In the last decades, the incorporation of copper in polymeric membranes for water treatment has received greater attention, as an innovative potential solution against biofouling formation on membranes, as well as, by its ability to improve other relevant membrane properties. Copper has attractive characteristics: excellent antimicrobial activity, high natural abundance, low cost and the existence of multiple cost-effective synthesis routes for obtaining copper-based materials with tunable characteristics, which favor their incorporation into polymeric membranes. This study presents a comprehensive analysis of the progress made in the area regarding modified membranes for water treatment when incorporating copper. The notable use of copper materials (metallic and oxide nanoparticles, salts, composites, metal-polymer complexes, coordination polymers) for modifying microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), forward osmosis (FO) and reverse osmosis (RO) membranes have been identified. Antibacterial and anti-fouling effect, hydrophilicity increase, improvements of the water flux, the rejection of compounds capacity and structural membrane parameters and the reduction of concentration polarization phenomena are some outstanding properties that improved. Moreover, the study acknowledges different membrane modification approaches to incorporate copper, such as, the incorporation during the membrane synthesis process (immobilization in polymer and phase inversion) or its surface modification using physical (coating, layer by layer assembly and electrospinning) and chemical (grafting, one-pot chelating, co-deposition and mussel-inspired PDA) surface modification techniques. Thus, the advantages and limitations of these modifications and their methods with insights towards a possible industrial applicability are presented. Furthermore, when copper was incorporated into membrane matrices, the study identified relevant detrimental consequences with potential to be solved, such as formation of defects, pore block, and nanoparticles agglomeration during their fabrication. Among others, the low modification stability, the uncontrolled copper ion releasing or leaching of incorporated copper material are also identified concerns. Thus, this article offers modification strategies that allow an effective copper incorporation on these polymeric membranes and solve these hinders. The article finishes with some claims about scaling up the implementation process, including long-term performance under real conditions, feasibility of production at large scale, and assessment of environmental impact.

Type of metal and metal-oxide NPs added to modify Thin-Film Composites Reverse Osmosis Membranes (TFC-RO) can alter their anti-biofouling properties by changing the dissolution process. The development of a mathematical model can facilitate the selection of these NPs. This work consists of a mathematical and experimental methodology to understand copper-based NPs dissolution of three copper species incorporated into TFC-RO membranes: Cu-NPs, CuO-NPs and Cu-Oligomer complexes formed in situ during the polymerization process. Biocidal capacity of copper species into the membrane was evaluated using colony forming unit method (CFU) over E. coli. In addition, copper ion release kinetics for both NPs and modified membranes were determined. A model based on the shrinking core model (SCM) was validated and applied to determine the limiting rate step in the dissolution process and simulate the ion release kinetics. Fitted curves reached a good adjustment with the experimental data, demonstrating the SCM can be applied to predict ion release process for copper-based NPs in suspension and the modified membranes. All membranes reached similar inhibition rate >50%, however, differences in the dissolution level of copper-based NPs in membrane were noted, suggesting a dual-type effect that defined the copper toxicity into the membrane, associated to the dissolution capacity and ROS production.

The influence of the lateral size and the content of graphene oxide (GO) flakes in specific oxygenate functional groups on the anti-biofouling properties and performance of thin-film composite membrane (TFC) was studied. Three different multidimensional GO samples were prepared with small (500–1200 nm), medium (1200–2300 nm), and large (2300–3600 nm) size distribution, and with different degrees of oxidation (GO3 > GO2 > GO1), varying the concentration of the hydrogen peroxide amount during GO synthesis. GO1 sheets’ length have a heterogeneous size distribution containing all size groups, whilst GO2 is contained in a medium-size group, and GO3 is totally contained within a small-size group. Moreover, GO oxygenate groups were controlled. GO2 and GO3 have hydroxyl and epoxy groups at the basal plane of their sheets. Meanwhile, GO1 presented only hydroxyl groups. GO sheets were incorporated into the polyamide (PA) layer of the TFC membrane during the interfacial polymerization reaction. The incorporation of GO1 produced a modified membrane with excellent bactericidal properties and anti-adhesion capacity, as well as superior desalination performance with high water flow (133% as compared with the unmodified membrane). For GO2 and GO3, despite the significant anti-biofouling effect, a detrimental impact on desalination performance was observed. The high content of large sheets in GO2 and small sheet stacking in GO3 produced an unfavorable impact on the water flow. Therefore, the synergistic effect due to the presence of large- and small-sized GO sheets and high content of OH-functional groups (GO1) made it possible to balance the performance of the membrane.

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