In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient actinide extraction and the selectivity toward minor actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.

Amine grafting on MOFs greatly enhances the adsorbability of Cr-MIL-101 towards U(vi) from an aqueous solution, and the enhancement depends on the coverage and flexibility of the grafted amino group.

MOF-76 exhibits not only high sensitivity for the detection of U(vi), but also high adsorption capacity of 298 mg g(-1) at a low pH value of ∼3.0. Furthermore, the high selectivity for uranium adsorption over a series of competing metal ions is also illustrated.

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The separation and recovery of uranium from radioactive wastewater is important from the standpoints of environmental protection and uranium reuse. In the present work, magnetically collectable TiO 2 /Fe 3 O 4 and its graphene composites were fabricated and utilized for the photocatalytical removal of U(VI) from aqueous solutions. It was found that, under ultraviolet (UV) irradiation, the photoreactivity of TiO 2 /Fe 3 O 4 for the reduction of U(VI) was 19.3 times higher than that of pure TiO 2 , which is strongly correlated with the Fe 0 and additional Fe(II) generated from the reduction of Fe 3 O 4 by TiO 2 photoelectrons. The effects of initial uranium concentration, solution pH, ionic strength, the composition of wastewater, and organic pollutants on the U(VI) removal by TiO 2 /Fe 3 O 4 were systematically investigated. The results demonstrated its excellent performance in the cleanup of uranium contamination. As graphene can efficiently attract the TiO 2 photoelectrons and thus decrease their transfer to Fe 3 O 4 , the photodissolution of Fe 3 O 4 in the TiO 2 /graphene/Fe 3 O 4 composite can be largely alleviated compared to that of the TiO 2 /Fe 3 O 4 , rendering this ternary composite a much higher stability. In addition, scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray absorption near edge spectroscopy (XANES), and X-ray photoelectron spectroscopy (XPS) were used to explore the reaction mechanisms.

Efficient nuclear waste treatment and environmental management are important hurdles that need to be overcome if nuclear energy is to become more widely used. Herein, we demonstrate the first case of using two-dimensional (2D) multilayered V2CTx nanosheets prepared by HF etching of V2AlC to remove actinides from aqueous solutions. The V2CTx material is found to be a highly efficient uranium (U(VI)) sorbent, evidenced by a high uptake capacity of 174 mg g(-1), fast sorption kinetics, and desirable selectivity. Fitting of the sorption isotherm indicated that the sorption followed a heterogeneous adsorption model, most probably due to the presence of heterogeneous adsorption sites. Density functional theory calculations, in combination with X-ray absorption fine structure characterizations, suggest that the uranyl ions prefer to coordinate with hydroxyl groups bonded to the V-sites of the nanosheets via forming bidentate inner-sphere complexes.

Although a variety of tetradentate ligands, 6,6'-bis(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2'-bipyridines (BTBPs), have been proved as effective ligands for selective extraction of Am(III) over Eu(III) experimentally, the origin of their selectivity is still an open question. To elucidate this question, the geometric and electronic structures of the actinide and lanthanide complexes with the BTBPs have been investigated systematically by using relativistic quantum chemistry calculations. We show herein that in 1:1 (metal:ligand) type complexes substitution of electron-donating groups to the BTBP molecule can enhance its coordination ability and thus the energetic stability of the formed Am(III) and Eu(III) complexes in the gas phase. According to our results, Eu(III) can coordinate to the BTBPs with higher stability in energy than Am(III), no matter whether there are nitrate ions in the inner-sphere complexes. The presence of nitrate ions leads to formation of the probable Am(III) and Eu(III) complexes, M(NO(3))(3)(H(2)O)(n) (M = Am, Eu), in nitric acid solutions. It has been found that the changes of Gibbs free energy play an important role for Am(III)/Eu(III) separation. In fact, the weaker complexing ability of Am(III) with nitrate ions and water molecules makes the decomposition of Am(NO(3))(3)(H(2)O)(4) more favorable in energy, which may thus increase the possibility of formation of Am(BTBPs)(NO(3))(3). Our work may shed light on the design of novel extractants for Am(III)/Eu(III) separation.