High reusability and adsorption capacity of acid washed calcium alginate/chitosan composite hydrogel spheres in the removal of norfloxacin

Abstract

Calcium alginate (CA) hydrogel spheres were widely used as adsorbents to remove organics, but their adsorption capacities and reusability to some antibiotics are unsatisfactory. In this study, calcium alginate/chitosan (CA/CTS) hydrogel spheres were prepared as precursors. Acid-washed CA/CTS (CA/CTS-M) hydrogel spheres (310.6 mg/g) behaved much better adsorption capacity of norfloxacin (NOR) than CA (69.5 mg/g) and CA/CTS (87.7 mg/g) hydrogel spheres. Astonishingly, after being reused for 15 cycles, CA/CTS-M has no loss of NOR adsorption capacity. In the original idea, acid wash was expected to remove the chitosan in CA/CTS hydrogel spheres for obtaining a larger specific surface area. Both scanning electron microscopy and Brunauer-Emmett-Teller test showed that acid wash can remove CTS from CA/CTS hydrogel spheres to increase the specific surface area. However, part of the chitosan remained in CA/CTS-M, having a role to enhance the structural stability of the material, because the acid-washed CA (about 2 mm) has a significantly smaller diameter than CA/CTS-M (about 3 mm). According to the influence of pH and density functional theory calculations, electrostatic attraction is the key driving force of NOR adsorption. Importantly, acid wash led to more negative-charged surface characterized by Zeta potential, which is the main reason of the significantly enhanced adsorption capacity of CA/CTS-M in removal of NOR. In short, CA/CTS-M hydrogel spheres are environment friendly and highly stable adsorbents with high adsorption capacity in the removal of NOR.