Integrating spectroscopic analysis and theoretical calculations to elucidate the adsorption efficiency and mechanisms of Cd, Pb, and Cu using novel carboxymethyl cellulose/pectin-based hydrogel beads.

Herein, a series of novel carboxymethyl cellulose (CMC)/pectin-based hydrogel beads were synthesized with chitosan as a cross-linker. The hydrogel composites were denoted as CPC-1/2/3/4/5, with varying mass ratios of CMC, pectin, and chitosan (6:0:1, 5:1:1, 4:2:1, 3:3:1, and 2:4:1). This is a pioneering study that investigates the synergistic effects of these biopolymers in a single hydrogel system for the adsorption of heavy metals, specifically Cd, Pb, and Cu. CPC-4 was identified as the optimal adsorbent, and its adsorption behavior, efficiency, and mechanisms were systematically explored. The adsorption kinetics of CPC-4 for Cd, Pb, and Cu adhered to the pseudo-second-order model, while equilibrium adsorption isotherms were best described by the Langmuir model. Notably, CPC-4 achieved maximum adsorption capacities for Cd, Pb, and Cu of 139.4, 270.3, and 143.6 mg/g, respectively. Spectroscopic analyses including FTIR and XPS revealed abundant oxygen- and nitrogen-bearing functional groups (carboxyl, hydroxyl, and amine) in CPC-4, which facilitated metal ion binding through complexation reactions. Density functional theory calculations demonstrated that the incorporation of chitosan significantly enhanced the interaction between CMC and pectin, identifying the coupled regions as the most favorable sites for metal adsorption, with adsorption energies of -4.03 eV for Cd, -4.59 eV for Pb, and -5.59 eV for Cu. The superior adsorption performance of CPC-4 is primarily attributed to complexation and hydrogen bonding at the cross-linked sites. In summary, this study highlights the potential of this biopolymer-based hydrogel composite as a promising new adsorbent for the effective management of heavy metal contamination in aquatic environments.