Facile incorporation of technetium into magnetite, magnesioferrite, and hematite by formation of ferrous nitrate in situ: precursors to iron oxide nuclear waste forms.

The fission product, 99Tc, presents significant challenges to the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate (TcO4-), the stable Tc species in aerobic environments. Migration of 99Tc from disposal sites can potentially be prevented by incorporating it into durable waste forms based on environmentally stable minerals. Since Tc(iv) and Fe(iii) have the same ionic radius, Tc(iv) can replace Fe(iii) in iron oxides. Environmentally durable iron oxides include goethite (α-FeOOH), hematite (α-Fe2O3), and magnesioferrite (MgFe2O4). The incorporation of Tc into two of these, hematite and magnesioferrite, as well as magnetite (Fe3O4) by means of simple, aqueous chemistry is presented starting from TcO4- in 5 M nitric acid. A combination of X-ray diffraction and X-ray absorption fine structure spectroscopy reveals that Tc(iv) replaces Fe(iii) within the iron oxide structures. Following incorporation, Tc doped samples were suspended in deionized water under aerobic conditions, and the release rates of Tc were determined. The results of this work show that Tc leaches more quickly from Fe3O4 than from α-Fe2O3 or MgFe2O4. Modeling the leach rates and comparison with the leach rate of Tc from TiO2 indicate that release of Tc is controlled by solid state diffusion

Organic layer formation and sorption of U(vi) on acetamide diethylphosphonate-functionalized mesoporous silica.

Acetamide diethylphosphonate (AcPhos)-functionalized silica has been shown to have a high affinity for U(vi) in pH 2-3 nitric acid. Previous work with AcPhos-functionalized silica has focused on actinide and lanthanide extraction under various conditions, but has shown poor reproducibility in the functionalization process. For this work, four AcPhos-functionalized SBA-15 materials were synthesized and evaluated based on their U(vi) sorption capacity and their stability in nitric acid. Materials synthesized using pyridine as a basic catalyst were shown to form a greater fraction of polymeric structures at the silica surface, which correlated with higher structural integrity upon contact with acidic solutions. Single-pulse 31P and 1H NMR spectra of these materials show evidence of phosphonic acid groups, as well as hydrogen-bonding interactions either between ligands or with the silica surface. Additionally, these materials were found to have significantly higher U(vi) sorption capacities and Keq values than the materials synthesized without pyridine, most likely due to the ion-exchange properties of the phosphonic acid groups. The 31P-31P DQ-DRENAR NMR technique was used to compare the average strength of dipolar coupling interactions between phosphorus atoms for the four materials. Because the strength of dipolar coupling interactions depends on the number and proximity of neighboring spins, this technique provides information about the average density of ligands on the surface. The conventional functionalization procedure yielded materials with the lowest average surface ligand density, while those using extended reaction times and the pyridine base catalyst yielded materials with higher surface ligand densities

Reduction of CO2 and CS2 with Uranium(III) Metallocene Aryloxides

The reactivity of two metallocene aryloxide U(III) complexes, [(C5Me5)2U(O-Ar)], Ar = 4-tBuC6H4, 1; Ar = 2,6-tBu2-4-CH3C6H2(BHT), 3, with CO2and CS2has been investigated. The reaction of 1 with CO2produces a bridging oxo complex, [{(C5Me5)2(4-tBuC6H4-O)U}2(μ2-O)], 4, while 3 with CO2results in reductive disproportionation to form the bridging carbonate species, [{(C5Me5)2(BHT)U}2(μ2-κ2:η1-CO3)], 5. The difference in reactivity can be attributed to the steric properties of the ligand because the reaction of 3 with an oxo-delivering agent yields a U(V) terminal oxo complex, [(C5Me5)2(BHT)U═O], 6. Reduction of CS2to form a bridging (CS2)2-ligand, [{(C5Me5)2(tBuC6H4-O)U}2(μ2-CS2)], 7, is observed with 1, while the reaction of 3 with CS2also produces a bridging (CS2)2-reduced ligand complex, followed by C-H bond activation of a methyl group from one (C5Me5)1-ring, [(C5Me5)2(BHT)U{μ2-C(H)S2}U(C5Me4CH2)(C5Me5)(BHT)], 8. All compounds are characterized by NMR and IR spectroscopy, and their solid-state structures are determined by X-ray crystallography

Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy.

