Ligand-selective turn-off sensing, harvesting and post-adsorptive use of Dy(III) and Yb(III) by intrinsically fluorescent flower-shaped Gum Acacia-grafted hydrogels

Abstract

Rare earth metals (REMs), such as Dysprosium (Dy) and Ytterbium (Yb), have experienced unprecedented demand in recent times due to their applications in high-end technologies. REMs are found only in select geographic locations placing tremendous economic constraints on their use. In this work, we have developed Gum Acacia-grafted hydrogels (GmAc-FluoroTerPs) that are capable of selective detection and capture of Dy and Yb. The intrinsically blue fluorescent polymer hydrogel GmAc-FluoroTerP has been optimized for Dy(III) and Yb(III) specific quenching, enabling limit of detection of the REMs at 0.13 nM and 60.8 pM, respectively. A comprehensive structural characterization of the fluorescent hydrogel has been performed via NMR, FTIR, XPS, EPR, TGA, XRD, TEM, SEM, EDX, TCSPC, and DLS. In addition to an in situ generated fluorophore, GmAc-FluoroTerP displays a distinctive aggregation induced emission enhancement in mixed solvents. The complexation of Dy(III)/Yb(III) with GmAc-FluoroTerP hydrogel has been characterized by XPS, TCSPC, and logic gate analyses, and the adsorptive capacity for Dy(III) and Yb(III) are found to be best reported till date as 125.57 mg g−1 and 102.27 mg g−1, respectively. Desorption at acidic pH allows recovery of the REMs. We also report semiconducting behaviour of the native fluorescent hydrogel, that is enhanced upon adsorptive capture of Dy(III) and Yb(III), with calculated band gaps at 1.37, 0.77, and 0.49 eV, respectively. The convergent sensing, capture, and reuse of Dy(III) and Yb(III) presented in this work promises a hitherto unreported template for application on other REMs.