skip to main content

DOE PAGESDOE PAGES

14 results for: All records
Author ORCID ID is 0000000265016594
Full Text and Citations
Filters
  1. The novel metal ion complexant N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-BuA) uses an amide functionalization to increase the total ligand acidity and attain efficient 4f/5f differentiation in low pH conditions. The amide, when located on the diethylenetriamine platform containing four acetate pendant arms maintains the octadentate coordination sphere for all investigated trivalent f-elements. This compact coordination environment inhibits the protonation of LnL- complexes, as indicated by lower K 111 constants relative to the corresponding protonation site of the free ligand. For actinide ions, the enhanced stability of AnL- lowers the K 111 for americium and curium beyond the aptitude of potentiometric detection. Densitymore » functional theory computations indicate the difference in the back-donation ability of Am 3+ and Eu 3+ f-orbitals is mainly responsible for stronger proton affinity of EuL- compared to AmL-. The measured stability constants for the formation of AmL- and CmL- complexes are consistently higher, relative to ML- complexes with lanthanides of similar charge density. When compared with the conventional aminopolycarboxylate diethylenetriamine pentaacetic acid (DTPA), the modified DTTA-BuA complexant features higher ligand acidity and the important An 3+/Ln 3+ differentiation when deployed on a liquid–liquid distribution platform.« less
  2. Accurate prediction of melting points of ILs is important both from the fundamental point of view and from the practical perspective for screening ILs with low melting points and broadening their utilization in a wider temperature range. In this work, we present an ab initio approach to calculating melting points of ILs with known crystal structures and illustrate its application for a series of 11 ILs containing imidazolium/pyrrolidinium cations and halide/polyatomic fluoro-containing anions. The melting point is determined as a temperature at which the Gibbs free energy of fusion is zero. The Gibbs free energy of fusion can be expressedmore » through the use of the Born-Fajans-Haber cycle via the lattice free energy of forming a solid IL from gaseous phase ions and the sum of the solvation free energies of ions comprising IL. Dispersion-corrected density functional theory (DFT) involving (semi)local (PBE-D3) and hybrid exchange-correlation (HSE06-D3) functionals is applied to estimate the lattice enthalpy, entropy, and free energy. The ions solvation free energies are calculated with the SMD-generic-IL solvation model at the M06-2X/6-31+G(d) level of theory under standard conditions. The melting points of ILs computed with the HSE06-D3 functional are in good agreement with the experimental data, with a mean absolute error of 30.5 K and a mean relative error of 8.5%. The model is capable of accurately reproducing the trends in melting points upon variation of alkyl substituents in organic cations and replacement one anion by another. The results verify that the lattice energies of ILs containing polyatomic fluoro-containing anions can be approximated reasonably well using the volume-based thermodynamic approach. However, there is no correlation of the computed lattice energies with molecular volume for ILs containing halide anions. Moreover, entropies of solid ILs follow two different linear relationships with molecular volume for halides and polyatomic fluoro-containing anions. As a result, continuous progress in predicting crystal structures of organic salts with halide anions will be a key factor for successful prediction of melting points with no prior knowledge of the crystal structure.« less
  3. Amidoxime-functionalized polymeric adsorbents are the current state-of-the-art materials for collecting uranium (U) from seawater. However, marine tests show that vanadium (V) is preferentially extracted over U and many other cations. Here in this paper, we report a complementary and comprehensive investigation integrating ab initio simulations with thermochemical titrations and XAFS spectroscopy to understand the unusually strong and selective binding of V by polyamidoximes. While the open-chain amidoxime functionalities do not bind V, the cyclic imide-dioxime group of the adsorbent forms a peculiar non-oxido V 5+ complex, exhibiting the highest stability constant value ever observed for the V 5+ species. XAFSmore » analysis of adsorbents following deployment in environmental seawater confirms V binding solely by the imide-dioximes. Our fundamental findings offer not only guidance for future optimization of selectivity in amidoxime-based sorbent materials, but may also afford insight to understanding the extensive accumulation of V in some marine organisms.« less
  4. Here, the design of new ligands and investigation of UO 2 2+ complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime–UO 2 2+ complexes were quantified for the first time and compared with the binding strengths of salicylic acid–UO 2 2+ and representative amidoxime–UO 2 2+ complexes. We found that the binding strengths of salicylaldoxime–UO 2 2+ complexes are ~2–4 log β 2 units greater in magnitude than their correspondingmore » salicylic acid–UO 2 2+ and representative amidoxime–UO 2 2+ complexes; moreover, the selectivity of salicylaldoxime towards the UO 2 2+ cation over competing Cu 2+ and Fe 3+ cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO 2 2+ selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime–UO 2 2+ and salicylaldoxime–transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO 2 2+ as a dianion species formed by η 2 coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO 2 2+ cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives.« less
  5. Crystal truncation rod (CTR) measurements and density functional theory (DFT) calculations were performed to determine the atomic structure of the mineral–water interface of the {100} surface of xenotime (nominally YPO 4). This mineral is important, because it incorporates a variety of rare earth elements (REEs) in its crystal structure. REEs are critical materials necessary for a variety of renewable and energy efficient technologies. Current beneficiation techniques are not highly selective for REE ore minerals, and large amounts go to waste; this is a first step toward designing more efficient beneficiation. Evidence is found for minor relaxation of the surface withinmore » the topmost monolayer with little or no relaxation in subsurface layers. Justification for ordered water at the interface is found, where water binds to surface cations and donates hydrogen bonds to surface phosphates. The average bond lengths between cations and oxygens on water are 228 pm in the best fit to the CTR data, versus 243 and 251 pm for the DFT. No agreement on water positions bound to surface phosphates is obtained. Altogether, the findings suggest that ligands used in beneficiation with a single anionic headgroup, such as fatty acids, will have limited selectivity for xenotime relative to undesirable minerals.« less
