Abstract
Removal of Cu(II) and Cd(II) from wastewater using porous chitosan beads is likely to be enhanced by the introduction of thiol groups (−SH). This is because, in accordance with the Hard Soft Acid Base concept, the soft Lewis base of –SH forms a strong bond with soft Lewis acid of Cd(II) or with borderline Lewis acids such as Cu(II). Possible formation of thiourea and disulfide crosslinks (−S–S–) may also confer increased bead stability in acidic solution. Thiolated chitosan beads (ETB) prepared and investigated in this study had a total sulfur content of 7.9 %. The thiolation process slightly increased the Brunauer-Emmett-Teller surface area of the chitosan beads from 39.5 to 46.3 m2/g. This ETB was categorised as a microporous material (pore aperture: 1.8 nm) with multiple and uniform porous layers. Analysis by X-ray photoelectron spectroscopy indicated the presence of three sulfur species, S(−I), S(−II) and S(V) attributed to –S–S–, –SH and sulfonate (−SO3 −) groups. The Langmuir sorption capacity, q max, for Cd(II) was improved by 18 times by thiolation of chitosan. However, the q max for Cu(II) by ETB was seven times lower than that of pristine chitosan beads, possibly due to exhaustion of amine groups (−NH2). The batch sorption data was generally fitted well by a linearised Freundlich isotherm model and a Ho’s pseudo-second-order kinetic model, indicating metal interaction with the heterogeneous surface of ETB and chemical adsorption as the possible rate-limiting step, respectively. The metal uptake has resulted in the oxidation of –SH to –SO3 − group in ETB, thereby decreasing the stability of metal-sulfide bonds as well as their metal uptake.
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The senior author would like to thank University of South Australia for UniSA President Scholarship award and Universiti Teknologi MARA for UiTM Staff Scholarship award.
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Guest Editors: R Naidu, Euan Smith, MH Wong, Megharaj Mallavarapu, Nanthi Bolan, Albert Juhasz, and Enzo Lombi
This article is part of the Topical Collection on Remediation of Site Contamination
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Yong, S.K., Bolan, N., Lombi, E. et al. Synthesis and Characterization of Thiolated Chitosan Beads for Removal of Cu(II) and Cd(II) from Wastewater. Water Air Soil Pollut 224, 1720 (2013). https://doi.org/10.1007/s11270-013-1720-0
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DOI: https://doi.org/10.1007/s11270-013-1720-0