Efficient removal and environmentally benign detoxification of Cr(VI) in aqueous solutions by Zr(IV) cross-linking chitosan magnetic microspheres

Abstract

Zirconium(IV) cross-linking chitosan (CTS) magnetic microspheres (Fe3O4@Zr-CTS) as a recoverable adsorbent were synthesized through the coordination reaction between zirconium oxychloride and CTS biopolymeric matrix for efficient adsorption and simultaneous detoxification of hexavalent chromium, Cr(VI), in aqueous solutions. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) confirmed the formation of core@shell magnetite microspheres. X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR) verified the crosslinking of Zr(IV) to CTS on the microspheres. Batch Cr(VI) adsorption performances of the resultant Fe3O4@Zr-CTS microspheres revealed that the maximum adsorption capacity of 280.97 mg/g were achieved under pH 4.0 at 298 K. The XPS analyses indicated that 61.1% of the adsorbed Cr(VI) was reduced to Cr(III) due to the oxidization of alcoholic groups on C-6 in CTS which served as electron donors to carbonyl groups. The adsorbent showed preferential Cr(VI) adsorption with the existence of co-existing cations (K+, Na+, Cu2+, Zn2+, Ca2+, Mg2+) and anions (NO3−, Cl−, SO42−, CO32−). The adsorbent exhibited excellent reusability, lower the effluent Cr(VI) contents down to the ppb level, which satisfied the drinking water standard recommended by the World Health Organization and was a promising candidate for water purification.