Abstract
Generalized Sorption Scheme: The heterogeneous sorption of adsorbates in the framework of a β-cyclodextrin polyurethane-based sorbent, where both inclusion and non-inclusion binding are observed in aqueous solution.
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► β-cyclodextrin (β-CD) based polyurethane sorbents exhibit tunable sorption properties according to the co-monomer composition. ► Inclusion and non-inclusion binding observed for p-nitrophenol (PNP), phenolphthalein (phth) and naphthenates (NAs). ► Tunable sorption capacity and binding affinity are observed according to the nature of the adsorbate, copolymer sorbent, and experimental (i.e. concentration and pH) conditions.
The sorption of p-nitrophenol (PNP), phenolphthalein (phth) and naphthenates (NAs) with β-cyclodextrin (β-CD) based polyurethane sorbents from aqueous solutions are reported. The copolymer sorbents were synthesized at various β-CD/diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and hydrogen deficiency. The copolymer sorbents were characterized in the solid state using
13C CP-MAS NMR spectroscopy, IR spectroscopy and elemental (C,
H,
N) analysis. The equilibrium sorption properties of the copolymer sorbents in aqueous solution were characterized using isotherm models at pH 4.6 and 9.0 for PNP, pH 9.0 for naphthenates and pH 10.5 for phth. UV–Vis spectroscopy was used to monitor the unbound fraction of the phenolic dyes in the aqueous phase, whereas, electrospray ionization mass spectrometry was used to monitor the unbound fraction of naphthenates. The sorption results of the copolymer sorbents were compared with a commercially available carbonaceous standard; granular activated carbon (GAC). The sorption properties and capacities of the copolymer sorbents (
Q
m
) were estimated using the Sips isotherm. The sorption capacity for GAC was 2.15
mmol PNP/g, 0.0698
mmol phth/g, and 142
mg NAs/g, respectively, whereas the polymeric materials ranged from 0.471 to 1.60
mmol/g (PNP), 0.114 to 0.937
mmol/g (phth), and 0 to 75.5
mg/g (naphthenates), respectively, for the experimental conditions investigated. The observed differences in the sorption properties were attributed to the accessible surface areas and pore structure characteristics of the copolymer sorbents. The binding constant,
K
eq
, for copolymer materials for each sorbate is of similar magnitude to the binding affinity observed for native β-CD. PNP showed significant binding onto the copolymer framework containing diisocyanate domains, whereas, negligible sorption to the sites was observed for phth and naphthenates. The β-CD inclusion sites in the copolymer framework are concluded to be the main sorption site for phth and naphthenates through the formation of well-defined inclusion complexes.