Experimental and computational studies of photoelectrochemical degradation of atrazine by modified nanoporous titanium dioxide

The presence of herbicides like Atrazine (ATZ) in groundwater from non-target runoff of the agriculture industry becomes a big concern due to its potential negative impacts on the environment and human health. The use of advanced oxidative processes (AOP) to remove harmful contaminants has been shown to be effective for wastewater treatment. Herein, we report on an advanced photoelectrochemical (PEC) approach based on electrochemically modified nanoporous TiO2 electrode for efficient degradation of ATZ. The electrochemical treated TiO2 electrodes were shown to have a six-fold increase in the photo-current density over the untreated ones. This increase in PEC activity was attributed to the increase in Ti3+ sites after the electrochemical modification, which was corroborated by low-temperature electron paramagnetic resonance (EPR) studies. The removal of ATZ by the PEC process resulted in a rate constant of 1.91 × 10−3 s−1, compared to 3.12 × 10−4 s−1 obtained by a strictly photocatalytic process. Liquid-Chromatography Mass-Spectrometric measurements showed the modified TiO2 electrodes highly effective at removing ATZ, with 96.1% removed after 10 h. Monitoring of the common degradation products desethyl atrazine (DEA), desisopropyl atrazine (DIA) and desethyl desisopropyl atrazine (DDA) revealed very low concentrations throughout the degradation process, indicating that further degradation was achieved. Quantum mechanical-based test for overall free radical scavenging activity (QM-ORSA) computational studies were performed and a mechanism for the N-dealkylation processes of ATZ has been proposed. [Display omitted] •Herbicides like atrazine can be very stable and persist in the environment and waterways.•Photoelectectrocatalysis can be used to break down herbicides.•The degradation process could be complicated and hard to monitor.•Computational investigations can help understand the breakdown mechanism.•Nanoporous TiO2 exhibits high efficacy for the photoelectrochemical removal of atrazine.