Molecular insights into the selective action of a magnetically removable complexone-grafted adsorbent

The binding and release of trivalent rare earth element (REE) cations (Dy(3+), Nd(3+) and La(3+)) from solutions by a new fully characterized magnetic nano adsorbent material, consisting of iminodiacetic acid ligand (H2IDA) grafted onto SiO2 covered γ-Fe2O3 nanoparticles, was investigated. The nano adsorbent revealed a slightly higher capacity towards heavier REE and appreciable selectivity, especially on desorption. It was found that the composition of the surface complex was RE(3+) : L = 1 : 1. The complexation of the molecular H2IDA with RE(3+) in this ratio under non-basic conditions was therefore investigated by X-ray crystallography to produce relevant molecular models. Unexpectedly big differences in coordination numbers and binding mode of IDA along with distinct analogies in packing of the ligand molecules in the obtained 2D-coordination polymer structures provided valuable insights into possible reasons for the observed selectivity.