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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  x  MnO  y  -TiO 2 , and on the identification of the corresponding degradation pathways and reaction intermediates. Ca  x  MnO  y  -TiO 2 was formed by mixing Ca  x  MnO  y  and TiO 2 by mechanical grinding followed by annealing at 500 °C. A complete structural characterization of Ca  x  MnO  y  -TiO 2 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  x  MnO  y  -TiO 2 showed a higher rate (10.6 μM·h -1 ) as compared to unmodified TiO 2 (7.4 μM·h -1 ) for Imazapyr degradation under UV-Vis irradiation. The mineralization rate was 4.07 µM·h -1 for Ca  x  MnO  y  -TiO 2 and 1.21 μM·h -1 for TiO 2 . In the Ca  x  MnO  y  -TiO 2 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 2 , the intermediates continuously increased with irradiation time with no decrease observed in their concentration. The enhanced efficiency of the Ca  x  MnO  y  -TiO 2 for the complete degradation of the Imazapyr and intermediates is attributed to an increased adsorption of polar species on the surface of Ca  x  MnO  y  . 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  x  MnO  y  -TiO 2 . Hydroxyl radicals were found to be main reactive oxygen species responsible for the photocatalytic degradation through radical scavenger investigations.

nanomaterials

Enhanced Photocatalytic Degradation of the Imidazolinone Herbicide Imazapyr upon UV/Vis Irradiation in the Presence of CaxMnOy-TiO2 Hetero-Nanostructures: Degradation Pathways and Reaction Intermediates