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This study aims the development of photoelectrodes to be incorporated in a photoelectrocatalytic ozonation (PECO) process for tertiary treatment of urban wastewaters, targeting the removal of contaminants of emerging concern (CEC). PECO tests were performed using urban wastewater after secondary treatment fortified with Cefadroxil (CFX, C 16 H 17 N 3 O 5 S), as target model CEC. Three Nitrogen and Carbon doped TiO 2 (CN-TiO 2 ) electrodes were synthesized by anodizing at 50, 70, and 90 V, and calcined. These materials were characterized by X-Ray diffraction and Rietveld refinement, Scanning Electron Microscopy, Diffuse Reflectance Spectroscopy, X-ray photoelectron spectroscopy, chronoamperometry, and electrochemical impedance spectroscopy, to correlate defects with photoactivity. All photoanodes considerably reduced their main bandgaps by the incorporation of C and N species, to enable absorption capacities in the UV region using a Xe lamp. The lowest oxygen vacancy content and largest crystallite size were found for CN-TiO 2 -70, favoring the reduction of bulk defects that could act as recombination of charge carriers. Therefore, oxygen vacancies affect more the TiO 2 photoactivity compared to the crystallite size or the light absorption capacity, confirming that a lower content of vacancies in the material bulk and surface doping significantly influence the activity as detected by Rietveld refinement, DRS, and XPS. The electrochemical techniques confirm that the highest photocurrent was obtained for CN-TiO 2 -70, whence this photoanode was chosen to carry out the CFX degradation. A point defect model simulating Nyquist plot reveals that the photoactivity depends on the speed to diffuse oxygen vacancies through the TiO 2 coating. All abatement processes were followed by high-performance liquid chromatography, and Total Organic Carbon (TOC). At neutral and alkaline conditions, CFX is eliminated to levels below the analytical detection limit after 90 min of treatment (TOC removals of 87 and 91%, respectively), indicating that the coupling between the CN-TiO 2 -70 photocatalyst and ozone is effective in eliminating the contaminant due to parallel routes forming • OH species. Lower CFX degradation observed at acidic pH (TOC removal of 70%) is assigned to the difficulty of oxidizing protonated CFX species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this study, composite material films of pyridine-based polymer and metal oxides (ZnO and TiO 2 ) were successfully deposited by spin coating method for environmental remediation. Firstly, the polymers poly(2-vinylpyridine) P(2-VP), and poly(4-vinylpyridine) P(4-VP) were synthesized via solution polymerization. The analysis by grazing incidence X-ray diffraction (GIXRD) reveals semicrystalline nature and scanning electron microscopy (SEM) indicates that the poly(vinylpyridines) clusters of particles were observed on the surface of the films. It was also shown that the morphology of composite materials is completely dependent on the chemical nature of the oxide. In the case of P(2-VP)-TiO 2 and P(4-VP)-TiO 2 , some channels or pathways of TiO 2 on the surface of films were observed. However, the surface morphology of the polymer composites formulated with ZnO shows a homogeneous distribution in P(2-VP) and P(4-VP) matrix. The effectiveness of the composite materials in the photodegradation of methyl orange (MO) was evaluated by photocatalysis. According to the results, the P(4-VP)-ZnO composite exhibited the highest photodegradation of MO, allowing the separation of photogenerated species required for the photocatalytic reaction. The P(4-VP)-ZnO composite was also tested in benzoic acid (BA) photodegradation in water. The presence of some scavengers in the reaction system reveals that hydroxyl radicals (OH•), superoxide radicals (O 2 -•) and holes (h+) are responsible for the BA reduction by photocatalysis.