Summary: | The determination of reaction pathways and identification of products of pollutants degradation is central to photocatalytic environmental remediation. This work focuses on the photocatalytic degradation of the herbicide Imazapyr (2-(4-methyl-5-oxo-4-propan-2-yl-1H-imidazol-2-yl) pyridine-3-carboxylic acid) under UV-Vis and visible-only irradiation of aqueous suspensions of Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub>, and on the identification of the corresponding degradation pathways and reaction intermediates. Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> was formed by mixing Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i> and TiO<sub>2</sub> by mechanical grinding followed by annealing at 500 °C. A complete structural characterization of Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> was carried out. The photocatalytic activity of the hetero-nanostructures was determined using phenol and Imazapyr herbicide as model pollutants in a stirred tank reactor under UV-Vis and visible-only irradiation. Using equivalent loadings, Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> showed a higher rate (10.6 μM·h<sup>−1</sup>) as compared to unmodified TiO<sub>2</sub> (7.4 μM·h<sup>−1</sup>) for Imazapyr degradation under UV-Vis irradiation. The mineralization rate was 4.07 µM·h<sup>−1</sup> for Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> and 1.21 μM·h<sup>−1</sup> for TiO<sub>2</sub>. In the Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> system, the concentration of intermediate products reached a maximum at 180 min of irradiation that then decreased to a half in 120 min. For unmodified TiO<sub>2</sub>, the intermediates continuously increased with irradiation time with no decrease observed in their concentration. The enhanced efficiency of the Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub> for the complete degradation of the Imazapyr and intermediates is attributed to an increased adsorption of polar species on the surface of Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>. Based on LC-MS, photocatalytic degradation pathways for Imazapyr under UV-Vis irradiation have been proposed. Some photocatalytic degradation was obtained under visible-only irradiation for Ca<i><sub>x</sub></i>MnO<i><sub>y</sub></i>-TiO<sub>2</sub>. Hydroxyl radicals were found to be main reactive oxygen species responsible for the photocatalytic degradation through radical scavenger investigations.
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