A novel ion separation methodology using a cation-exchange membrane modified with iron oxide nanoparticles (Fe3O4 NPs) coated with polyhexamethylene guanidine (PHMG) is proposed. The separation is performed in an electrodialysis cell, where firstly phosphate is electro-adsorbed to the PHMG@Fe3O4 NP coating, followed by a desorption step by applying an electric current.

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We report an advanced treatment method for phosphoric acid recovery from leached sewage sludge ash. Layer-by-layer (LbL) polyelectrolyte deposition has been used as a tool to modify and convert a hollow ultrafiltration membrane into a nanofiltration (NF) LbL membrane for H₃PO₄ recovery. To build the LbL membrane, poly(styrenesulfonate) PSS was chosen as polyanion, while three different polycations were used: a permanently charged polyelectrolyte, poly(diallyldimethylammonium chloride), PDADMAC; a pH-dependent charged polyelectrolyte poly(allylamine hydrochloride), PAH; and a PAH modified with guanidinium groups (PAH-Gu). Based on detailed surface characterizations (AFM, XPS and Zeta-potential) it was concluded that both charge density and pH-responsiveness of the polycations are key parameters to control the final membrane surface structure and transport properties. The surface properties of LbL-coated membranes were correlated with the membrane filtration performance, when exposed to the real leached sewage sludge ash solution. The highest permeability was recorded for (PDADMAC/PSS)₆, a result that was rationalized on its loose, and possibly less interpenetrated, structure, followed by (PAH-Gu/PSS)₆ characterized by a more dense, compact layer. H₃PO₄ recovery was the highest in the case of (PDADMAC/PSS)₆, but the retention of multivalent metals (Fe³⁺ and Mg²⁺) was low, leading to a more contaminated permeate. The opposite trend was observed for (PAH-Gu/PSS)_6, resulting in a less metal-contaminated, but also a less H₃PO₄-concentrated permeate. Our LbL-modified membranes were found to improve the permeability and H₃PO₄ recovery compared to a commercially available acid-resistant NF membrane.

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Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

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We have investigated in detail properties of hybrid polyelectrolyte-anion exchange membranes (AEMs) having different amounts of a guanidinium-modified poly(allylamine hydrochloride) (PAH-Gu) derivative (2, 5, and 8 wt%). The presence of guanidinium groups at the membrane surface was confirmed by XPS. For 2 and 5 wt% the blended membranes are homogeneous, while at 8 wt% segregation is observed by AFM. The membrane permselectivity and ionic electrical resistance for phosphate reduce upon incorporation of the PAH-Gu in the membrane, reflecting an increased co-ion (H⁺ and Na⁺) permeation. We conclude that PAH-Gu loaded in the AEM favors an interaction with phosphate. In electrodialysis, using sodium sulfate and sodium dihydrogen phosphate at equal concentrations in the source phase a slight preference for phosphate was observed. Our work shows that this facile membrane fabrication procedure shows great potential in terms of tuning the membrane properties. One way to boost selective ion transport could be by increasing the number of functional groups in the membrane.

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In this study, the preparation of a new, functional anion-exchange membrane (AEM), containing guanidinium groups as the anion-exchanging sites (Gu-100), is described as well as the membrane characterization by XPS, water uptake, permselectivities, and electrical resistances. The functional membrane was also employed in pH-dependent electrodialysis experiments using model dairy wastewater streams. The properties of the new membrane are compared to those of a commercially available anion-exchange membrane bearing conventional quaternary ammonium groups (Gu-0). Guanidinium was chosen for its specific binding properties toward oxyanions: e.g., phosphate. This functional moiety was covalently coupled to an acrylate monomer via a facile two-step synthesis to yield bulk-modified membranes upon polymerization. Significant differences were observed in the electrodialysis experiments for Gu-0 and Gu-100 at pH 7, showing an enhanced phosphate and citrate transport for Gu-100 in comparison to Gu-0. At pH 10 the difference is much more pronounced: for Gu-0 membranes almost no phosphate and citrate transport could be detected, while the Gu-100 membranes transported both ions significantly. We conclude that having guanidinium groups as anion-exchange sites improves the selectivity of AEMs. As the presented monomer synthesis strategy is modular, we consider the implementation of functional groups into a polymer-based membrane via the synthesis of tailor-made monomers as an important step toward selective ion transport, which is relevant for various fields, including water treatment processes and fuel cells.

