Synergistic Sono-Enhanced Photocatalytic Degradation of Antibiotics: Unlocking the Potential of Heterojunctions and Piezoactive Composite Membranes

The remediation of contaminants of emerging concern (CECs) requires innovative, high-efficiency, and sustainable technologies. Here, we investigate active polymeric membranes incorporating TiO2/ZnO heterojunctions for synergistic sono-enhanced photocatalytic water treatment under both UV and visible-light irradiation. TiO2/ZnO composites were synthesized and characterized, confirming the formation of type II heterojunctions with tailored optical properties for sunlight-driven photocatalysis. The catalysts were integrated into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) matrixes using electrospinning (ES) and thermally induced phase separation (TIPS). ES membranes, specifically the ZnO-rich heterojunction within a PVDF-TrFE matrix (3T-7Z@TrFE ES), achieved the highest performance toward ciprofloxacin (CIP) degradation, reaching 71 and 57% under UV and visible light, respectively. The hybridization of the method by coupling ultrasound induced significant synergistic effects, with relative enhancement factors up to 1.38. Furthermore, the sono-enhanced photocatalytic pathway shifted the degradation mechanism towards the early fragmentation of the harmful piperazine ring, yielding a more sustainable degradation process. In addition, the composite membranes showed selective antibacterial activity against S. aureus, making this a multifunctional platform able not only to degrade CECs but also to mitigate membrane fouling. Overall, this work demonstrates the potential of tailored heterojunctions and composite membranes as sustainable platforms for the remediation of recalcitrant CECs in water, highlighting the synergy between photoactivity, piezoelectricity, and mechanistic control.