Enhanced and Selective Adsorption of Zn(II), Pb(II), Cd(II), and Hg(II) Ions by a Dumbbell- and Flower-Shaped Potato Starch Phosphate Polymer: A Combined Experimental and DFT Calculation Study.

Abstract

Microwave–ultrasound-assisted facile synthesis of a dumbbell- and flower-shaped potato starch phosphate (PSP) polymer, hereafter PSP, was carried out by cross-linking the hydroxyl groups of native potato starch (NPS) using phosphoryl chloride as a cross-linking agent. Structural and morphological analysis manifested the successful formation of the dumbbell- and flower-shaped PSP biosorbent with enhanced specific surface area and thermal stability. Viscoelastic behavior of NPS and PSP suggested increased rigidity in PSP, which helped the material to store more deformation energy in an elastic manner. The synthesized PSP biosorbent material was successfully tested for efficient and quick uptake of Zn(II), Pb(II), Cd(II), and Hg(II) ions from aqueous medium under competitive and noncompetitive batch conditions with qm values of 130.54, 106.25, 91.84, and 51.38 mg g–1, respectively. The adsorption selectivity was in consonance with Pearson’s hard and soft acids and bases (HSAB) theory in addition to their order of hydrated radius. Adsorption of Zn(II), Pb(II), Cd(II), and Hg(II) followed a second-order kinetics and the adsorption data fitted well with the Langmuir isotherm model. Quantum computations using density functional theory (DFT) further supported the experimental adsorption selectivity, Zn(II) > Pb(II) > Cd(II) > Hg(II), in terms of metal–oxygen binding energy measurements. What was more intriguing about PSP was its reusability over multiple adsorption cycles by treating the metal(II)-complexed PSP with 0.1 M HCl without any appreciable loss of its adsorption capacity.