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. 2024 Dec 12;16(24):3469.
doi: 10.3390/polym16243469.

Novel Nanocomposites and Biopolymer-Based Nanocomposites for Hexavalent Chromium Removal from Aqueous Media

Adina-Elena Segneanu  1 , Ionela Amalia Bradu  1 , Mihaela Simona Calinescu Bocanici  2 , Gabriela Vlase  1   3 , Titus Vlase  1   3 , Daniel-Dumitru Herea  4 , Gabriela Buema  4 , Maria Mihailescu  5   6 , Ioan Grozescu  5
Affiliations

Novel Nanocomposites and Biopolymer-Based Nanocomposites for Hexavalent Chromium Removal from Aqueous Media

Adina-Elena Segneanu et al. Polymers (Basel). .

Abstract

Designing new engineered materials derived from waste is essential for effective environmental remediation and reducing anthropogenic pollution in our economy. This study introduces an innovative method for remediating metal-contaminated water, using two distinct waste types: one biowaste (eggshell) and one industrial waste (fly ash). We synthesized three novel, cost-effective nanoadsorbent types, including two new tertiary composites and two biopolymer-based composites (specifically k-carrageenan and chitosan), which targeted chromium removal from aqueous solutions. SEM analysis reveals that in the first composite, EMZ, zeolite, and magnetite nanoparticles are successfully integrated into the porous structure of the eggshell. In the second composite (FMZ), fly ash and magnetite particles are similarly loaded within the zeolite pores. Each biopolymer-based composite is derived by incorporating the corresponding tertiary composite (FMZ or EMZ) into the biopolymer framework. Structural modifications of the eggshell, zeolite, chitosan, and k-carrageenan resulted in notable increases in specific surface area, as confirmed by BET analysis. These enhancements significantly improve chromium adsorption efficiency for each adsorbent type developed. The adsorption performances achieved are as follows: EMZ (89.76%), FMZ (84.83%), EMZCa (96.64%), FMZCa (94.87%), EMZC (99.64%), and FMZC (97.67%). The findings indicate that chromium adsorption across all adsorbent types occurs via a multimolecular layer mechanism, which is characterized as spontaneous and endothermic. Desorption studies further demonstrate the high reusability of these nanomaterials. Overall, this research underscores the potential of utilizing waste materials for new performant engineered low-cost composites and biocomposites for environmental bioremediation applications.

Keywords: adsorbent; biopolymer-based composite; heavy metal pollution; wastes; water remediation.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 16
Figure 16
EDX spectrum of EMZ (a), FMZ (b), EMZCa (c), FMZCa (d), EMZC (e), and FMZC (f) after adsorption.
Figure 1
Figure 1
Schematic representation of composites, k-carrageenan-based nanocomposites, and chitosan-based nanocomposite preparation: EMZ/EMZC/EMZCa (a), and FMZ/FMZC/FMZCa (b).
Figure 2
Figure 2
The nitrogen adsorption–desorption isotherms (a); pore distribution (b) for all adsorbents.
Figure 3
Figure 3
XRD spectra of all adsorbent types prepared and their components (a), chitosan, carrageenan, FMZ, FMZCa, FMZC (b), and EMZ, EMZCa and EMZC (c).
Figure 4
Figure 4
SEM images of FZM (a), FMZCa (b), FMZC (c), EMZ (d), EMZCa (e), and EMZC (f).
Figure 5
Figure 5
FT-IR spectra of all adsorbent types prepared and their components (a), chitosan, carrageenan, FMZ, FMZCa, and FMZC (b), EMZ, EMZCa and EMZC (c).
Figure 6
Figure 6
VSM of FMZ:FMZCa:FMZC (a) and EMZ:EMZCa:EMZC (b).
Figure 7
Figure 7
TGA thermograms of EMZ (a), FMZ (b), EMZCa (c), FMZCa (d), EMZC (e), and FMZC (f).
Figure 8
Figure 8
Chromium removal efficiency (a) and adsorption capacity (b) as a function of adsorbent mass.
Figure 9
Figure 9
Relationship between chromium (a) initial concentration and chromium removal efficiency (%) and (b) initial concentration and adsorption capacity (mg/g).
Figure 10
Figure 10
Relationship between chromium (a) pH and chromium removal efficiency (%) and (b) pH and adsorption capacity (mg/g).
Figure 11
Figure 11
Relationship between chromium (a) time and chromium removal efficiency (%) and (b) time and adsorption capacity (mg/g).
Figure 12
Figure 12
Relationship between chromium (a) temperature and chromium removal efficiency (%) and (b) temperature and adsorption capacity (mg/g).
Figure 13
Figure 13
Removal efficiency and contact time relationship for all four adsorbents.
Figure 14
Figure 14
FT-IR spectrum of FMZ, EMZ, FMZCa, EMZCa, FMZC, and EMZC after adsorption.
Figure 15
Figure 15
SEM images of FZM (a), EMZ (b), FMZCa (c), EMZCa (d), FMZC (e), and EMZC (f) after adsorption.
Figure 17
Figure 17
Elemental composition (%) determined via EDX analysis for EMZCa (a); FMZCa (b); EMZC (c); FMZC (d); EMZ (e), and FMZ (f).
Figure 18
Figure 18
Comparative DTG curves of all prepared adsorbents before/after adsorption: EMZCa (a); FMZCa (b), EMZC (c), FMZC (d), EMZ (e), and FMZ (f).
Figure 19
Figure 19
Schematic representation of the adsorption mechanism of prepared adsorbents: FMZ/FMCa (a), FMZ/FMZC (b) EMZ/EMZCa (c), and EMZ/EMZC (d).
Figure 19
Figure 19
Schematic representation of the adsorption mechanism of prepared adsorbents: FMZ/FMCa (a), FMZ/FMZC (b) EMZ/EMZCa (c), and EMZ/EMZC (d).
Figure 20
Figure 20
(a) Relationship between desorption rate and time. (b) Reusability of all prepared adsorbents.
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