Complex formation between uranium(VI) and calix[6]arenes studied by time-resolved laser-induced fluorescence spectroscopy

Seepage and mine waters of the abandoned uranium mining and milling sites in Saxony and Thuringia are contaminated by uranium and its decay products. Therefore, efficient water purification technologies are necessary.
The separation of uranium(VI) from aqueous solution by calixarenes by means of solvent extraction is described in the literature. Calixarenes are macrocyclic molecules formed by 4, 6 or 8 para-substituted phenolic units linked by methylene bridges ortho to the OH functions. Thus, molecules of different ring sizes are formed. Especially calix[6]arenes functionalized with carboxylic or hydroxamic groups on the lower rim are suitable to separate uranium from aqueous solution.
In the present work, the extraction efficiency of various carboxylate derivatives of calix[6]arene, e.g., carboxymethoxy-p-tert-octyl-calix[6]arene, including their selectivity towards uranium(VI) is studied in a two phases solvent extraction system in dependence on pH value and the amount of competing ions in aqueous solution as well as in dependence on ligand concentration and solvent. The complex formation between uranium(VI) and calix[6]arenes is further studied by means of time-resolved laser-induced fluorescence spectroscopy (TRLFS). Uranium species are identified, complex formation constants are determined, and reaction mechanisms are discussed. The suitability of the calix[6]arenes as efficient reagents for selective separation of uranium from aqueous solution, even in the acidic pH region, is shown.