The extraction of actinides from nitric acid solutions with diamides of dipicolinic acid

Lapka, Joseph L.; Paulenová, Alena; Alyapyshev, M. Yu.; Бабаин, В. А.; Law, Jack D.; Herbst, Ronald

doi:10.1088/1757-899x/9/1/012068

Cited by 13 publications

(6 citation statements)

References 15 publications

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“…From the viewpoint of energy, the phenanthrolineamides extract actinides in the order of Pu IV > U VI > Pu VI > Np V . On the experimental side, Lapka et al reported that the order of extractability was determined to be An IV > An VI > An V by a diamide of dipicolinic acid extractant in 3.0 M HNO 3 . In addition, N , N , N ′, N ′-tetraalkyl-6,6″-(2,2′:6′,2″-terpyridine)diamides were found to hold the strongest extraction abilities toward Pu IV among An III , An IV , An V , and An VI ions .…”

Section: Resultsmentioning

confidence: 99%

Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands

Xiao

Wang

et al. 2014

Inorg. Chem.

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The preorganized tetradentate 2,9-diamido-1,10-phenanthroline ligand with hard-soft donors combined in the same molecule has been found to possess high selectivity toward actinides in an acidic aqueous solution. In this work, density functional theory (DFT) coupled with the quasi-relativistic small-core pseudopotential method was used to investigate the structures, bonding nature, and thermodynamic behavior of uranium(VI), neptunium(V), and plutonium(IV,VI) with phenanthrolineamides. Theoretical optimization shows that Et-Tol-DAPhen and Et-Et-DAPhen ligands are both coordinated with actinides in a tetradentate chelating mode through two N donors of the phenanthroline moiety and two O donors of the amide moieties. It is found that [AnO2L(NO3)](n+) (An = U(VI), Np(V), Pu(VI); n = 0, 1) and PuL(NO3)4 are the main 1:1 complexes. With respect to 1:2 complexes, the reaction [Pu(H2O)9](4+)(aq) + 2L(org) + 2NO3(-)(aq) → [PuL2(NO3)2](2+)(org) + 9H2O(aq) might be another probable extraction mechanism for Pu(IV). From the viewpoint of energy, the phenanthrolineamides extract actinides in the order of Pu(IV) > U(VI) > Pu(VI) > Np(V), which agrees well with the experimental results. Additionally, all of the thermodynamic reactions are more energetically favorable for the Et-Tol-DAPhen ligand than the Et-Et-DAPhen ligand, indicating that substitution of one ethyl group with one tolyl group can enhance the complexation abilities toward actinide cations (anomalous aryl strengthening).

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Section: Resultsmentioning

confidence: 99%

Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands

Xiao

Wang

et al. 2014

Inorg. Chem.

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“…Diamide ligands have been of interest as promising extractants in spent fuel reprocessing for several decades due to their great affinities toward lanthanide and actinide ions as well as their environmentally benign characters. − Extensive studies have been performed on the extraction properties of various substituted diamides. The family of glutaramide ligands (Figure a) shows excellent extraction ability to the hexavalent and tetravalent actinide ions but weak for the trivalent ions, − while diglycolamides (Figure b) extract trivalent actinide ions over tetravalent or hexavalent ions. − For the thiodiglycolamide ligands (Figure c), they can extract hexavalent, tetravalent, and trivalent actinides as well as trivalent lanthanides, but their extraction abilities are weaker than those of diglycolamides. ,, The diamides of dipicolinic acid (Figure d) dissolved in organic diluents have a large capacity for uranium and effectively extract tetravalent and hexavalent actinide ions. − These results demonstrate that the extraction properties of diamides strongly depend on their structures which affect the structures and stabilities of the coordination complexes formed between metal ions and diamide ligands.…”

Section: Introductionmentioning

confidence: 99%

Coordination Structures of the Uranyl(VI)–Diamide Complexes: A Combined Mass Spectrometric, EXAFS Spectroscopic, and Theoretical Study

Chen

Gong

2019

Inorg. Chem.

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The coordination structures of a series of uranyl–diamide complexes, namely UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ (TMGA: N,N,N′,N′-tetramethylglutaramide; TMTDA: N,N,N′,N′-tetramethyl-3-thiodiglycolamide; TMPDA: N,N,N′,N′-tetramethylpyridine-2,6-dicarboxamide), in the gas phase and solution were studied by electrospray ionization (ESI) mass spectrometry, density functional theory (DFT) calculations, and extended X-ray absorption fine structure (EXAFS) spectroscopy. ESI of UO2Cl2–TMGA, UO2Cl2–TMTDA, and UO2Cl2–TMPDA solutions produced UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ as the major complexes in the gas phase. The gas-phase fragmentation patterns of these three complexes upon collision-induced dissociation (CID) are quite similar, and the products arising from (CH3)2N–COcarbonyl, CH2–COcarbonyl, Cpyridine–COcarbonyl, and CH2–CH2/S bond cleavages were identified, which agree with the degradation patterns of diamides upon γ irradiation in solution. DFT calculations revealed similar bidentate coordination modes of TMGA and TMTDA in the UO2(TMGA)2 2+ and UO2(TMTDA)2 2+ complexes in the gas phase. For UO2(TMPDA)2 2+, UO2 2+ is coordinated by two Ocarbonyl and one Npyridine from each TMPDA, which acts as a tridentate ligand. The results from EXAFS analysis indicate that the coordination structures of UO2(TMGA)2 2+, UO2(TMTDA)2 2+, and UO2(TMPDA)2 2+ in solution are similar to those in the gas phase.

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“…If one of alkyl substituents at the amide nitrogen atom is replaced with an aryl substituent, the extraction ability of diamide toward trivalent actinides sharply increases. The organic solvents based on the dialkyl‐diaryl diamides of dipicolinic acid effectively remove actinides(III, IV, V, VI) and lanthanides(III), from aqueous nitric acid solutions. Such effect of structure on the extraction ability of ligands was observed earlier for neutral organophosphorus extractants and named “anomalous aryl strengthening” effect …”

Section: Introductionmentioning

confidence: 99%

Complexes of Uranyl Nitrate with 2,6-Pyridinedicarboxamides: Synthesis, Crystal Structure, and DFT Study

Alyapyshev

Бабаин

Ткаченко

et al. 2017

Z. Anorg. Allg. Chem.

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The extraction of actinides from nitric acid solutions with diamides of dipicolinic acid

Cited by 13 publications

References 15 publications

Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands

Quantum Chemistry Study of Uranium(VI), Neptunium(V), and Plutonium(IV,VI) Complexes with Preorganized Tetradentate Phenanthrolineamide Ligands

Coordination Structures of the Uranyl(VI)–Diamide Complexes: A Combined Mass Spectrometric, EXAFS Spectroscopic, and Theoretical Study

Complexes of Uranyl Nitrate with 2,6-Pyridinedicarboxamides: Synthesis, Crystal Structure, and DFT Study

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