In this study, citric acid (CA)-coated magnetite Fe₃O₄ magnetic nanoparticles (Fe₃O₄@CA MNPs) for use as draw solution (DS) agents in forward osmosis (FO) were synthesized by co-precipitation and characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic light scattering (DLS), transmission electron microscopy (TEM) and magnetic measurements. Prepared 3.7% w/w colloidal solutions of Fe₃O₄@CA MNPs exhibited an osmotic pressure of 18.7 bar after purification without aggregation and a sufficient magnetization of 44 emu/g to allow DS regeneration by an external magnetic field. Fe₃O₄@CA suspensions were used as DS in FO cross-flow filtration with deionized (DI) water as FS and with the active layer of the FO membrane facing the FS and NaCl as a reference DS. The same transmembrane bulk osmotic pressure resulted in different water fluxes for NaCl and MNPs, respectively. Thus the initial water flux with Fe₃O₄@CA was 9.2 LMH whereas for 0.45 M NaCl as DS it was 14.1 LMH. The reverse solute flux was 0.08 GMH for Fe₃O₄@CA and 2.5 GMH for NaCl. These differences are ascribed to a more pronounced internal dilutive concentration polarization with Fe₃O₄@CA as DS compared to NaCl as DS. This research demonstrated that the proposed Fe₃O₄@CA can be used as a potential low reverse solute flux DS for FO processes.

The synthesis of magnetic nanoparticles (MNPs) coated with hydrophilic poly-sodium-acrylate (PSA) ligands was studied to assess PSA-MNP complexes as draw solution (DS) solutes in forward osmosis (FO). For MNP-based DS, the surface modification and the size of the MNPs are two crucial factors to achieve a high osmolality. Superparamagnetic nanoparticles (NP) with functional groups attached may represent the ideal DS where chemical modifications of the NPs can be used in optimizing the DS osmolality and the magnetic properties allows for efficient recovery (DS re-concentration) using an external magnetic field. In this study MNPs with diameters of 4 nm have been prepared by controlled chemical co-precipitation of magnetite phase from aqueous solutions containing suitable salts of Fe²⁺ and Fe³⁺ under inert atmosphere and a pure magnetite phase could be verified by X-ray diffraction. Magnetic colloid suspensions containing PSA-coated MNPs with three different molar ratios of PSA:MNP = 1:1, 1:2 and 1:3 were prepared and assessed in terms of osmotic pressure, aggregation propensity and magnetization. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the presence of PSA on coated MNPs and pristine PSA-MNPs with a molar ratio PSA:MNP = 1:1 exhibited an osmotic pressure of 30 bar. Molar ratios of PSA:MNP = 1:2 and 1:3 lead to the formation of less stabile magnetic colloid solutions, which led to the formation of aggregates with larger average hydrodynamic sizes and modest osmotic pressures (5.5 bar and 0.2 bar, respectively). After purification with ultrafiltration, the 1:1 nanoparticles exhibited an osmotic pressure of 9 bar with no aggregation and a sufficient magnetization of 25 emu/g to allow for DS regeneration using an external magnetic field. However, it was observed that the amount of PSA molecules attached to the MNPs decreased during DS recycling steps, leaving only strong chelate-bonded core-shell PSA as coating on the MNPs. This demonstrates the crucial role of MNP coating robustness in designing an efficient MNP-based DS for FO.

Polyacrylic acid (PAA)-coated magnetic nanoparticles (MNP@PAA) were synthesized and evaluated as draw solutes in the forward osmosis (FO) process. MNP@PAA were synthesized by microwave irradiation and chemical co-precipitation from aqueous solutions of Fe²⁺ and Fe³⁺ salts. The results showed that the synthesized MNPs have spherical shapes of maghemite Fe₂O₃ and superparamagnetic properties, which allow draw solution (DS) recovery using an external magnetic field. Synthesized MNP, coated with PAA, yielded an osmotic pressure of ~12.8 bar at a 0.7% concentration, resulting in an initial water flux of 8.1 LMH. The MNP@PAA particles were captured by an external magnetic field, rinsed in ethanol, and re-concentrated as DS in repetitive FO experiments with deionized water as a feed solution (FS). The osmotic pressure of the re-concentrated DS was 4.1 bar at a 0.35% concentration, resulting in an initial water flux of 2.1 LMH. Taken together, the results show the feasibility of using MNP@PAA particles as draw solutes.

Multicoated magnetite (Fe₃O₄) magnetic nanoparticles (MNPs) with polyacrylic acid (PAA) as a terminal hydrophilic ligand were synthesized and examined for use as a draw solution (DS) agent in forward osmosis (FO). After coating superparamagnetic iron-oxide MNPs with (3-aminopropyl)triethoxysilane (APTES) the carboxyl groups of PAA were bound to APTES amino groups via the crosslinker 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) forming a peptide bond resulting in stable water-soluble particles (MNP@APTES@PAA) with a concentration-normalised osmotic pressure of 1.56 bar L g⁻¹. The MNP@APTES@PAA solution was evaluated as a DS in two FO filtrations with deionized (DI) water as a feed solution (FS): one using freshly prepared MNP@APTES@PAA and one using magnetically recovered (re-concentrated) MNP@APTES@PAA. The resulting MNP@APTES@PAA nanocomposites exhibit good colloidal stability in aqueous solution with a concentration-normalized osmotic pressure of 1.56 bar L g⁻¹. This is 12-fold higher than that in our previous studies of poly-sodium-acrylate coated MNPs and 3-fold higher than that of citric acid coated MNPs. The water recoveries of the two filtrations were 25.7% and 13.6%, respectively, after 2 h of FO filtration time resulting in a DS osmotic pressure of 2.5 bar with a concentration of 4.3 g L⁻¹ and a DS osmotic pressure of 2.6 with a concentration of 3.7 g L⁻¹ respectively.