Hydrothermal Syntheses of Uranium Oxide Hydrate Materials with Sm(III) Ions: pH-Driven Diversities in Structures and Morphologies and Sm-Doped Porous Uranium Oxides Derived from Their Thermal Decompositions.

We report the hydrothermal syntheses of three uranyl oxide hydroxy-hydrate (UOH) materials containing Sm(III) ions ( UOH-Sm ) by controlling the solution pH and a new way to make Sm-doped porous uranium oxides with different U-to-Sm atomic ratios via their thermal decompositions. While layer-structured UOH-Sm phases with U-to-Sm atomic ratios of 1 ( UOH-Sm1 ) and 4 ( UOH-Sm2 ) were obtained from the reaction of schoepite and samarium nitrate with final solution pH values of over 4, similar reactions without pH adjustment with final solution pH values of less than 4 led to the formation of a uranyl oxide framework ( UOF-Sm ) with a U-to-Sm atomic ratio of 5.5. The crystal structure of compound UOF-Sm was revealed with synchrotron single-crystal X-ray diffraction and confirmed with transmission electron microscopy. The two-dimensional uranyl oxide hydroxide layers, similar to that for β-U ₃ O ₈ , are linked by double pentagonal uranyl polyhedra to form a three-dimensional framework with Sm(III) ions in the channels. Scanning electron microscopy characterization revealed nanoplate crystal morphologies for the two UOH-Sm phases, in contrast to the needle morphology for UOF-Sm . Subsequent thermal treatments led to the formation of Sm-doped uranium oxides, maintaining the original crystal shapes and U-to-Sm ratios but with nanopores. This work demonstrated that the hydrothermal synthesis conditions, especially fine-tuning of the solution pH, have a significant impact on the uranium hydrolysis, thus leading to well-defined products. This will facilitate the targeted syntheses of UOH phases with lanthanide (Ln) ions and explore the subsequent applications of these materials and Ln-doped porous uranium oxides as potential nuclear or functional materials.