Itaconic Acid Grafted Starch Hydrogels as Metal Remover: Capacity,Selectivity and Adsorption Kinetics

Hydrogels were synthesized by free radical graft copolymerization of itaconic acid (IA) onto corn starch (S-g-IA). For this purpose, potassium permanganate (KMnO₄)-sodium bisulfite (NaHSO₃) was used as redox initiation system. The formation of grafted starches was confirmed by Fourier transform infrared spectroscopy, wide angle X-ray scattering, thermogravimetric analysis and scanning electron microscopy. The effect of monomer concentration, neutralization, addition of crosslinking agent, N,N-bismetilenacrilamide (MBAm), and initiator concentration on grafting efficiency and adsorption capacity of the starch hydrogels was investigated. It was demonstrated that the introduction of carboxyl and carbonyl groups promoted starch hydration and swelling. Grafting degree increased with the decrease of monomer concentration, increase of initiator concentration, grade of neutralization and the addition of MBAm without neutralization. Remarkably the resulting materials exhibited water absorption capacities between 258 and 1878% and the ability to adsorb metal ions. It was experimentally confirmed the metal uptake, obtaining the higher adsorption capacity (q _e  = 35 mg/g) for the product prepared with the pre-oxidation and lower initiator concentration. The removal capacity order was Pb²⁺>Ni²⁺>Zn²⁺>Cd²⁺. Moreover, the experimental kinetic and the equilibrium adsorption data for Ni²⁺ and Pb²⁺ were best fitted to the pseudo-second order and Freundlich isotherm models, respectively. This work describes for the first time the preparation of metal removal hydrogels based on starch and itaconic acid using the pair redox system KMnO₄/NaHSO₃, which avoids the starch hydrolysis and allows itaconic acid grafting incorporation without the requirement of more reactive comonomers.