Highly Efficient and Selective Recovery of Rare Earth Elements Using Mesoporous Silica Functionalized by Preorganized Chelating Ligands

Separating the rare earth elements (REEs) in an economically and environmentally sustainable manner is one of the most pressing technological issues of our time. Herein, a series of preorganized bidentate phthaloyl diamide (PA) ligands was synthesized and grafted on large-pore 3-dimensional (3-D) KIT-6 mesoporous silica. The synthesized sorbents were fully characterized by N-2 physisorption, FT-IR, C-13 cross-polarization (CP) and Si-29 magic-angle spinning (MAS) NMR, thermogravimetric analysis-differential thermal analysis (TGA-DTA), and elemental analysis. Overall, the grafting of PA-type ligands was found to have significantly improved the extraction performance of the sorbents toward REEs compared to the homogeneous analogues. Specifically, the sorbent modified with the 1,2-phtaloyl ligand shows high preference over lanthanides with smaller size, whereas the 1,3-phtaloyl ligand exhibits selectivity toward elements with larger ion radius. This selectivity drastically changes from the homogeneous models that do not exhibit any selectivity. The possibility of regenerating the mesoporous sorbents through simple stripping using oxalate salt is demonstrated over up to 10 cycles with no significant loss in REEs extraction capacity, suggesting adequate chemical and structural stability of the new sorbent materials. Despite the complex ion matrix and high ionic composition, the exposure of industrial mining deposits containing REEs to the sorbents results in selective recovery of target REEs.