Nowadays, the increased agro-industrial activities and the inability of traditional wastewater treatment plants (WWTPs) to eliminate recalcitrant organic contaminants are raising a potential worldwide risk for the environment. Among the various advanced water treatment technologies that are lately proposed for addressing this challenge, the development and optimization of an innovative hybrid photocatalytic nanofiltration reactor (PNFR) prototype emerges as a prominent solution that achieves synergistic beneficial effects between the photocatalytic degradation activity and size exclusion capacity for micropollutant molecules. Both these features can be contemporarily endued to a multitude of membrane monoliths. The physicochemical and the photoinduced decontamination properties of the titania materials were firstly determined in the powder form, and subsequently, the structural and morphological characterization of the obtained titania-modified membrane monoliths were accomplished. The PNFR unit can operate at high water recovery and low pressures, exhibiting promising removal efficiencies against Acetamiprid (ACT) and Thiabendazole (TBZ) pesticides and achieving the recycling of 15 m³/day of real agro-wastewater. The obtained results are very encouraging, demonstrating the integration of titania photocatalysts in a photocatalytic membrane reactor as a feasible technological solution for the purification of agricultural wastewater.

In the present work, Pebax-1657, a commercial multiblock copolymer (poly(ether-block-amide)), consisting of 40% rigid amide (PA6) groups and 60% flexible ether (PEO) linkages, was selected as the base polymer for preparing dense flat sheet mixed matrix membranes (MMMs) using the solution casting method. Carbon nanofillers, specifically, raw and treated (plasma and oxidized) multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) were incorporated into the polymeric matrix in order to improve the gas-separation performance and polymer’s structural properties. The developed membranes were characterized by means of SEM and FTIR, and their mechanical properties were also evaluated. Well-established models were employed in order to compare the experimental data with theoretical calculations concerning the tensile properties of MMMs. Most remarkably, the tensile strength of the mixed matrix membrane with oxidized GNPs was enhanced by 55.3% compared to the pure polymeric membrane, and its tensile modulus increased 3.2 times compared to the neat one. In addition, the effect of nanofiller type, structure and amount to real binary CO₂/CH₄ (10/90 vol.%) mixture separation performance was evaluated under elevated pressure conditions. A maximum CO₂/CH₄ separation factor of 21.9 was reached with CO₂ permeability of 384 Barrer. Overall, MMMs exhibited enhanced gas permeabilities (up to fivefold values) without sacrificing gas selectivity compared to the corresponding pure polymeric membrane.

Novel V₂O₅ bifunctional photocatalysts were prepared following a wet chemical process with the addition of anionic or non-ionic surfactants into the precursor solution and further heating under reflux. Detailed characterization and investigation of the relevant light-matter interactions proved that surfactants addition had a strong impact on the morphology, while also affecting the crystallinity, the optoelectronic properties, and the surface chemistry of the novel photocatalysts. The most efficient photocatalyst (T80) was based on tween 80, a surface-active agent employed for the first time in the synthesis of vanadium oxide materials. T80 presented crystalline nature without structural defects, which are usually centers of e⁻ − h⁺ recombination. This material also exhibited small crystal size, high porosity, and short migration paths for the charge carriers, enabling their effective separation during photocatalysis. Under UV light illumination, T80 was capable to reduce hexavalent chromium to trivalent up to 70% and showed high yields in degrading methylene blue azo-dye and tetracycline antibiotic water pollutants. This remarkably high bifunctional performance defines T80 as a promising and capable photocatalytic material for both advanced oxidation and reduction processes (AOPs-ARPs).

It is well known that water inside hydrophobic nano-channels diffuses faster than bulk water. Recent theoretical studies have shown that this enhancement depends on the size of the hydrophobic nanochannels. However, experimental evidence of this dependence is lacking. Here, by combining two-dimensional nuclear magnetic resonance diffusion–relaxation ($D$ –$T_{2eff}$ ) spectroscopy in the stray field of a superconducting magnet and molecular dynamics simulations, we analyze the size dependence of water dynamics inside Carbon Nanotubes (CNTs) of different diameters ($1.1$ –$6.0$ nm), in the temperature range of $265$ –$305$ K. Depending on the CNT diameter, the nanotube water is shown to resolve in two or more tubular components acquiring different self-diffusion coefficients. Most notably, a favorable CNT diameter range ($3.0$ –$4.5$ nm) is experimentally verified for the first time, in which water molecule dynamics at the center of the CNTs exhibits distinctly non-Arrhenius behavior, characterized by ultrafast diffusion and extraordinary fragility, a result of significant importance in the efforts to understand water behavior in hydrophobic nanochannels.

Pesticide residues, when present in agricultural wastewater, constitute a potential risk for the environment and human health. Hence, focused actions for their abatement are of high priority for both the industrial sectors and national authorities. This work evaluates the effectiveness of the photocatalytic process to decompose two frequently detected pesticides in the water effluents of the fruit industry: thiamethoxam-a neonicotinoid compound and flonicamid-a pyridine derivative. Their photocatalytic degradation and mineralization were evaluated in a lab-scale photocatalytic batch reactor under UV-A illumination with the commercial photocatalyst Evonik P25 TiO₂ by employing different experimental conditions. The complete degradation of thiamethoxam was achieved after 90 min, when the medium was adjusted to natural or alkaline pH. Flonicamid was proven to be a more recalcitrant substance and the removal efficiency reached ~50% at the same conditions, although the degradation overpassed 75% in the acidic pH medium. Overall, the pesticides’ degradation follows the photocatalytic reduction pathways, where positive charged holes and hydroxyl radicals dominate as reactive species, with complete mineralization taking place after 4 h, regardless of the pH medium. Moreover, it was deduced that the pesticides’ degradation kinetics followed the Langmuir-Hinshelwood (L-H) model, and the apparent rate constant, the initial degradation rate, as well as the L-H model parameters, were determined for both pesticides.