ThO2 and UO2 nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides.

Neptunium-237 is a radionuclide of great interest owing to its long half-life (2.14 × 10(6) years) and relative mobility as the neptunyl ion (NpO2(+)) under many surface and groundwater conditions. Reduction to tetravalent neptunium (Np(IV)) effectively immobilizes the actinide in many instances due to its low solubility and strong interactions with natural minerals. One such mineral that may facilitate the reduction of neptunium is magnetite (Fe(2+)Fe(3+)2O4). Natural magnetites often contain titanium impurities which have been shown to enhance radionuclide sorption via titanium's influence on the Fe(2+)/Fe(3+) ratio (R) in the absence of oxidation. Here, we provide evidence that Ti-substituted magnetite reduces neptunyl species to Np(IV). Titanium-substituted magnetite nanoparticles were synthesized and reacted with NpO2(+) under reducing conditions. Batch sorption experiments indicate that increasing Ti concentration results in higher Np sorption/reduction values at low pH. High-resolution transmission electron microscopy of the Ti-magnetite particles provides no evidence of NpO2 nanoparticle precipitation. Additionally, X-ray absorption spectroscopy confirms the nearly exclusive presence of Np(IV) on the titanomagnetite surface and provides supporting data indicating preferential binding of Np to terminal Ti-O sites as opposed to Fe-O sites.

Abstract.A tetravalent cerium macrocyclic complex (CeLK4) was prepared with an octadentate terephthalamide ligand comprised of hard catecholate donors, and characterized in the solution state by spectrophotometric titrations and electrochemistry, and in the crystal by X-ray diffraction. The solution state studies showed that L exhibits a remarkably high affinity towards Ce 4+ , with log β110 = 61(2) and ΔG = -348 kJ/mol, compared with log β110 = 32.02(2) for the analogous Pr 3+ complex. In addition, L exhibits an unusual preference for forming CeL 4-relative to formation of the analogous actinide complex, ThL 4-, which has β110 = 53.7(5). The extreme stabilization of tetravalent cerium relative to its trivalent state is also evidenced by the shift of 1.91 V in redox potential of the Ce 3+ /Ce 4+ couple of the complex (measured at -0.454 V vs. SHE). The unprecedented behavior prompted an electronic structure analysis using L3 and M5,4-edge X-ray absorption near-edge structure (XANES) spectroscopies and configuration interaction calculations, which showed that 4f orbital bonding in CeLK4 has partial covalent character owing to ligand-to-metal charge transfer (LMCT) in the ground state. The experimental results are presented in the context of earlier measurements on tetravalent cerium compounds, indicating that the amount LMCT for CeLK4 is similar to that observed for [Et4N]2[CeCl6] and CeO2, and significantly less than that for the organometallic sandwich compound cerocene, (C8H8)2Ce. A simple model to rationalize changes in 4f orbitals for tri-and tetravalent lanthanide and actinide compounds is also provided.