Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal

The fabrication of chitosan (CH) biocomposite beads with variable copper (Cu<sup>2+</sup>) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-<i>b</i>-Cu) with...

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Main Authors: Inimfon A. Udoetok, Abdalla H. Karoyo, Mohamed H. Mohamed, Lee D. Wilson
Format: Article
Language:English
Published: MDPI AG 2024-01-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/29/2/445
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author Inimfon A. Udoetok
Abdalla H. Karoyo
Mohamed H. Mohamed
Lee D. Wilson
author_facet Inimfon A. Udoetok
Abdalla H. Karoyo
Mohamed H. Mohamed
Lee D. Wilson
author_sort Inimfon A. Udoetok
collection DOAJ
description The fabrication of chitosan (CH) biocomposite beads with variable copper (Cu<sup>2+</sup>) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-<i>b</i>-Cu) without CL; (2) cross-linking of the CH beads, followed by imbibition of Cu(II) ions (CH-<i>b</i>-CL-Cu); and (3) cross-linking of pristine CH, followed by bead formation with Cu(II) imbibing onto the beads (CH-CL-<i>b</i>-Cu). The biocomposites (CH-<i>b</i>-Cu, CH-<i>b</i>-CL-Cu, and CH-CL-<i>b</i>-Cu) were characterized via spectroscopy (FTIR, <sup>13</sup>C solid NMR, XPS), SEM, TGA, equilibrium solvent swelling methods, and phosphate adsorption isotherms. The results reveal variable cross-linking and Cu(II) doping of the CH beads, in accordance with the step-wise design strategy. CH-CL-<i>b</i>-Cu exhibited the greatest pillaring of chitosan fibrils with greater cross-linking, along with low Cu(II) loading, reduced solvent swelling, and attenuated uptake of phosphate dianions. Equilibrium and kinetic uptake results at pH 8.5 and 295 K reveal that the non-CL Cu-imbibed beads (CH-<i>b</i>-Cu) display the highest affinity for phosphate (Q<i><sub>m</sub></i> = 133 ± 45 mg/g), in agreement with the highest loading of Cu(II) and enhanced water swelling. Regeneration studies demonstrated the sustainability and cost-effectiveness of Cu-imbibed chitosan beads for controlled phosphate removal, whilst maintaining over 80% regenerability across several adsorption–desorption cycles. This study offers a facile synthetic approach for controlled Cu<sup>2+</sup> ion doping onto chitosan-based beads, enabling tailored phosphate oxyanion uptake from aqueous media by employing a sustainable polysaccharide biocomposite adsorbent for water remediation by mitigation of eutrophication.
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spelling doaj.art-2eab1f12a26f4c9cb3bc0f399a4b78582024-01-29T14:08:42ZengMDPI AGMolecules1420-30492024-01-0129244510.3390/molecules29020445Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate RemovalInimfon A. Udoetok0Abdalla H. Karoyo1Mohamed H. Mohamed2Lee D. Wilson3Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, CanadaDepartment of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, CanadaDepartment of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, CanadaDepartment of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, CanadaThe fabrication of chitosan (CH) biocomposite beads with variable copper (Cu<sup>2+</sup>) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-<i>b</i>-Cu) without CL; (2) cross-linking of the CH beads, followed by imbibition of Cu(II) ions (CH-<i>b</i>-CL-Cu); and (3) cross-linking of pristine CH, followed by bead formation with Cu(II) imbibing onto the beads (CH-CL-<i>b</i>-Cu). The biocomposites (CH-<i>b</i>-Cu, CH-<i>b</i>-CL-Cu, and CH-CL-<i>b</i>-Cu) were characterized via spectroscopy (FTIR, <sup>13</sup>C solid NMR, XPS), SEM, TGA, equilibrium solvent swelling methods, and phosphate adsorption isotherms. The results reveal variable cross-linking and Cu(II) doping of the CH beads, in accordance with the step-wise design strategy. CH-CL-<i>b</i>-Cu exhibited the greatest pillaring of chitosan fibrils with greater cross-linking, along with low Cu(II) loading, reduced solvent swelling, and attenuated uptake of phosphate dianions. Equilibrium and kinetic uptake results at pH 8.5 and 295 K reveal that the non-CL Cu-imbibed beads (CH-<i>b</i>-Cu) display the highest affinity for phosphate (Q<i><sub>m</sub></i> = 133 ± 45 mg/g), in agreement with the highest loading of Cu(II) and enhanced water swelling. Regeneration studies demonstrated the sustainability and cost-effectiveness of Cu-imbibed chitosan beads for controlled phosphate removal, whilst maintaining over 80% regenerability across several adsorption–desorption cycles. This study offers a facile synthetic approach for controlled Cu<sup>2+</sup> ion doping onto chitosan-based beads, enabling tailored phosphate oxyanion uptake from aqueous media by employing a sustainable polysaccharide biocomposite adsorbent for water remediation by mitigation of eutrophication.https://www.mdpi.com/1420-3049/29/2/445chitosan beadsbiocomposite adsorbentglutaraldehyde cross-linkingCu(II) ion complexationphosphate
spellingShingle Inimfon A. Udoetok
Abdalla H. Karoyo
Mohamed H. Mohamed
Lee D. Wilson
Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
Molecules
chitosan beads
biocomposite adsorbent
glutaraldehyde cross-linking
Cu(II) ion complexation
phosphate
title Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
title_full Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
title_fullStr Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
title_full_unstemmed Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
title_short Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal
title_sort chitosan biocomposites with variable cross linking and copper doping for enhanced phosphate removal
topic chitosan beads
biocomposite adsorbent
glutaraldehyde cross-linking
Cu(II) ion complexation
phosphate
url https://www.mdpi.com/1420-3049/29/2/445
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AT mohamedhmohamed chitosanbiocompositeswithvariablecrosslinkingandcopperdopingforenhancedphosphateremoval
AT leedwilson chitosanbiocompositeswithvariablecrosslinkingandcopperdopingforenhancedphosphateremoval