  6. Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N',N'-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies.more » Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Lastly, our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides.« less
  7. Bastnaesite is an important mineral because of its abundance and rare earth content. Calcite and barite are the most common gangue minerals associated with bastnaesite. The importance of finding a suitable collector that can be selective against the gangue minerals without heated conditioning is critical to the advancement of the beneficiation of bastnaesite. Here, this review will present some previous research that has been done on bastnaesite flotation and a comparison of new collectors used.
  8. Nuclear power is a relatively carbon-free energy source that has the capacity to be utilized today in an effort to stem the tides of global warming. The growing demand for nuclear energy, however, could put significant strain on our uranium ore resources, and the mining activities utilized to extract that ore can leave behind long-term environmental damage. A potential solution to enhance the supply of uranium fuel is to recover uranium from seawater using amidoximated adsorbent fibers. This technology has been studied for decades but is currently plagued by the material’s relatively poor selectivity of uranium over its main competitormore » vanadium. In this work, we investigate the binding schemes between uranium, vanadium, and the amidoxime functional groups on the adsorbent surface. Using quantum chemical methods, binding strengths are approximated for a set of complexation reactions between uranium and vanadium with amidoxime functionalities. Those approximations are then coupled with a comprehensive aqueous adsorption model developed in this work to simulate the adsorption of uranium and vanadium under laboratory conditions. Experimental adsorption studies with uranium and vanadium over a wide pH range are performed, and the data collected are compared against simulation results to validate the model. It was found that coupling ab initio calculations with process level adsorption modeling provides accurate predictions of the adsorption capacity and selectivity of the sorbent materials. Furthermore, this work demonstrates that this multiscale modeling paradigm could be utilized to aid in the selection of superior ligands or ligand compositions for the selective capture of metal ions. Furthermore, this first-principles integrated modeling approach opens the door to the in silico design of next-generation adsorbents with potentially superior efficiency and selectivity for uranium over vanadium in seawater.« less
  9. The durability of anion-exchange membranes (AEMs) in alkaline fuel cells is largely determined by the stability of anion-exchange groups. Despite continuous research efforts, the commonly employed cations still have limited stability against hydroxide that can act as a strong base and nucleophile. This work is concerned with base-catalyzed degradation of organic cations initiated by proton abstraction to form reactive ylides or carbenes. We report on the performance of 24 methods combining density functional theory and electronic structure methods with implicit solvation calculations for predicting pK a values of organic cations in water and DMSO. The most accurate computational protocols aremore » obtained using a combination of M06-2X/6-311++G** with the SMD solvation model for water (the mean absolute error of 0.4 pK a units) and B3LYP/aug-cc-pVTZ with the IEFPCM solvation model for DMSO (the mean absolute error of 1.4 pK a units). The aqueous pK a calculation protocol is cross-validated against the experimental C–H acidity constants outside the conventional range of 0–14 pK a values. In conclusion, this study rationalizes alkaline degradation of imidazolium cations with C2-alkyl substituents and provides a theoretical scale of C–H acidity for potential anion-exchange groups in AEMs.« less
    Cited by 2
  10. Here, the novel metal chelator – N-2-pyridylmethyl-diethylenetriamine- N,N',N'',N''-tetraacetic acid, DTTA-PyM – was designed to replace a single O-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine- N,N,N',N'',N''-pentaacetic acid (DTPA) with an N-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen bearing heterocyclic moiety. The Am 3+, Cm 3+, Ln 3+ complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexationmore » of trivalent europium is found in mixtures containing EuHL (aq) complexes at the same aqueous acidity. The denticity change observed for Eu 3+ suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL(aq) complex is likely due to the protonation of an available carboxylate group since the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the Cm complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from p back-bonding interactions between singly occupied 5 f orbitals of Am 3+ and the pyridyl nitrogen. The differences between the stability of trivalent actinide chelates (Am 3+, Cm 3+) and trivalent lanthanide chelates (La 3+-Lu 3+) are observed in liquid-liquid extraction systems, yielding unprecedented 4 f/5 f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced N-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)-diethylenetriamine- N,N',N'',N''-tetraacetic acid, DTTA-3-F-PyM, showed subdued 4 f/5 f differentiation due to the presence of this electron-withdrawing group.« less

"Cited by" information provided by Web of Science.

DOE PAGES offers free public access to the best available full-text version of DOE-affiliated accepted manuscripts or articles after an administrative interval of 12 months. The portal and search engine employ a hybrid model of both centralized and distributed content, with PAGES maintaining a permanent archive of all full text and metadata.