Membrane filtration is an effective technique for separating micro- and nano-sized oil droplets from harmful oil-contaminated waters produced by numerous industrial activities. However, significant flux reduction discourages the extensive application of this technology; therefore, developing antifouling membranes is necessary. For this purpose, various titanium dioxide/carbon nanotube (TiO₂/CNT) nanocomposites (containing 1, 2, and 5 wt.% multi-walled CNTs) were used for the modification of polyvinylidene fluoride (PVDF) ultrafilter (250 kDa) membrane surfaces. The effects of surface modifications were compared in relation to the flux, the filtration resistance, the flux recovery ratio, and the purification efficiency. TiO₂/CNT_2% composite modification reduced both irreversible and total filtration resistances the most during the filtration of 100 ppm oil emulsions. The fluxes were approximately 4–7 times higher compared to the unmodified PVDF membrane, depending on the used transmembrane pressure (510, 900, and 1340 L/m²h fluxes were measured at 0.1, 0.2, and 0.3 MPa pressures, respectively). Moreover, the flux recovery ratio (up to 68%) and the purification efficiency (95.1–99.8%) were also significantly higher because of the surface modification, and the beneficial effects were more dominant at higher transmembrane pressures. TiO₂/CNT_2% nanocomposites are promising to be applied to modify membranes used for oil–water separation and achieve outstanding flux, cleanability, and purification efficiency.

Membrane separation processes are promising methods for wastewater treatment. Membrane fouling limits their wider use; however, this may be mitigated using photocatalytic composite materials for membrane preparation. This study aimed to investigate photocatalytic polyvinylidene fluoride (PVDF)-based nanocomposite membranes for treating model dairy wastewater containing bovine serum albumin (BSA). Membranes were fabricated via physical coating (with TiO₂, and/or carbon nanotubes, and/or BiVO₄) and blending (with TiO₂). Another objective of this study was to compare membranes of identical compositions fabricated using different techniques, and to examine how various TiO₂ concentrations affect the antifouling and cleaning performances of the blended membranes. Filtration experiments were performed using a dead-end cell. Filtration resistances, BSA rejection, and photocatalytic cleanability (characterized by flux recovery ratio (FRR)) were measured. The surface characteristics (SEM, EDX), roughness (measured by atomic force microscopy, AFM), wettability (contact angle measurements), and zeta potential of the membranes were also examined. Coated PVDF membranes showed higher hydrophilicity than the pristine PVDF membrane, as evidenced by a decreased contact angle, but the higher hydrophilicity did not result in higher fluxes, unlike the case of blended membranes. The increased surface roughness resulted in increased reversible fouling, but decreased BSA retention. Furthermore, the TiO₂-coated membranes had a better flux recovery ratio (FRR, 97%) than the TiO₂-blended membranes (35%). However, the TiO₂-coated membrane had larger total filtration resistances and a lower water flux than the commercial pristine PVDF membrane and TiO₂-blended membrane, which may be due to pore blockage or an additional coating layer formed by the nanoparticles. The BSA rejection of the TiO₂-coated membrane was lower than that of the commercial pristine PVDF membrane. In contrast, the TiO₂-blended membranes showed lower resistance than the pristine PVDF membrane, and exhibited better antifouling performance, superior flux, and comparable BSA rejection. Increasing the TiO₂ content of the TiO₂-blended membranes (from 1 to 2.5%) resulted in increased antifouling and comparable BSA rejection (more than 95%). However, the effect of TiO₂ concentration on flux recovery was negligible.

This study aimed to investigate the performance of composite photocatalytic membranes fabricated by incorporating multiple nanoparticles (TiO₂, carbon nanotubes, BiVO₄) into polyvinylidene fluoride membrane material for real dairy wastewater treatment. The composite photocatalytic membranes exhibited superior antifouling behavior, lower filtration resistance, better flux, and higher flux recovery ratio than the pristine membrane. Salinity, pH, and lactose concentration are determinant factors that affect filtration resistance and rejection performance during the ultrafiltration of dairy wastewater. Generally, higher irreversible and total resistances and slightly lower chemical oxygen demand (COD) rejections were found at higher salinity (expressed by electric conductivity values of >4 mS/cm) than lower salinity (<4 mS/cm) levels. The presence of lactose in dairy wastewater increased irreversible resistance and severely reduced COD rejection during ultrafiltration due to the ability of lactose to pass through the membranes. It was ascertained that membranes require further treatment after filtrating such wastewater. Lower resistances and slightly better COD rejections were observed at pH 7.5 and pH 9.5 compared to those observed at pH 4. Photocatalytic membranes fouled during the ultrafiltration of real dairy wastewater were regenerated by visible light irradiation. The membrane containing all constituents (i.e., TiO₂, carbon nanotubes, and BiVO₄) showed the best regeneration performance, exceeding that of the pristine membrane by 30%.

