Efficient Sorption of Cu2+ by Composite Chelating Sorbents Based on Potato Starch-graft-Polyamidoxime Embedded in Chitosan Beads

Ionic composites based on cross-linked chitosan (CS) as matrix and poly(amidoxime) grafted on potato starch (AOX) as entrapped chelating resin were prepared as beads, for the first time in this work, by two strategies: (1) thorough mixing of previously prepared AOX in the CS solution followed by the bead formation and (2) thorough mixing of the potato starch-g-poly(acrylonitrile) (PS-g-PAN) copolymer in the initial CS solution, followed by bead formation, the amidoximation of the nitrile groups taking place inside the beads. Ionotropic gelation in tripolyphosphate was used to obtain the composite beads, and in situ covalent cross-linking by epichlorohydrin was carried out to stabilize the beads in the acidic pH range. Fourier transform infrared spectroscopy and the swelling ratio values in the acidic pH range confirmed the influence of the synthesis strategy on the structure of the CS/AOX composites. Scanning electron microscopy was employed to reveal the morphology of the novel composites, both before and after their loading with Cu(2+). The binding capacity of Cu(2+) ions as a function of sorbent composition, synthesis strategy, pH, sorbent dose, contact time, initial concentration of Cu(2+), and temperature was examined in batch mode. The main difference between the composites prepared with the two strategies consisted of the higher sorption capacity and the much faster settlement of the equilibrium sorption for the composite prepared by the in situ amidoximation of PS-g-PAN. The Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Sips isotherms were applied to fit the sorption equilibrium data. The maximum equilibrium sorption capacity, qm, evaluated by the Langmuir model at 25 °C was 133.15 mg Cu(2+)/g for the CS/AOX composite beads prepared with the first strategy and 238.14 mg Cu(2+)/g for the CS/AOX composite beads prepared with the second strategy, at the same AOX content. The pseudo-second order kinetic model well fitted the sorption kinetics data, supporting chemisorption as the mechanism of interaction between the chelating composites and the Cu(2+) ions. The CS/AOX composite sorbents could be reused up to five sorption/desorption cycles with no significant decrease in Cu(2+) sorption capacity.