The hydrolysis of uranium(VI) investigated using EXAFS and 17O-NMR

The hydrolysis of uranium(VI) has been the subject of extensive studies since 50 years because uranyl forms strong comlexes with OH- in solution. A comprehensive discussion and review of the thermodynamic data is published in [1]. We investigated the structure of UO22+ as a function of pH with the aid of U LIII-edge EXAFS spectroscopy. The experiments were carried out at beamline BM20. The equipment allows excellent XAS measurements up to high k-values, 17.5 Å-1 in our case.
The speciation of uranium(VI) at a total concentration of 0.05 M in slightly acidic (pH: 3 to 4) solutions is dominated by the two polynuclear complexes (UO2)2(OH)22+ and (UO2)3(OH)5+. Sample A is an example from this pH region, where (UO2)3(OH)5+ is the dominant species. Structure investigations of these polymeric cations in solution at such uranium concentrations are rare. The formation of polynuclear complexes is clearly confirmed by the U-U interaction at 3.81 Å (Figure 1). Approximately 5 oxygen atoms are coordinated in the equatorial plane at 2.41 Å.
In the following pH region from 6 to 11, the U(VI) speciation is dominated by the precipitation of schoepite phases, UO2(OH)2xH2O (sample B). A longer U-U distance of 3.87 Å was measured. Similar U bond lengths of Ë 3.9 Å were found in schoepite phases. Their structure consists of a network of UO2(OH)2 sheets, where the uranyl centers are connected via a double OH bridge.
In the alkaline pH region (sample C and D), monomeric uranium species are formed. As compared to our previous study [2], we were able to extend the k-space region from 15 Å-1 in [2] up to 17.5 Å-1 and thereby to increase the accuracy. The EXAFS measurements confirm the speciation calculations indicating that UO2(OH)42- is the major species at 0.5 M tetramethylammonium hydroxide (TMA-OH). There are two trends in the EXAFS data, the U-Oaxial bond length increases 1.79, 1.81, and 1.83 Å moving from pH 4.1 to 13.7, while the average U-Oequatorial bond length decreases, 2.41, 2.34, 2.26 Å, respectively. This indicates a stronger bonding of equatorial OH groups with increasing pH. Clark et al. have presented spectroscopic evidence for the formation of a penta-hydroxide complex at high TMA-OH concentrations, however with no information about the equilibrium constant [3]. We have tested the hypothesis of Clark et. al. using 17O-NMR spectroscopy with 17O-enriched "yl" oxygens. The spectrum recorded at 258 K (Figure 2) shows only one peak for UO2(OH)42- in 1 M TMA-OH. However, when increasing the hydroxide concentration to 3 M two peaks were obtained, one with the same shift as in the 1 M TMA-OH solution, 1132.2 ppm, the other at 1135.8 ppm presumably due to UO2(OH)53- (Figure 2). To conclude, the complex UO2(OH)42- has a very broad range of existence in strongly alkaline solution. At very high total concentrations of hydroxide [> 1 M TMA-OH], an additional OH- ligand may coordinate in an associative reaction.