Tailoring metal oxide photocatalysts in the form of heterostructured photonic crystals has spurred particular interest as an advanced route to simultaneously improve harnessing of solar light and charge separation relying on the combined effect of light trapping by macroporous periodic structures and compositional materials’ modifications. In this work, surface deposition of FeOx nanoclusters on TiO2 photonic crystals is investigated to explore the interplay of slow-photon amplification, visible light absorption, and charge separation in FeOx–TiO2 photocatalytic films. Photonic bandgap engineered TiO2 inverse opals deposited by the convective evaporation-induced co-assembly method were surface modified by successive chemisorption-calcination cycles using Fe(III) acetylacetonate, which allowed the controlled variation of FeOx loading on the photonic films. Low amounts of FeOx nanoclusters on the TiO2 inverse opals resulted in diameter-selective improvements of photocatalytic performance on salicylic acid degradation and photocurrent density under visible light, surpassing similarly modified P25 films. The observed enhancement was related to the combination of optimal light trapping and charge separation induced by the FeOx–TiO2 interfacial coupling. However, an increase of the FeOx loading resulted in severe performance deterioration, particularly prominent under UV-Vis light, attributed to persistent surface recombination via diverse defect d-states.
Heterojunction formation between BiVO4 nanomaterials and benchmark semiconductor photocatalysts has been keenly pursued as a promising approach to improve charge transport and charge separation via interfacial electron transfer for the photoelectrocatalytic degradation of recalcitrant pharmaceutical pollutants. In this work, a heterostructured TiO2/Mo-BiVO4 bilayer photoanode was fabricated by the deposition of a mesoporous TiO2 overlayer using the benchmark P25 titania catalyst on top of Mo-doped BiVO4 inverse opal films as the supporting layer, which intrinsically absorbs visible light below 490 nm, while offering improved charge transport. A porous P25/Mo-BiVO4 bilayer structure was produced from the densification of the inverse opal underlayer after post-thermal annealing, which was evaluated on photocurrent generation in aqueous electrolyte and the photoelectrocatalytic degradation of the refractory anti-inflammatory drug ibuprofen under back-side illumination by visible and UV–Vis light. Significantly enhanced photoelectrochemical performance on both photocurrent density and pharmaceutical degradation was achieved for the bilayer structure with respect to the additive effect of the constituent layers, which was related to the improved light harvesting arising from the backscattering by the mesoporous TiO2 layer in combination with the favorable charge transfer at the TiO2/Mo-BiVO4 interface.
This study highlights the effectiveness of photocatalytically modified ceramic ultrafiltration (UF) membranes in alleviating two major drawbacks of membrane filtration technologies. These are the generation of a highly concentrated retentate effluent as a waste stream and the gradual degradation of the water flux through the membrane due to the accumulation of organic pollutants on its surface. The development of two types of novel tubular membranes, featuring photocatalytic Mo-BiVO4 inverse opal coatings, demonstrated a negligible impact on water permeance, ensuring consistent filtration and photocatalytic efficiency and suggesting the potential for maintaining membrane integrity and avoiding the formation of highly concentrated retentate effluents. Morphological analysis revealed well-defined coatings with ordered domains and interconnected macropores, confirming successful synthesis of Mo-BiVO4. Raman spectroscopy and optical studies further elucidated the composition and light absorption properties of the coatings, particularly within the visible region, which is vital for photocatalysis driven by vis-light. Evaluation of the tetracycline removal efficiency presented efficient adsorption onto membrane surfaces with enhanced photocatalytic activity observed under both UV and vis-light. Additionally, vis-light irradiation facilitated significant degradation, showcasing the versatility of the membranes. Total Organic Carbon (TOC) analysis corroborated complete solute elimination or photocatalytic degradation without the production of intermediates, highlighting the potential for complete pollutant removal. Overall, these findings emphasize the promising applications of Mo-BiVO4 photocatalytic membranes in sustainable water treatment and wastewater remediation processes, laying the groundwork for further optimization and scalability in practical water treatment systems.