A new experimental approach was developed to measure the concentration of charged functional groups (FGs) in the active layer of thin-film composite reverse osmosis (RO) and nanofiltration (NF) membranes as a function of solution pH. FT30 RO membrane, with a fully aromatic polyamide (PA) active layer sandwiched between a polysulfone support and a coating layer, was used. The experiments consisted of saturating charged FGs with heavy ion probes, and determining the ion probe concentration by Rutherford backscattering spectrometry (RBS). Deprotonated carboxylic groups were saturated with Ag+, and protonated amine groups with W04(2-). The ionization behavior of carboxylic and amine groups was modeled based on acid-base equilibrium theory. While the ionization behavior of amine groups was satisfactorily described by one dissociation constant (pKa = 4.74), two pKa values (5.23 and 8.97) were necessary to describe the titration curve of carboxylic groups. These results were consistent with the bimodal pore size distribution (PSD) of FT30 active layer reported in the literature. The calculated total concentrations of carboxylic and amine groups in the active layer of the FT30 RO membrane studied were 0.432 and 0.036 M, respectively, and the isoelectric point (IEP) was 4.7. The total concentration of carboxylic and amine groups revealed that the degree of cross-linking of the PA active layer of the FT30 RO membrane studied was 94%.
We characterized the fully aromatic polyamide (PA) active layers of six commercial reverse osmosis (RO) and nanofiltration (NF) membranes and found that in contrast to their similar elemental composition, total concentration of functional groups, and degree of polymerization, the ionization behavior and spatial distribution of carboxylic (R-COOH) groups within the active layers can be significantly different. We also studied the steric effects experienced by barium ion (Ba2+) in the active layers by determining the fraction of carboxylate (R-COO-) groups accessible to Ba2+; such fraction, referred to as the accessibility ratio (AR), was found to vary within the range AR=0.40-0.81, and to be generally independent of external solution pH. Additionally, we studied an NF membrane with a sulfonated polyethersulfone (SPES) active layer, and found that the concentration of sulfonate (R-SO3-) groups in the active layer was 1.67 M, independent of external solution pH and approximately three times higher than the maximum concentration (approximately 0.45+/-0.25 M) of R-COO- groups in PA active layers. The R-SO3- groups were found to be highly accessible to Ba2+ (AR=0.95+/-0.01).
We studied the depth heterogeneity of fully aromatic polyamide (PA) active layers in commercial reverse osmosis (RO) and nanofiltration (NF) membranes by quantifying near-surface (i.e., top 6 nm) and volume-averaged properties of the active layers using X-ray photoelectron spectrometry (XPS) and Rutherford backscattering spectrometry (RBS), respectively. Some membranes (e.g., ESPA3 RO) had active layers that were depth homogeneous with respect to the concentration and pK(a) distribution of carboxylic groups, degree of polymer cross-linking, concentration of barium ion probe that associated with ionized carboxylic groups, and steric effects experienced by barium ion. Other membranes (e.g., NF90 NF) had active layers that were depth heterogeneous with respect to the same properties. Our results therefore support the existence of both depth-homogeneous and depth-heterogeneous active layers. It remains to be assessed whether the depth heterogeneity consists of gradually changing properties throughout the active layer depth or of distinct sublayers with different properties.
Per- and polyfluorinated
alkyl substances (PFASs) contaminate groundwater,
surface water, and finished drinking water internationally. Their
ecological persistence and adverse human health effects demand effective
remediation approaches. Motivated by the limitations in selectivity
and performance of current PFAS removal technologies, we report a
platform approach for the development of ionic fluorogel resins that
effectively remove a chemically diverse mixture of PFAS from water.
The synthesis of a material library with systematic variation in fluorous
and ionic components led to the identification of a resin that demonstrated
rapid removal of PFASs with high affinity and selectivity in the presence
of nonfluorous contaminants commonly found in groundwater. The material
can be regenerated and reused multiple times. We demonstrate ionic
fluorogels as effective adsorbents for the removal of 21 legacy and
emerging PFASs from settled water collected at the Sweeney Water Treatment
Plant in Wilmington, North Carolina.
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