Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species.

Abstract

Studies of the complexation of new promising ligands with uranyl (UO22+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. In this work, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO22+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the complexes of UO22+, VO2+, and VO2+ with the highly preorganized ligand 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) using a combination of fluorescence and absorbance techniques, along with density functional theory (DFT) calculations. The measured stability constant value, log K1, of 16.5 for the UO22+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined stability constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). The structures of the corresponding UO22+, VO2+, and VO2+ complexes with PDA were identified by systematic DFT calculations and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Because of its high chemical stability, selectivity, and structural preorganization for UO22+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from seawater.