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In this work commercially available Fe3O4 NPs were coated with polyallylamine hydrochloride (PAH) and PAH functionalized with guanidinium groups (PAH–Gu) for investigating the phosphate adsorption properties under alkaline conditions. The coating can be prepared easily and rapidly and results in Fe3O4 NPs with improved properties related to phosphate binding and colloidal stability. At a low initial phosphate concentration (2 mg L−1), the novel Fe3O4@PAH–Gu material was able to remove phosphate rather independently of the pH condition (4.0, 3.6 and 3.7 mg g−1 at pH = 5, 8 and 10, respectively), whereas for the uncoated Fe3O4 NPs the amount of adsorbed phosphate drops by >75% upon changing from acidic to alkaline conditions (0.84 mg g−1 at pH = 10). Under alkaline conditions, the fastest adsorption was observed for Fe3O4@PAH–Gu followed by Fe3O4@PAH and Fe3O4. This can be related to the additional interaction forces due to the presence of primary amine groups (in PAH and PAH–Gu) and Gu groups (in PAH–Gu only) in coatings. Over 80% of the phosphate adsorbed on the novel Fe3O4@PAH–Gu material was successfully desorbed and the coated NPs were re-used over three adsorption/desorption cycles. This work will stimulate the design and preparation of functionalized polyelectrolytes for an extended area of applications, especially for the selective removal of target compounds from wastewater.@en

The recovery of carboxylic acids from fermentation broth is one of the main bottlenecks for the industrial production of bio-based esters. This paper proposes an alternative for the recovery of carboxylates produced by fermentations at pH values above the pKa of the carboxylic acid. In this approach, the aqueous carboxylate anion is recovered using anion exchange, followed by desorption and esterification with CO2-expanded alcohols. Using CO2-expanded methanol, we achieved a high desorption yield at 10 bar of CO2 and 20 °C. An ester yield of 1.03 ± 0.07 mol methyl acetate/acetatein was obtained for the combined desorption–esterification at 5 bar of CO2 and 60 °C. The proposed process has low chemical consumption and low waste production. The proposed process works, with a lower yield, for other carboxylates (e.g. lactate and succinate) and alcohols (e.g. ethanol).@en

A major challenge in nanotechnology is that of determining how to introduce green and sustainable principles when assembling individual nanoscale elements to create working devices. For instance, textile nanofinishing is restricted by the many constraints of traditional pad-dry-cure processes, such as the use of costly chemical precursors to produce nanoparticles (NPs), the high liquid and energy consumption, the production of harmful liquid wastes, and multistep batch operations. By integrating low-cost, scalable, and environmentally benign aerosol processes of the type proposed here into textile nanofinishing, these constraints can be circumvented while leading to a new class of fabrics. The proposed one-step textile nanofinishing process relies on the diffusional deposition of aerosol NPs onto textile fibers. As proof of this concept, we deposit Ag NPs onto a range of textiles and assess their antimicrobial properties for two strains of bacteria (i.e., Staphylococcus aureus and Klebsiella pneumoniae). The measurements show that the logarithmic reduction in bacterial count can get as high as ca. 5.5 (corresponding to a reduction efficiency of 99.96%) when the Ag loading is 1 order of magnitude less (10 ppm; i.e., 10 mg Ag NPs per kg of textile) than that of textiles treated by traditional wet-routes. The antimicrobial activity does not increase in proportion to the Ag content above 10 ppm as a consequence of a "saturation" effect. Such low NP loadings on antimicrobial textiles minimizes the risk to human health (during textile use) and to the ecosystem (after textile disposal), as well as it reduces potential changes in color and texture of the resulting textile products. After three washes, the release of Ag is in the order of 1 wt %, which is comparable to textiles nanofinished with wet routes using binders. Interestingly, the washed textiles exhibit almost no reduction in antimicrobial activity, much as those of as-deposited samples. Considering that a realm of functional textiles can be nanofinished by aerosol NP deposition, our results demonstrate that the proposed approach, which is universal and sustainable, can potentially lead to a wide number of applications.

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