Functionalized magnetic chitosan-based adsorbent for efficient tetracycline removal: Deep investigation of adsorption behaviors and mechanisms

As removal performance of tetracyclines in traditional wastewater treatment plants cannot satisfy the increasingly strict discharge requirements, developing an efficient approach to overcome this problem is quite urgent. Herein, a novel functionalized magnetic chitosan-based adsorbent (Fe3O4@CAA) with core-shell structure and unique magnetic responsiveness was facilely prepared by ultrasound-initiated radical grafting copolymerization and cross-link reaction. The as-prepared Fe3O4@CAA was fully characterized with TEM, SEM, BET, FTIR, TGA, XRD, VSM, and served as an efficient adsorbent for tetracycline hydrochloride (TCH) removal. Adsorption behaviors of TCH by Fe3O4@CAA were deeply evaluated at different adsorption time, initial TCH concentration, reaction temperature, solution pH, and background pollutant concentration. Results showed that Fe3O4@CAA presented a more competitive adsorption capacity of 325.04 mg g-1 compared with Fe3O4@CS and other reported adsorbent, due to the introduction of more active adsorption sites by abundant functional groups, including amino groups, hydroxyl groups, and sulfonic acid groups. After saturated adsorption, TCH loaded Fe3O4@CAA was easily collected by magnetic separation, and recycled after acid pickling. Fe3O4@CAA was successfully reused in five adsorption-desorption cycles, without obvious adsorption capacity loss. In binary pollutant systems, inorganic cations and Pb(II) restrained TCH adsorption by competitive effect, while proper amount of Cu(II) promoted TCH adsorption by bridge effect. FTIR and XPS analyses revealed that the adsorption mechanism of TCH by Fe3O4@CAA mainly included electrostatic interaction and hydrogen bonding, and Cu(II) could play a "mediator" role to form a strong Cu(II)-TCH complex to enhance TCH removal performance. This study provides an effective strategy for the design of magnetic chitosan-based adsorbents and valuable guidance for the removal of tetracyclines from wastewater.