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The effect of iron binding on uranyl(v) stability
Radmila Faizova1, Sarah White1, Rosario Scopelliti1
1Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , CH-1015 Lausanne , Switzerland .
Chemical Science
|October 16, 2018
Summary
Iron binding to uranyl(V) complexes enhances their stability against proton-induced disproportionation. This cation-cation interaction is crucial for stabilizing uranyl(V) species, offering insights into uranium(VI) reduction in the environment.
Area of Science:
- Inorganic Chemistry
- Coordination Chemistry
- Environmental Chemistry
Background:
- Uranyl complexes are central to uranium chemistry and environmental processes.
- Understanding the stability of uranyl(V) species is critical for managing uranium.
- Proton-induced disproportionation poses a challenge to uranyl(V) stability.
Purpose of the Study:
- To investigate the effect of UO2+···Fe2+ cation-cation interactions on uranyl(V) redox properties.
- To assess the impact of these interactions on stability against proton-induced disproportionation.
- To explore the role of iron binding in stabilizing uranyl(V) compounds relevant to environmental uranium reduction.
Main Methods:
- Synthesis and characterization of uranyl(VI) and uranyl(V) complexes using a tripodal heptadentate Schiff base ligand (trensal3-).
- Investigation of cation-cation interactions, including UO2+···K+ and UO2+···Fe2+.
- Electrochemical studies using cyclic voltammetry to determine redox properties and stability ranges.
- Protonation studies to evaluate stability against disproportionation.
Main Results:
- Uranyl(V) complexes with Fe2+ bound to uranyl(V) oxygen showed increased stability against proton-induced disproportionation.
- Formation of a stable Fe2+-UO2+-U4+ intermediate was observed upon protonation of a Fe2+-bound uranyl(V) complex.
- Cyclic voltammetry revealed an expanded stability range for uranyl(V) species in the presence of Fe2+ against both oxidation and reduction.
- The presence of a proton in uranyl complexes generally reduced the stability range of uranyl(V).
Conclusions:
- UO2+···Fe2+ cation-cation interactions significantly enhance the stability of uranyl(V) complexes.
- Iron binding plays a key role in stabilizing uranyl(V) species, particularly against proton-induced disproportionation.
- These findings provide valuable insights into the environmental mineral-mediated reduction of uranium(VI).
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