Non-solvent induced phase-inversion is one of the most used methods to fabricate membranes. However, there are only a few studies supported by statistical analysis on how the different fabrication conditions affect the formation and performance of membranes. In this paper, a central composite design was employed to analyze how different fabrication conditions affect the pure water flux, pore size, and photocatalytic activity of polyvinylidene fluoride (PVDF) membranes. Polyvinylpyrrolidone (PVP) was used to form pores, and titanium dioxide (TiO₂) to ensure the photocatalytic activity of the membranes. The studied bath temperatures (15 to 25 °C) and evaporation times (0 to 60 s) did not significantly affect the pore size and pure water flux of the membranes. The concentration of PVDF (12.5 to 17.5%) affected the viscosity, formation capability, and pore sizes. PVDF at high concentrations resulted in membranes with small pore sizes. PVP affected the pore size and should be used to a limited extent to avoid possible hole formation. TiO₂ contents were responsible for the decolorization of a methyl orange solution (10⁻⁵ M) up to 90% over the period studied (30 h). A higher content of TiO₂ did not increase the decolorization rate. Acidic conditions increased the photocatalytic activity of the TiO₂-membranes.

Six different TiO₂/CNT nanocomposite-coated polyvinylidene-fluoride (PVDF) microfilter membranes (including –OH or/and –COOH functionalized CNTs) were evaluated in terms of their performance in filtering oil-in-water emulsions. In the early stages of filtration, until reaching a volume reduction ratio (VRR) of ~1.5, the membranes coated with functionalized CNT-containing composites provided significantly higher fluxes than the non-functionalized ones, proving the beneficial effect of the surface modifications of the CNTs. Additionally, until the end of the filtration experiments (VRR = 5), notable flux enhancements were achieved with both TiO₂ (~50%) and TiO₂/CNT-coated membranes (up to ~300%), compared to the uncoated membrane. The irreversible filtration resistances of the membranes indicated that both the hydrophilicity and surface charge (zeta potential) played a crucial role in membrane fouling. However, a sharp and significant flux decrease (~90% flux reduction ratio) was observed for all membranes until reaching a VRR of 1.1–1.8, which could be attributed to the chemical composition of the oil. Gas chromatography measurements revealed a lack of hydrocarbon derivatives with polar molecular fractions (which can act as natural emulsifiers), resulting in significant coalescent ability (and less stable emulsion). Therefore, this led to a more compact cake layer formation on the surface of the membranes (compared to a previous study). It was also demonstrated that all membranes had excellent purification efficiency (97–99.8%) regarding the turbidity, but the effectiveness of the chemical oxygen demand reduction was slightly lower, ranging from 93.7% to 98%.

The accumulation of proteins in filter membranes limits the efficiency of filtering technologies for cleaning wastewater. Efforts are ongoing to coat commercial filters with different materials (such as titanium dioxide, TiO₂) to reduce the fouling of the membrane. Beyond monitoring the desired effect of the retention of biomolecules, it is necessary to understand what the biophysical changes are in water-soluble proteins caused by their interaction with the new coated filter membranes, an aspect that has received little attention so far. Using spin-label electron paramagnetic resonance (EPR), aided with native fluorescence spectroscopy and dynamic light scattering (DLS), here, we report the changes in the structure and dynamics of bovine serum albumin (BSA) exposed to TiO₂ (P25) nanoparticles or passing through commercial polyvinylidene fluoride (PVDF) membranes coated with the same nanoparticles. We have found that the filtering process and prolonged exposure to TiO₂ nanoparticles had significant effects on different regions of BSA, and denaturation of the protein was not observed, neither with the TiO₂ nanoparticles nor when passing through the TiO₂-coated filter membranes.