Degradation kinetics of isoproturon and its subsequent products in contact with TiO2 functionalized silica nanofibers

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2020-05, Vol.387, p.124143, Article 124143
• Main Authors: Loccufier, Eva, Deventer, Koen, Manhaeghe, Dave, Van Hulle, Stijn W.H., D'hooge, Dagmar R., De Buysser, Klaartje, De Clerck, Karen
• Format: Article
• Language: English
• Subjects: Electrospinning; Hydroxylation; Kinetic Monte Carlo modeling; Photodegradation kinetics; Respirometry; Water treatment
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2020.124143

[Display omitted] •Direct electrospinning of silica sol–gel results in a stable photocatalytic support.•Optimized TiO2 dip-coated silica nanofibers as reusable heterogeneous catalysts.•Kinetics of photocatalytic degradation products based on LC-MS and kMC modeling.•Hydroxylation as dominant reaction for several reaction steps and molecule locations.•Photocatalytic degradation restores aerobic biological activity of activated sludge. A challenge for the photodegradation of (organic) micro-pollutants in waste water treatment is the mechanistic and kinetic understanding beyond the degradation of the initial (parent) harmful product, e.g. the phenylurea herbicide isoproturon (IPU). By combining liquid chromatography–mass spectrometry and kinetic Monte Carlo modeling, we demonstrate that upon optimizing the dip-coating conditions (0.34 mol L−1 TiO2 solution at a coating speed of 160 mm min−1) for the functionalization of a superhydrophilic electrospun silica nanofibrous membrane (i) hydroxylation is a dominant reaction pathway and (ii) once IPU reacts on the surface of the TiO2 nanoparticles, further hydroxylation occurs sufficiently fast, with complete IPU removal under the detection limit (5–10 mg Lsolution−1) as a result of UV irradiation within 8 h. As hydroxylation is dominant, degradation intermediates with a higher water solubility are formed and therefore a decreased toxicity is obtained upon reintroducing the treated solution into the environment. This is confirmed by respirometry, with an increase in the oxygen uptake rate of an activated sludge from 5.9 mg O2 gactivated sludge−1h−1 for an untreated 10 mg L−1 IPU solution to 8.2 mg O2 gactivated sludge−1 h−1 for a solution irradiated for 8 h, in line with a blank solution.