The photocatalytic efficiency of TiO₂ was significantly enhanced by coupling with WO₃ to form a TiO₂/WO₃ heterostructure, designed to operate effectively under UV-LED irradiation. The nanocomposites were synthesized via a hydrothermal route, and their activity was evaluated through the degradation of the pharmaceutical pollutant venlafaxine. Contaminants are rarely addressed in photocatalytic studies. Unlike a simple physical mixture of commercial TiO₂ and WO₃ powders, the hydrothermally synthesized TiO₂/WO₃ photocatalyst exhibited superior efficiency, attributable to its nanoscale dimensions achieved via the hydrothermal route, which promoted improved charge carrier separation, enhanced surface homogeneity, and the formation of an effective heterojunction interface. An optimization study varying the WO₃ content (5, 10, 20, and 30 wt.%) within the TiO₂ revealed that the 10 wt.% WO₃ composition achieved the highest performance, with ~52% venlafaxine degradation within 60 min. SEM, TEM, FTIR, Raman spectroscopy, XRD, and UV-Vis DRS revealed the successful incorporation of WO3 into the TiO₂ matrix, confirming phase purity and composition-dependent structural evolution of the nanocomposite, and evidencing extended light absorption and superior charge-transfer properties. Importantly, the optimized photocatalyst thin film retained excellent stability and reusability, maintaining high degradation efficiency over three consecutive cycles with negligible activity loss, which avoids slurry separation. These findings establish hydrothermally synthesized TiO₂/10%WO₃ thin film heterostructures as effective and sustainable photocatalytic platforms for the removal of pharmaceutical pollutants in wastewater under UV-LED irradiation.

The detection of organic carbon in wastewater is essential for process monitoring and regulatory assessment. Yet conventional chemical oxygen demand (COD) and total organic carbon (TOC) methods remain reagent-dependent, slow, and unsuitable for inline operation. Photoelectrochemical (PEC) sensing based on TiO₂ offers a reagent-free alternative, but its response to wastewater-relevant dissolved organic matter (DOM) and real effluent matrices is still poorly understood. In this study, a TiO₂-based PEC system was systematically evaluated using four representative model compounds—glucose, potassium hydrogen phthalate, L-tryptophan, and urea—covering major fractions typically present in municipal wastewater. For the first time, representative wastewater-associated organic compound classes, conductivity effects, and the transferability of the PEC response to real wastewater effluent were systematically investigated. The photocurrent response showed distinct, highly linear concentration–signal relationships for each substance, suggesting a dominant contribution of surface-associated electronic effects. Conductivity variations across a relevant range had no measurable influence on sensitivity or photocurrent magnitude, indicating that the PEC response is not governed by bulk ionic transport but primarily is an interfacial process at the site of TiO₂. When applied to real wastewater effluent, the sensor exhibited an excellent linear correlation with dilution level (R² = 0.9954), demonstrating a linear response within a defined matrix and an LOD of 1.12 mg L⁻¹ COD. For the investigated model compounds, LOD values ranged from 1.06 to 3.00 mg L⁻¹ COD, while a linear response was maintained up to approximately 80–100 mg L⁻¹ COD. These findings establish TiO₂-based PEC sensing as a promising platform for the reagent-free, online monitoring of organic loads in wastewater treatment.