Crosslinked modified chitosan biopolymer for enhanced removal of toxic Cr(VI) from aqueous solution

Two new crosslinked modified chitosan biopolymers, namely (CTS-VAN) and (Fe₃O₄@CTS-VAN) bioadsorbents were prepared starting from chitosan and 4-hydroxy-3-methoxybenzaldehyde (VAN) in presence of epichlorohydrin. The analytical techniques FT-IR, EDS, XRD, SEM and XPS besides BET surface analysis were utilized for full characterization of the bioadsorbents. Batch experiments were conducted to study the effect of various influencing parameters in Cr (VI) removal such as initial pH, contact time, adsorbent amount and initial Cr (VI) concentration. The adsorption of Cr (VI) was found out to be maximum at pH = 3 for both bioadsorbents. Langmuir isotherm fit well the adsorption process with a maximum adsorption capacity of 188.68 and 98.04 mg/g for CTS-VAN and Fe₃O₄@CTS-VAN, respectively. The adsorption process followed pseudo second-order kinetics with R² values of 1 and 0.9938 for CTS-VAN and Fe₃O₄@CTS-VAN, respectively. X-ray photoelectron spectroscopy (XPS) analysis showed that Cr(III) accounted for 83 % of the total Cr bound to bioadsorbents surface, which indicated reductive adsorption was responsible for Cr(VI) removal by the bioadsorbents. Cr(VI) was initially adsorbed on the positively charged surface of the bioadsorbents and reduced to Cr(III) by electrons provided by oxygen-comprising functional groups (e.g., CO), and consequently part of the converted Cr(III) stayed on the surface and the rest released into solution.