Uranyl peroxide nanoclusters at high-pressure


U60 ([UO2(O2)(OH)]6060− in water) is a uranyl peroxide nanocluster with a fullerene topology and Oh symmetry. U60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U60-bearing material: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 (\(Fm\bar 3\); a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), and the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U60 clusters at high pressure may have been enhanced by the interaction between U60 nanoclusters and the alcohol pressure medium. Once formed, U60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.

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This work was supported as part of the Materials Science of Actinides, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Science under Award #DE-SC0001089. KMT gratefully acknowledges funding from the Stanford VPGE, DARE program. Portions of this work were performed at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA under Award No. DE-NA0001974 and DOE-BES under Award No. DE-FG02-99ER45775, with partial instrumentation funding by NSF. The Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors thank Dr. Changyong Park and Dr. Curtis Kenney-Benson for their help setting up these experiments.

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Turner, K.M., Szymanowski, J.E.S., Zhang, F. et al. Uranyl peroxide nanoclusters at high-pressure. Journal of Materials Research 32, 3679–3688 (2017). https://doi.org/10.1557/jmr.2017.301

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