Insight into γ-Irradiation-Induced Structure Evolution of Uranium(IV) Germanates as Crystalline Nuclear Waste Forms.

Abstract

New kinds of crystalline waste forms with improved structural stability are desirable for actinide immobilization. In this work, using a molten salt method, two uranium(IV) germanate compounds, namely, K2UGe3O9 (1) and K2UGe2O7 (2), were synthesized, whose compositions consisted of trimeric and dimeric units of germanate, as well as tetravalent uranium, as proved by bond valence calculation and X-ray absorption spectra. Radiation stability assessment is further performed by γ-irradiation to assess the potential of as-synthesized uranium germanate compounds as nuclear waste forms. Powder X-ray diffraction and single-crystal diffraction analyses reveal that 1 remains stable within 1 MGy dosage and undergoes a significant structural change with increasing dosage at 2 MGy, leading to a transformation of 1 to 1-ir analogous to 2 in chemical structure. The underlying mechanism was further studied through a combination of different characterization techniques, including Raman, UV-vis, and electron paramagnetic resonance spectroscopies. Density functional theory calculations of 1 and 2 were also conducted to probe the coordination interaction of germanium and uranium with oxygen atoms. This work reports new crystalline uranium germanates by flux growth and, most importantly, provides insights into the irradiation stability of these materials, which will be beneficial to developing waste forms for long-term immobilization of radionuclides.