Synthesis of novel copper ion-selective material based on hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate)

A novel hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate) using a double-imprinting approach for the Cu ²⁺ selective separation from aqueous medium was prepared. In the imprinting process, both Cu²⁺ ions and surfactant micelles (cetyltrimethylammonium bromide - CTAB) were employed as templates. The hierarchically imprinted organic polymer named (IIP-CTAB), single-imprinted (IIP-no CTAB) and non-imprinted (NIP-CTAB and NIP-no CTAB) polymers were characterized by SEM, FTIR, TG, elemental analysis and textural data from BET (Brunauer-Emmett-Teller) and BJH (Barrett-Joyner-Halenda). Compared to these materials, IIP-CTAB showed higher selectivity, specific surface area and adsorption capacity toward Cu²⁺ ions. Good selectivity for Cu ²⁺ was obtained for the Cu²⁺/Cd²⁺, Cu ²⁺/Zn²⁺ and Cu²⁺/Co²⁺ systems when IIP-CTAB was compared to the single-imprinted (IIP-no CTAB) and non double-imprinted polymer (NIP-CTAB), thereby confirming the improvement in the polymer selectivity due to double-imprinting effect. For adsorption kinetic data, the best fit was provided with the pseudo-second-order model for the four materials, thereby indicating the chemical nature of the Cu²⁺ adsorption process. Cu²⁺ adsorption under equilibrium was found to follow dual-site Langmuir-Freundlich model isotherm, thus suggesting the existence of adsorption sites with low and high binding energy on the adsorbent surface. From column experiments 600 adsorption-desorption cycles using 1.8 mol L^-1 HNO₃ as eluent confirmed the great recoverability of adsorbent. The synthesis approach here investigated has been found to be very attractive for the designing of organic ion imprinted polymer and can be expanded to the other polymers to improve performance of ion imprinted polymers in the field of solid phase extraction.