Superparamagnetic Multifunctionalized Chitosan Nanohybrids for Efficient Copper Adsorption: Comparative Performance, Stability, and Mechanism Insights

Polymers (Basel). 2023 Feb 24;15(5):1157. doi: 10.3390/polym15051157.

Abstract

To limit the dangers posed by Cu(II) pollution, chitosan-nanohybrid derivatives were developed for selective and rapid copper adsorption. A magnetic chitosan nanohybrid (r-MCS) was obtained via the co-precipitation nucleation of ferroferric oxide (Fe3O4) co-stabilized within chitosan, followed by further multifunctionalization with amine (diethylenetriamine) and amino acid moieties (alanine, cysteine, and serine types) to give the TA-type, A-type, C-type, and S-type, respectively. The physiochemical characteristics of the as-prepared adsorbents were thoroughly elucidated. The superparamagnetic Fe3O4 nanoparticles were mono-dispersed spherical shapes with typical sizes (~8.5-14.7 nm). The adsorption properties toward Cu(II) were compared, and the interaction behaviors were explained with XPS and FTIR analysis. The saturation adsorption capacities (in mmol.Cu.g-1) have the following order: TA-type (3.29) > C-type (1.92) > S-type (1.75) > A-type(1.70) > r-MCS (0.99) at optimal pH0 5.0. The adsorption was endothermic with fast kinetics (except TA-type was exothermic). Langmuir and pseudo-second-order equations fit well with the experimental data. The nanohybrids exhibit selective adsorption for Cu(II) from multicomponent solutions. These adsorbents show high durability over multiple cycles with desorption efficiency > 93% over six cycles using acidified thiourea. Ultimately, QSAR tools (quantitative structure-activity relationships) were employed to examine the relationship between essential metal properties and adsorbent sensitivities. Moreover, the adsorption process was described quantitatively, using a novel three-dimensional (3D) nonlinear mathematical model.

Keywords: chitosan derivatives; copper adsorption; mathematical modeling; polyamine and amino acid moieties; selectivity; superparamagnetic nanohybrids.