The electronic structure in the complete series of stable lanthanide sesquioxides, Ln2O3 (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy (XAS) with a scanning transmission X-ray microscope (STXM). The experimental results agree with recent synthetic, spectroscopic and theoretical investigations that provided evidence for 5d orbital involvement in lanthanide bonding, while confirming the traditional viewpoint that there is little Ln 4f and O 2p orbital mixing. However, the results also showed that changes in the energy and occupancy of the 4f orbitals can impact Ln 5d and O 2p mixing, leading to several different bonding modes for seemingly identical Ln2O3 structures. On moving from left to right in the periodic table, abrupt changes were observed for the energy and intensity of transitions associated with Ln 5d and O 2p antibonding states. These changes in peak intensity, which were directly related to the amounts of O 2p and Ln 5d mixing, were closely correlated to the well-established trends in the chemical accessibility of the 4f orbitals towards oxidation or reduction. The unique insight provided by the O K-edge XAS is discussed in the context of several recent theoretical and physical studies on trivalent lanthanide compounds

Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce2(C8H8)3 and Ce(C8H8)2

New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolated f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a"triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules

Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone.

The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex

Spectroscopic Characterization of Aqua [ fac-Tc(CO)3]+ Complexes at High Ionic Strength.

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I-VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac-Tc(CO)3(OH2)3- n(OH) n]1- n (where n = 0-3) were examined by a range of spectroscopic techniques including 99Tc/13C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc-C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac-Tc(CO)3(OH2)3]+ > [ fac-Tc(CO)3(OH2)2(OH)] > [ fac-Tc(CO)3(OH2)(OH)2]-. These results correlate with established trends of the 99Tc upfield chemical shift and carbonyl 13C downfield chemical shift. The lone exception is [ fac-Tc(CO)3(OH)]4 which exhibits a comparatively low electron density at the metal center attributed to the μ3-bridging nature of the -OH ligands causing less σ-donation and no π-donation. This work also reports the first observations of these compounds by XPS and [ fac-Tc(CO)3Cl3]2- by XAS. The unique and distinguishable spectral features of the aqua [ fac-Tc(CO)3]+ complexes lay the foundation for their identification in the complex aqueous matrixes

Getters for improved technetium containment in cementitious waste forms.

A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This work focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ∼0.08wt% of the total waste form mass. The observed diffusion (Dobs) of Tc decreased from 4.6±0.2×10-12cm2/s for Cast Stone that did not contain a getter to 5.4±0.4×10-13cm2/s for KMS-2 containing Cast Stone. It was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc Dobs when using the KMS-2

Research program to investigate the fundamental chemistry of technetium

The objective of this research is to increase the knowledge of the fundamental technetium chemistry necessary to address challenges to the safe, long-term disposal of high-level nuclear waste posed by this element. The primary issues examined during the course of this project were the behavior of technetium and its surrogate rhenium during waste vitrification and glass corrosion. Since the redox behavior of technetium can play a large role in determining its volatility, one goal of this research was to better understand the behavior of technetium in glass as a function of the redox potential of the glass melt. In addition, the behavior of rhenium was examined, since rhenium is commonly used as a surrogate for technetium in waste vitrification studies. A number of glasses similar to Hanford Low Activity Waste (LAW) glasses were prepared under controlled atmospheres. The redox state of the glass was determined from the Fe(II)/Fe(III) ratio in the cooled glass, and the speciation of technetium and rhenium was determined by x-ray absorption fine structure (XAFS) spectroscopy. The behavior of rhenium and technetium during glass alteration was also examined using the vapor hydration test (VHT)