Selective adsorption of tetracycline and copper(II) on ion-imprinted porous alginate microspheres: performance and potential mechanisms

A novel epichlorohydrin and thiourea grafted porous alginate adsorbent (UA-Ca/IIP) was synthesized using ion-imprinting and direct templating to remove copper ions (Cu(II)) and tetracycline (TC) in aqueous solution. UA-Ca/IIP demonstrated great selectivity for Cu(II) and TC among different coexisting anions (CO32−, PO43− and SO42−), cations (Ca2+, Mg2+ and NH4+), and antibiotics (oxytetracycline and sulfamethoxazole). The adsorption of TC and Cu(II) by UA-Ca/IIP was significantly affected by the pH of the solution, and the quantity of TC and Cu(II) adsorbed reached a maximum at pH 5. A pseudo-second-order model better fitted the kinetic data; the Langmuir model predicted the maximum adsorption quantities 3.527 mmol TC g−1 and 4.478 mmol Cu(II) g−1 at 298 K. Thermodynamic studies indicated that the TC and Cu(II) adsorption was more rapid at a higher temperature. Antagonistic and synergistic adsorption experiments showed that the adsorption capacity of TC would increase significantly with the increase of Cu(II) concentration. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy indicated that along with the influence of pH, electrostatic interaction and complexation were the main mechanisms of TC and Cu(II) adsorption. Regeneration experiments revealed that TC and Cu(II) were removed efficiently and that UA-Ca/IIP was recyclable over the long term. These results show that the modified porous alginate microsphere is a green and recyclable adsorbent, which has good selectivity and high adsorption performance for the removal of TC and Cu(II).