Monitoring Redox Behaviour of Actinide Ions by a Combination of Emission and NMR Spectroscopy

Europe currently holds a substantial nuclear legacy arising from fission activities, with a large proportion of high activity wastes that pose a radiological threat to natural and engineered environments. The decision to dispose of these high level wastes (following separation) in a suitable geological disposal facility (GDF) has provided some of the most demanding technical, and environmental challenges facing the EU in the coming century. In order to address these issues, we have begun a programme of work to establish a comprehensive understanding of the electronic properties and physical and chemical properties of the radioactive actinide metals using state of the art emission spectroscopic techniques in combination with NMR and computational methods.[1,2]
Our approach to this is to firstly use coordination chemistry to synthesise uranium compounds with ligands that model environmentally complexed species and use optical spectroscopy to understand and map both the chemical and physical behaviour of these species (Figure 1). We have recently established that U(IV) complexes are emissive and will demonstrate that uranium in the +IV and +VI oxidation states can be detected simultaneously at relatively low concentrations. Time gating techniques enable the long lived uranyl(VI) species to be separated from the shorter lived uranium(IV) species. Furthermore, the form of the emission spectra of uranyl(VI) compounds are extremely sensitive to the nature of the ligand bound in the equatorial plane and the complex nuclearity (extent of aggregation), potentially giving a sensitive method of assessing the solution forms of uranium in environmental conditions. We will next discuss how the optical properties of these model compounds can be extended to the trans-uranics and applied to disproportionation reactions and redox events in solution.
Financial support for this research was provided by the UK Engineering and Physical Sciences Research Council (EPSRC) and The Leverhulme Trust. The authors thank the European Commission Euratom FP7 funded project
(no. 269923) EURACT-NMR for support.
1. L.S. Natrajan, Coord. Chem. Rev., 2012, 256, 1583; Coord. Chem. Rev., 2014, 266–267, 171.
2. S.D. Woodall, A.N. Swinburne, N. lal Banik, A. Kerridge, P. Di Pietro, C. Adam, P. Kaden and L.S. Natrajan, Chem. Commun., 2015, 51, 5402.