Here, we describe surface functionalized, superparamagnetic iron oxide nanocrystals (IONCs) for ultra-high PFAS sorption and precise, low energy (magnetic) separation, considering perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). As a function of surface coating, sorption capacities described are considerably higher than previous studies using activated carbon, polymers, and unmodified metal/metal oxides, among others. In particular, positively charged polyethyleneimine (PEI) coated IONCs demonstrate extreme sorption capacities for both PFOA and PFOS due to electrostatic and hydrophobic interactions, along with high polymer grafting densities, while remaining stable in water, thus maintaining available surface area. Further, through a newly developed method using a quart crystal microbalance with dissipation (QCM-D), we present real-time, interfacial observations (e.g., sorption kinetics). Through this method, we explore underpinning mechanism(s) for differential PFAS (PFOA vs PFOS) sorption behavior(s), demonstrating that PFAS functional head group strongly influence molecular orientation on/at the sorbent interface. The effects of water chemistry, including pH, ionic composition of water, and natural organic matter on sorption behavior are also evaluated and along with material (treatment) demonstration via bench-scale column studies.

In this work, we develop and demonstrate highly stable organic-coated engineered superparamagnetic iron oxide nanoparticles (IONPs), which provide effective osmotic pressure without aggregation, reverse diffusion, or membrane blocking (by nanoparticles) for osmotically driven membrane systems, considering both forward osmosis (FO) and pressure-retarded osmosis (PRO). For this, we synthesized highly water stable, monodisperse 12 nm IONPs with a rational series of water stabilizing surface coatings, including sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and polyethylene glycol (PEG). We then compared the library of surface functionalized IONPs as draw solutes for osmotic pressure-driven membrane processes. As synthesized, surface (organic) coatings are compact, thin, and can have very similar surface charge as the membrane itself, which results in effective osmotic pressure in forward osmosis (FO) mode configuration. To increase the osmotic pressure further, on a per mass basis, we synthesized and demonstrated novel hollow IONPs with identical surface coatings. Finally, water flux was further enhanced for stable particle systems using an oscillating magnetic field, thus physically altering concentration gradients, as a function of particle magnetic properties.

Surface modified graphene oxide (GO) has received broad interest as a potential platform material for sensors, membranes, and sorbents, among other environmental applications. However, compared to parent (unmodified) GO, there is a dearth of information regarding the behavior of subsequently (secondary) modified GO, other than bulk natural organic matter (NOM) coating(s). Here, we systematically explore the critical role of organic functionalization with respect to GO stability in water. Specifically, we synthesized a matrix of GO-based materials considering a carefully chosen range of bound organic molecules (hydrophobic coatings: propylamine, tert-octylamine, and 1-adamantylamine; hydrophilic coatings: 3-amino-1-propanol and 3-amino-1-adamantanol), so that chemical structures and functional groups could be directly compared. GO (without organic functionalization) with varying oxidation extent(s) was also included for comparison. The material matrix was evaluated for aqueous stability by comparing critical coagulation concentration (CCC) as a function of varied ionic strength and type (NaCl, CaCl₂, MgCl₂, and MgSO₄) at pH 7.0. Without surface derivatization (i.e., pristine GO), increased stability was observed with an increase in the GO oxidation state, which is supported by plate–plate Derjaguin, Landau, Verwey and Overbeek (DLVO) energy interaction analyses. For derivatized GO, we observed that hydrophilic additions (phi-GO) are relatively more stable than hydrophobic organic coated GO (pho-GO). We further explored this by altering a single OH group in the adamantane-x structure (3-amino-1-adamantanol vs. 1-adamantylamine). As expected, Ca²⁺ and monovalent co-ions play an important role in the aggregation of highly oxidized GO (HGO) and phi-GO, while the effects of divalent cations and co-ions were less significant for pho-GO. Taken together, this work provides new insight into the intricate dynamics of GO-based material stability in water as it relates to surface functionalization (surface energies) and ionic conditions including type of co- and counter-ion, valence, and concentration.