced contact between the pollutants and the membranes photocatalytic sites where reactive species were generated. These results confirm the advantages of working in a flow-through mode with submerged photocatalytic membranes for the treatment of water polluted with persistent organic molecules, thanks to the reduction in the mass transfer limitations.

Shedding light on the performance of magnetically recoverable TiO2/Fe3O4/rGO-5 photocatalyst. Degradation of S-metolachlor as case study.

Recalcitrant contaminants are not usually removed in conventional wastewater treatment plants. Therefore, they are transferred to the water resources that receive treated wastewaters and their presence can cause health and environmental issues. Herbicides are among these compounds. In particular, S-metolachlor (MTLC) is specifically of high concern because its molecule incorporates a chlorine atom that contributes to its toxicity. For its removal, a magnetically recoverable photocatalyst, TiO2/Fe3O4/rGO-5, was synthesised following a hydrothermal method. The performance of TiO2/Fe3O4/rGO-5 has been experimentally assessed and compared to TiO2 and TiO2/rGO-5 catalysts. A characterisation of the materials properties was carried out including adsorption isotherms of MTLC that provided the maximum adsorption capacity of the materials (qm), being 140.85 ± 5.14 mg g-1 for TiO2/Fe3O4/rGO-5. Furthermore, the ternary composite exhibited good recoverability from liquid media after four consecutive cycles thanks to its magnetic character (magnetic saturation of 13.85 emu g-1). Photocatalytic degradation of MTLC started after a dark adsorption step following first order kinetics (0.0197 ± 1.2 × 10-4 min-1 for the degradation of 100 mg L-1 of MTLC with 0.5 g L-1 of TiO2/Fe3O4/rGO-5) similar to the rate of appearance of chloride in solution; after total removal of the solubilized MTLC the chloride concentration in the solution continued increasing with zero-th order kinetics up to the value corresponding to the total MTLC concentration. This second step in the chloride formation was attributed to the degradation of adsorbed MTLC. Specific experiments in the presence of scavengers of reactive oxygen species (ROS) were carried out shedding light on the degradation mechanisms. It was concluded the predominant role of free hydroxyl radicals in the photocatalytic degradation in all the investigated materials, whereas the presence of rGO in the composite photocatalysts improved their electronic conductivity, enhancing the activity of superoxide radicals. The results of this work provide important information for further development of photocatalysis.