Perrhenate and pertechnetate complexation by an azacryptand in nitric acid medium

Technetium is present as the pertechnetate anion in spent nuclear fuel solutions, and its extraction by several extractant systems is a major problem for the liquid-liquid extraction processes used to separate uranium and plutonium. To prevent technetium extraction into the organic phase, a complexing agent may be added to the aqueous nitric acid phase to selectively bind the pertechnetate anion. In the present study, liquid-liquid extraction experiments reveal that technetium distribution ratios are considerably lowered with addition of an azacryptand, which is a good receptor for pertechnetate anion recognition. This ligand is able to overcome the Hofmeister bias and selectively bind techetium in nitric acid solution. Coordination studies using infrared and Raman spectoscopies and DFT calculations show the formation of an inclusion complex with hydrogen bonds stabilizing the oxo-anion within the cavity. For the first time, the cage molecules are studied for an extraction process.