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A cellulose graft copolymer (cellulose nanoresin) was synthesized by the all-aqueous functionalization of cellouronic acid with poly (vinyl benzyl trimethyl ammonium chloride) (poly(vbTMAC)). Cellulose was oxidized using the highly reported 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated selective C-6 oxidation reaction. Fischer–Speier esterification of cellouronic acid was used to graft poly(vbTMAC) to the cellulosic backbone in a facile click-like mechanism. Synthesis of cellulose nanoresin was confirmed using dynamic light scattering and zeta potential measurements. Conductometric titration was used to determine the carboxylate content of cellouronic acid and the percent functionalization of the cellulose nanoresin, which was 1.69 ± 0.03 mmol/g and 61.2 ± 4%, respectively. Using a disodium fluorescein (NaFL) surrogate adsorbate, the maximum adsorption capacity of CNR was measured to be 26.8 ± 1.3 mg NaFL per gram of CNR with a Langmuir equilibrium binding constant of Ks = 10.5 ± 2 ppm−1. When examined as a thin film membrane, a breakthrough study of CNR showed that equilibrium loading was achieved in less than 30 s, and that > 90% of loading occurred in under 5 s. This data suggests that these films can be used as contact resins for anion-exchange water purification. We show in this work that these films maintain > 99% of loading performance over 40 trials of regeneration and reuse, meaning that these films are green and regenerable. Initial testing shows that CNR is effective at the removal of perfluorooctane sulfonate (PFOS) from water to below our limit of detection of 100 ppt.more » « less
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Sahu, Abhispa; Dosi, Raghav; Kwiatkowski, Carly; Schmal, Stephen; Poler, Jordan C. (, Polymers)Nanomaterials have been extensively used in polymer nanocomposite membranes due to the inclusion of unique features that enhance water and wastewater treatment performance. Compared to the pristine membranes, the incorporation of nanomodifiers not only improves membrane performance (water permeability, salt rejection, contaminant removal, selectivity), but also the intrinsic properties (hydrophilicity, porosity, antifouling properties, antimicrobial properties, mechanical, thermal, and chemical stability) of these membranes. This review focuses on applications of different types of nanomaterials: zero-dimensional (metal/metal oxide nanoparticles), one-dimensional (carbon nanotubes), two-dimensional (graphene and associated structures), and three-dimensional (zeolites and associated frameworks) nanomaterials combined with polymers towards novel polymeric nanocomposites for water and wastewater treatment applications. This review will show that combinations of nanomaterials and polymers impart enhanced features into the pristine membrane; however, the underlying issues associated with the modification processes and environmental impact of these membranes are less obvious. This review also highlights the utility of computational methods toward understanding the structural and functional properties of the membranes. Here, we highlight the fabrication methods, advantages, challenges, environmental impact, and future scope of these advanced polymeric nanocomposite membrane based systems for water and wastewater treatment applications.more » « less
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