Specialized extractant ligands – such as tri-butyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-2-ethylhexylisobutryamide (DEHiBA) – have been developed for the recovery of uranium from used nuclear fuel by reprocessing solvent...
A comprehensive multiscale model determines the fundamental reaction mechanisms of the radical-induced degradation of acetohydroxamic acid in acidic aqueous solutions.
Aqueous geochemistry could be extended considerably if nuclear-magnetic resonance (NMR) methods could be adapted to study solutions at elevated temperatures and pressures. We therefore designed an NMR probe that can be used to study aqueous solutions at gigapascal pressures. Fluoride solutions were chosen for study because 19 F couples to other nuclei in the solutions (31 P and 11 B) in ways that make peak assignments unequivocal. Correspondingly, NMR spectra of 19 F-and 11 B were collected on aqueous HBF 4-NH 4 PF 6 solutions to pressures up to 2.0 GPa. At pressure, peaks in the 19 F spectra were clear and assignable to the BF 4 À (aq), F À (aq) and BF 3 OH À (aq) ions, and these aqueous complexes varied in signal intensity with pressure and time, for each solution. Peaks in the 11 B spectra at pressure could be assigned to the BF 4 À (aq) and BF 3 OH À (aq) species. Additionally, there is a single peak that is assignable to H 3 BO 3 o (aq) and B(OH) 4 À (aq) in rapid-exchange equilibria. These peaks broaden and move with pressure in ways that suggest reversible interconversion of borate and fluoroborate species. The PF 6 À ion was found to provide a suitable 19 F shift and intensity standard for high-pressure spectra because it was chemically inert. The positions and intensities of the doublet peak also remains constant as a function of pressure and pH. Addition of electrolytes considerably distorts the phase diagram of water such that the stability region of the aqueous solution expands to well beyond the 0.8 GPa freezing pressure of pure water; some fluoroborate solutions remain liquid until almost 2.0 GPa.
Good quality drinking water is necessary to maintain a high quality of life. Millions lack access to clean and safe drinking water, and current trends suggest that billions will face acute water shortages in the coming decades. Development of new materials has led to technological impacts on water purification, from desalination membranes to atmospheric water scavenging. However, the most challenging aspect of technological solutions is cost: if the community being serviced cannot afford the solution, it is not likely to be sustainable. Repurposing Earth‐abundant materials to replace highly engineered solutions is an atractive solution. Herein, minimal processing of bauxite rocks produces a high‐porosity and reactive activated alumina in situ, without purification directly from the ore. This acid‐treated, thermally activated bauxite (ATAB) exhibits a high surface area of 401 ± 6 m2 g−1, a 40‐fold increase relative to its parent ore, and a 2× increase relative to the state‐of‐the‐art fluoride adsorbent, activated alumina. The composition, preparation, and mechanism of adsorption are studied by X‐ray diffraction, X‐ray photoelectron spectroscopy, and multiple‐quantum magic‐angle spinning 27Al nuclear magnetic resonance (NMR). The maximum adsorption density of ATAB is comparable with that of activated alumina, but ATAB requires fewer processing steps, thus warranting future consideration as a primary adsorbent of choice for fluoride removal from water.
The solution chemistry of aluminum has long interested scientists due to its relevance to materials chemistry and geochemistry. The dynamic behavior of large aluminum-oxo-hydroxo clusters, specifically [Al O (OH) (H O) ] (Al ), is the focus of this paper. Al NMR, H NMR, and H DOSY techniques were used to follow the isomerization of the ϵ-Al in the presence of glycine and Ca at 90 °C. Although the conversion of ϵ-Al to new clusters and/or Baker-Figgis-Keggin isomers has been studied previously, new H NMR and H DOSY analyses provided information about the role of glycine, the ligated intermediates, and the mechanism of isomerization. New H NMR data suggest that glycine plays a critical role in the isomerization. Surprisingly, glycine does not bind to Al clusters, which were previously proposed as an intermediate in the isomerization. Additionally, a highly symmetric tetrahedral signal (δ=72 ppm) appeared during the isomerization process, which evidence suggests corresponds to the long-sought α-Al isomer in solution.
Conformational changes of the pyrophosphate (Pp)-functionalized uranyl peroxide nanocluster [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 12 ] 48− ({U 24 Pp 12 }), dissolved as a Li/Na salt, can be induced by the titration of alkali cations into solution. The most symmetric conformer of the molecule has idealized octahedral (O h ) molecular symmetry. One-dimensional 31 P NMR experiments provide direct evidence that both K + and Rb + ions trigger an O h -to-D 4h conformational change within {U 24 Pp 12 }. Variable-temperature 31 P NMR experiments conducted on partially titrated {U 24 Pp 12 } systems show an effect on the rates; increased activation enthalpy and entropy for the D 4h -to-O h transition is observed in the presence of Rb + compared to K + . Twodimensional, exchange spectroscopy 31 P NMR revealed that magnetization transfer links chemically unique Pp bridges that are present in the D 4h conformation and that this magnetization transfer occurs via a conformational rearrangement mechanism as the bridges interconvert between two symmetries. The interconversion is triggered by the departure and reentry of K (or Rb) cations out of and into the cavity of the cluster. This rearrangement allows Pp bridges to interconvert without the need to break bonds. Cs ions exhibit unique interactions with {U 24 Pp 12 } clusters and cause only minor changes in the solution 31 P NMR signatures, suggesting that O h symmetry is conserved. Single-crystal X-ray diffraction measurements reveal that the mixed Li/Na/Cs salt adopts D 2h molecular symmetry, implying that while solvated, this cluster is in equilibrium with a more symmetric form. These results highlight the unusually flexible nature of the actinide-based {U 24 Pp 12 } and its sensitivity to countercations in solution.
One-dimensional Al,Na Magic-Angle-Spinning (MAS) NMR and Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the δ-isomer of the Al Keggin structure at high spinning speed and 14.1 T field. Values for the C and η parameters are on the same scale as those seen in other isomers of the Al structure. Density functional theory (DFT) calculations are performed for comparison to the experimental fits using the B3PW91/6-31+G* and PBE0/6-31+G* levels of theory, with the Polarizable Continuum Model (PCM).
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