Understanding competitive Cu²⁺ and Zn²⁺ adsorption onto functionalized cellulose fiber via experimental and...

Amidoxime groups were successfully introduced to develop a novel amidoxime-functionalized cellulose fiber (AO-Cell) for absorptive removal of heavy metal ions in wastewater. The chemical structure, and the competitive adsorption of Cu²⁺ and Zn²⁺ by AO-Cell were investigated by experiments study, Density functional theory (DFT) and molecular dynamic (MD) simulation. The results showed the N and O atoms in the amidoxime group can spontaneously interact with Cu²⁺ and Zn²⁺ through sharing long pair electrons to generate stable coordination structure, which was the dominant adsorption mechanism. Besides, the enlarged surface area, improved hydrophilicity and dispersion offered by AO-Cell facilitate the adsorption process by increasing the accessibility of absorption sites. As results of these synergetic modification, AO-Cell can remain effective in a wide pH range (1-6) and reach adsorption equilibrium within 60 min. At optimal conditions, the achieved theoretical adsorption capacity is as high as 84.81 mg/g for Cu²⁺ and 61.46 mg/g for Zn²⁺ in the solution with multiple ions. The competition between Cu²⁺ and Zn²⁺ in occupying the absorption sites arises from the difference in the metallic ion affinity and covalent index with the adsorbent as demonstrated by the MD analysis. Importantly, AO-Cell demonstrated favorable recyclability after up to 10 adsorption-desorption cycles.