Structural study on 2,2'-(methylimino)bis(N,N-dioctylacetamide) complex with Re(VII)O4- and Tc(VII)O4- by 1H NMR, EXAFS, and IR spectroscopy

The structures of the complex of 2,2'-(methylimino)bis(N,N-dioctylacetamide) (MIDOA) with M(VII)O(4)(-) (M = Re and Tc), which were prepared by liquid-liquid solvent extraction, were investigated by using (1)H nuclear magnetic resonance (NMR), extended X-ray absorption fine structure (EXAFS), and infrared (IR) spectroscopy. The (1)H NMR spectra of the complex of MIDOA with Re(VII)O(4)(-) prepared in the organic solution suggest the transfer of a proton from aqueous to organic solution and the formation of the H(+)MIDOA ion. The EXAFS spectra of the complexes of H(+)MIDOA with Re(VII)O(4)(-) and Tc(VII)O(4)(-) show only the M-O coordination of the aquo complexes, suggesting that the chemical state of M(VII)O(4)(-) was unchanged during the extraction process. The results from (1)H NMR and EXAFS, therefore, provide evidence of M(VII)O(4)(-)···H(+)MIDOA complex formation in the organic solution. The IR spectra of Re(VII)O(4)(-)···H(+)MIDOA and Tc(VII)O(4)(-)···H(+)MIDOA were analyzed based on the structures and the IR spectra that were calculated at the B3LYP/cc-pVDZ level. Comparison of the observed and calculated IR spectra demonstrates that an intramolecular hydrogen bond is formed in H(+)MIDOA, and the M(VII)O(4)(-) ion interacts with H(+)MIDOA through multiple C-H(n)···O hydrogen bonds.     

An EXAFS and TRLFS investigation on uranium(VI) sorption to pristine and leached albite surfaces

Uranium(VI) was sorbed to freshly ground and leached albite in batch and flow-through systems in the pH range 5.0-6.4. The uranium(VI) surface complexes were studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The EXAFS analysis of uranium(VI) sorbed on albite at pH 5.8 and 5 x 10(-6) M U(VI) showed one silicon atom at a USi distance of 3.09 A, which is indicative of the formation of an inner-sphere, mononuclear, bidentate uranium(VI) surface complex, Si(O)2UO2, on the silicate tetrahedra of albite. Two additional uranium(VI) sorption complexes were detected by TRLFS at higher initial aqueous U(VI) concentrations. However, the structure of these surface complexes could not be derived from EXAFS, since the measured EXAFS spectra represent the average of two surface complex structures. In order to simulate U(VI) sorption onto weathered feldspar surfaces, albite was leached with 0.01 M HClO4, resulting in surface material similar to amorphous silica gel. EXAFS showed that the equatorial oxygen shell of uranium(VI) sorbed on this material at pH 5.0 and 5.8 was split in two distances of 2.23 and 2.44 A. This indicates the formation of an inner-sphere surface complex.     

Singularities of the solution of a mixed problem for a general second order elliptic equation and boundary stabilizationof the wave equation

We deal here with a second order elliptic mixed problem which is posed in a regular open bounded domain of . We study the regularity of its solution. We apply our results to the boundary stabilization of the wave equation.     

A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO2 Nanoparticles

Here we provide evidence that the formation of PuO₂ nanoparticles from oxidized Pu^VI under alkaline conditions proceeds through the formation of an intermediate Pu^V solid phase, similar to NH₄PuO₂CO₃, which is stable over a period of several months. For the first time, state‐of‐the‐art experiments at Pu M₄ and at L₃ absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase.     

Shedding Light on the Enigmatic TcO2 ⋅ xH2O Structure with Density Functional Theory and EXAFS Spectroscopy**

The β-emitting ⁹⁹Tc isotope is a high-yield fission product in ²³⁵U and ²³⁹Pu nuclear reactors, raising special concern in nuclear waste management due to its long half-life and the high mobility of pertechnetate (TcO₄⁻). Under the conditions of deep nuclear waste repositories, Tc is retained through biotic and abiotic reduction of TcO₄⁻ to compounds like amorphous TcO₂ ⋅ xH₂O precipitates. It is generally accepted that these precipitates have linear (Tc(μ-O)₂(H₂O)₂)_n chains, with trans H₂O. Although corresponding Tc−Tc and Tc−O distances have been obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy, this structure is largely based on analogy with other compounds. Here, we combine density-functional theory with EXAFS measurements of fresh and aged samples to show that, instead, TcO₂ ⋅ xH₂O forms zigzag chains that undergo a slow aging process whereby they combine to form longer chains and, later, a tridimensional structure that might lead to a new TcO₂ polymorph.     

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.     

Stoichiometry and structure of uranylVI hydroxo dimer and trimer complexes in aqueous solution

We studied the structure and stoichiometry of aqueous uranylVI hydroxo dimers and trimers by spectroscopic (EXAFS, FTIR, UV-vis) and quantum chemical (DFT) methods. FTIR and UV-vis spectroscopy were used for the speciation of uranyl complexes in aqueous solution. DFT calculations show that (UO2)2(OH)22+ has two bridging hydroxo groups with a U-U distance of 3.875 A. This result is in good agreement with EXAFS, where a U-U distance of 3.88 A was found. For the hydroxo trimer complex, DFT calculations show that the species (UO2)3(O)(OH)3+ with oxo bridging in the center is energetically favored in comparison to its stoichiometric equivalent (UO2)3(OH)5+. This is again in line with the EXAFS result, where a shorter U-U distance of 3.81-3.82 A and evidence for oxo bridging in the center were found. Several stable intermediates which lie several tens of kJ/mol above that of (UO2)3(O)(OH)3+ were identified, and their structures, energies, and intramolecular proton-transfer reaction are discussed.