Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system

Soon Kong Yong; William M. Skinner; Nanthi S. Bolan; Enzo Lombi; Anitha Kunhikrishnan; Yong Sik Ok

doi:10.1007/s11356-015-5654-5

Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system

Soon Kong Yong, William M. Skinner, Nanthi S. Bolan, Enzo Lombi, Anitha Kunhikrishnan, Yong Sik Ok

Research output: Contribution to journal › Article › peer-review

20 Citations (Scopus)

Abstract

Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS₂)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS₂/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (–SH)/thione, disulfide (–S–S–), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in –SH oxidation to produce –S–S– crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.

Original language	English
Pages (from-to)	1050-1059
Number of pages	10
Journal	Environmental Science and Pollution Research
Volume	23
Issue number	2
DOIs	https://doi.org/10.1007/s11356-015-5654-5
Publication status	Published - 2016 Jan 1
Externally published	Yes

Bibliographical note

Funding Information:
The senior and corresponding author would like to thank the University of South Australia for his UniSA President’s Scholarship award and Universiti Teknologi MARA for his UiTM Staff Scholarship award. We are grateful to Dr. Jeremy Deverell for his assistance with the micro-CT imaging of chitosan beads, and we acknowledge access to instrumentation at the University of South Australia nodes of the Australian National Fabrication Facility (ANFF) and Australian Microscopy and Microanalysis Research Facility (AMMRF).

Publisher Copyright:
© 2015, Springer-Verlag Berlin Heidelberg.

Keywords

Chemisorption
Chitosan
Mercapto group
Oxidation
Soft Lewis base
Thioamide

ASJC Scopus subject areas

Environmental Chemistry
Pollution
Health, Toxicology and Mutagenesis

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10.1007/s11356-015-5654-5

Cite this

Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system. / Yong, Soon Kong; Skinner, William M.; Bolan, Nanthi S. et al.
In: Environmental Science and Pollution Research, Vol. 23, No. 2, 01.01.2016, p. 1050-1059.

Research output: Contribution to journal › Article › peer-review

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abstract = "Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (–SH)/thione, disulfide (–S–S–), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in –SH oxidation to produce –S–S– crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.",

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Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

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