Insights into Selective Removal by Dye Adsorption on Hydrophobic vs Multivalent Hydrophilic Functionalized MWCNTs

Hydrophilic functionalized carbon nanotubes (MWCNT-COOH) were developed via hydrothermal glucose-coated carbonization, mixing MWCNTs with glucose in different weight ratios. Methyl violet (MV), methylene blue (MB), alizarin yellow (AY), and methyl orange (MO) were used as dye models for adsorption studies. Comparative dye adsorption capacity onto the pristine (MWCNT-raw) and functionalized (MWCNT-COOH-11) CNTs was evaluated in aqueous solution. These results revealed that MWCNT-raw is capable of adsorbing either anionic or cationic dyes. In contrast, an induced selective cation dye adsorption capacity is significantly enhanced on multivalent hydrophilic MWCNT-COOH, in comparison to a pristine surface. This ability can be tuned to the selective adsorption of cations over anionic dyes or between anionic mixtures from binary systems. An insight into adsorbate-adsorbent interactions shows that hierarchical supramolecular interactions dominate the adsorption processes, which is ascribed to the chemical modification by switching from a hydrophobic to a hydrophilic surface, dye charge, temperature, and potential matching multivalent acceptor/donor capacity between chemical groups in the adsorbent interface. The dye adsorption isotherm and thermodynamics on both surfaces were also studied. Changes in the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were evaluated. Thermodynamic parameters were endothermic on MWCNT-raw, whereas the adsorption process on MWCNT-COOH-11 revealed that adsorption processes were spontaneous and exothermic, accompanied by a significant reduction of entropy values as a consequence of a multivalent effect. This approach provides an eco-friendly, low-cost alternative for the preparation of supramolecular nanoadsorbents with unprecedented properties to achieve remarkable selective adsorption independent of the presence of intrinsic porosity.