This work proposes an innovative integration of Membrane Distillation (MD) and photo-oxidation for a continuous recovery of water from arsenic (As) contaminated solutions coupled with the oxidation of arsenite (As(III)) into arsenate (As(V)). Polyvinylidene fluoride (PVDF) mixed matrix membranes (MMMs) containing titanium dioxide nanoparticles (TiO₂ NPs) as photocatalyst were developed. A systematic study elucidated the effect of TiO₂ NPs on membranes’ morphology prepared via non-solvent-induced phase separation (NIPS) using triethyl phosphate (TEP) as a green solvent for PVDF solubilization. Vacuum membrane distillation (VMD) tests carried out by irradiating the MMMs with ultraviolet (UV) radiation demonstrated the possibility of recovering up to 80 % of the water from As-contaminated synthetic and real multi-ions aqueous solutions from Sila Massif (Italy). The distillate was recovered at a rate of 6.9–7.2 kg·m⁻²·h⁻¹ (feed inlet temperature of 60 °C), while the presence of 7 wt% of TiO₂ in PVDF membranes enabled the photo-oxidation of 95 % of the As(III) to As(V) at a first order kinetic constant of 0.0106 min⁻¹. After 5 cycles of As-remediation experiments, post-hoc mechanical testing on the membrane suggested the emergence of polymer embrittlement induced by UV radiation (total irradiation time of 7.5 h), highlighting the urgent need for developing photocatalytic membranes with long-term stability. Overall, this study elucidates at laboratory scale the performance of a coupled and continuous Membrane Distillation (MD) and photo-oxidation system for arsenic (As) remediation, employing microporous hydrophobic green membranes doped with a photocatalyst.

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Water and energy are two strategic drivers of sustainable development, intimately interlaced and vital for a secure future of humanity. Given that water resources are limited, whereas global population and energy demand are exponentially growing, the competitive balance between these resources, referred to as the water-energy nexus, is receiving renewed focus. The desalination industry alleviates water stress by producing freshwater from saline sources, such as seawater, brackish or groundwater. Since the last decade, the market has been dominated by membrane desalination technology, offering significant advantages over thermal processes, such as lower energy demand, easy process control and scale-up, modularity for flexible productivity, and feasibility of synergic integration of different membrane operations. Although seawater reverse osmosis (SWRO) accounts for more than 70% of the global desalination capacity, it is circumscribed by some significant technological limitations, such as: (i) the relatively low water recovery factor (around 50%) due to the negative impact of osmotic and polarization phenomena; (ii) an energy consumption in the range of 3–5 kWh m−3, still far from the theoretical energy demand (1.1 kWh m−3) to produce potable water from seawater (at 50% water recovery factor). Ultimately, desalination is an energy intensive practice and research efforts are oriented toward the development of alternative and more energy-efficient approaches in order to enhance freshwater resources without placing excessive strain on limited energy supplies. Recent years have seen a relevant surge of interest in membrane distillation (MD), a thermally driven membrane desalination technology having the potential to complement SWRO in the logic of Process Intensification and Zero Liquid Discharge paradigm. Due to its peculiar transport mechanism and negligibility of osmotic phenomena, MD allows high-quality distillate production (theoretically, non-volatile species are completely rejected) with a recovery factor of up to 80% at a relatively low operative temperature (typically 60 °C–80 °C). Although low operative temperatures make MD technology attractive for renewable power applications (e.g. solar thermal, wind or geothermal energy sources) or for efficient exploitation of low-grade or waste heat streams, the low energy efficiency intrinsically due to heat losses—and specifically to temperature polarization—has so far hindered the application at industrial scale. Nowadays, photothermal materials able to absorb and convert natural or artificial irradiation into heat have gained great attention, demonstrating the potential to mitigate the 'anthropic' energy input to MD and to mitigate the impact of thermal inefficiencies. On this road, a step-change improvement in light-to-heat conversion is expected through high-throughput computational screening over thermoplasmonic materials based on electronic and optical properties of advanced materials including novel topological phases of matter used as nanofillers in polymeric membranes. Coherently with the concept of Circular Economy, waste hypersaline solutions rejected from desalination process (referred as 'brine') are now the subject of valorization activities along two main exploitation routes: (1) recovery of valuable minor and trace metals and minerals, with special focus on critical raw materials (including, among others, Mg, Na, Ca, K, Sr, Li, Br, B, and Rb); (2) production of salinity gradient power (SGP) renewable energy resulting from the recovery of the Gibbs energy of mixing (mainly represented by the entropic contribution) of two solutions having different ionic concentration. The exciting new frontier of sustainable mining of seawater concentrates is accelerating the appearance of a plethora of innovative membrane materials and methods for brine dehydration and selective extraction of trace ions, although under the sword of Damocles represented by cost feasibility for reliable commercial application. On the other hand, among several emerging technologies, reverse electrodialysis (SGP-RED) was already proven capable—at least at the kW scale–of turning the chemical potential difference between river water, brackish water, and seawater into electrical energy. Efforts to develop a next generation of ion exchange membranes exhibiting high perm-selectivity (especially toward monovalent ions) and low electrical resistance, to improve system engineering and to optimize operational conditions, pursue the goal of enhancing the low power density so far achievable (in the order of a few W per m2). This Roadmap takes the form of a series of short contributions written independently by worldwide experts in the topic. Collectively, such contributions provide a comprehensive picture of the current state of the art in membrane science and technology at the water-energy nexus, and how it is expected to develop in the future. In addition, this Roadmap acknowledges the challenges and advances in membrane systems, particularly emphasizing the interplay of material innovation and system optimization, which collectively contribute to advancing the desalination field within the water-energy nexus framework.@en