Diglycolamide Research Articles

Stoichiometric Lanthanide Compounds with Diglycolamides: A Synthetic Approach toward Understanding Rare-Earth Speciation in Solution.

A fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining the chemical behavior of rare-earth metals in complex liquid-liquid extraction processes. Probing the exact bonding between the extractant and the metal is sometimes done through the synthesis of solid-state compounds that can serve as models for metal speciation in solution. In the case of diglycolamide (DGA), a commonly used neutral diamide extractant, extensive studies identify the stepwise formation of 1:1 [Ln(DGA)(H2O)6]3+, 1:2 [Ln(DGA)2(H2O)3]3+, and 1:3 [Ln(DGA)3]3+ complexes in solution. The crystallographic reports, however, exclusively show a 1:3 [Ln(DGA)3]3+ moiety in the solid state, while the structures of 1:1 and 1:2 complexes are yet to be isolated and comprehensively studied. In this work, we report the synthesis and characterization of three new families of stoichiometric N,N,N',N'-tetramethyldiglycolamide (TMDGA) compounds: [Ln(TMDGA)(H2O)5Cl]Cl2·2H2O, [Ln(TMDGA)2(H2O)3]Cl3·3H2O, and [Ln(TMDGA)3]Cl3·7H2O, where Ln = Nd, Eu, Gd, with Ln:TMDGA ratios of 1:1, 1:2, and 1:3, respectively. The compounds have been analyzed using vibrational spectroscopy (both Raman and FT-IR), as well as variable temperature fluorescence spectroscopy. A spectrophotometric titration of Eu(III) was performed to confirm the presence of the [Eu(TMDGA)n]3+ (n = 1, 2, and 3) species in solution and to compare the individual solid-state emission spectra to their respective analogues in solution.

Effect of branching in the alkyl chain of diglycolamide on the sequestration of tetravalent actinides: solvent extraction and theoretical studies.

DGA (diglycolamide) ligands show a different extraction behavior of trivalent metal ions by changing the branching alkyl chain length as well as the branching at the methylene position. There are no studies of these factors on the extraction efficiency of these DGA derivatives for the extraction of tetravalent actinides. We have evaluated four different DGA derivatives for the extraction of Np, Pu, and Th from molecular diluents. The n-butyl derivative shows enhanced extraction efficiency and branching gives rise to a reduction in the extraction efficiency of tetravalent ions. The distribution ratios are higher in pure octanol than in a mixture of 30% octanol and 70% n-dodecane. This behavior is in marked difference to that of the extraction of trivalent ions where the addition of an alcohol generally decreases the distribution ratio of trivalent ions due to the ligand-modifier intercation, poor aggregation or micelle formation tendency of DGAs in polar solvents. This suggests that micelle-mediated extraction may not be the dominating factor for the extraction of tetravalent metal ions. Slope analysis suggests the involvement of only two DGA molecules in the extracted species suggesting no/poor possibility of micelle formation in the present system. The higher extraction in pure octanol may be due to a better solubility of the extracted complexes in this polar medium compared to the mixture of octanol and n-dodecane. The water and acid uptake, the back extraction, and the radiation stability of the solvent systems were also investigated. DFT studies were performed to get a better insight into the extraction and complexation of the different DGA solvent systems.

Process for the Recovery of Actinide and Lanthanide Oxides via Thermal Decomposition and Calcination of Loaded Diglycolamide Resin

Diglycolamide (DGA) resin, a product produced by Eichrom Technologies, Inc. employs TODGA (N,N,N′,N′-tetraoctyldiglycolamide) as the active extractant, which will be used by Savannah River National Laboratory to extract trivalent actinides and lanthanides from dissolved irradiated Mark-18A targets. The final form of the extracted material will be an oxide suitable for shipment. A two-step process was developed and validated for the direct recovery of actinides and lanthanides loaded on I-grade DGA resin as nitrates by thermally drying and decomposing resin loaded with Nd(III), a surrogate for trivalent actinides and lanthanides, under inert conditions followed by calcining the resultant residue in air to provide an oxide product. A stepwise heating profile up to 385°C under argon gas flow resulted in 85% to 89% mass loss during the resin drying and decomposition step, and calcination of the resultant Nd-loaded resin residue provided an overall material mass loss of ≥ 98%. Recoveries from resin saturated with Nd(III) from 7 M and 0.35 M nitric acid subjected to this process were 30.7 mg and 27.6 mg Nd/g dry resin, respectively, representing an average of 96.1% of Nd retained in the resin bed.

Evaluation of an Extraction Chromatographic Resin Based on the DOODA Extractant: Characterization, Comparison to DGA, and Potential Applications

ABSTRACT The extraction of selected metal ions by an extraction chromatographic (EXC) resin containing N,N,N’,N’-tetraoctyl-3,6-dioxaoctane diamide (DOODA) on a porous methacrylate support was measured from nitric acid and hydrochloric acid. Metal ion extraction with the DOODA resin was compared to structurally similar diglycolamide (DGA) resins containing the extractants N,N,N’,N’-tetraoctyl-diglycolamide (TODGA; DGA, Normal resin) and N,N,N’,N’-tetra(2-ethyl-1-hexyl)-diglycolamide (TEHDGA; DGA, Branched resin). The EXC resins were studied via batch uptake, column elution, extraction capacity, and column stability experiments focusing on potential applications in analytical radiochemistry and nuclear medicine isotope production and purification. The DOODA resin exhibited similar extraction trends to the DGA resins for many metal ions, however, the capacity factors (k’) were reduced, typically following the trend of DGA, normal > DGA, branched > DOODA. The selectivity of DOODA resin towards rare earth elements, trivalent actinides, and some transition metal ions, particularly Cd, Ca, and Ac, is quite different from the existing DGA resins, but follows trends previously identified in solvent extraction experiments. The capacity for extraction of Ca(II) and Eu(III) from nitric acid was higher for the DOODA resin than either DGA resin, while all resins exhibited little extractant loss to the mobile phase over >18,000 bed volumes of elution.

DGA-grafting pyridine for ultra-selective and prior extraction of 99TcO4− from simulated spent nuclear fuel

Selective and prior extraction of 99TcO4− ahead of uranium and plutonium separation is a beneficial strategy for the modern nuclear fuel cycle. Herein, a novel DGA-grafting pyridine ligand BisDODGA-DAPy (L1) was tailored for the efficient separation of TcO4− from simulated spent nuclear fuel based on the selectivity of pyridine and synergistic effect of diglycolamide (DGA) group. Compared to the ligands BisDOSCA-DAPy (L2) and BisDODGA-MPDA (L3) with similar structure, BisDODGA-DAPy (L1) demonstrated the better separation performance including good extraction efficiency, reusability, and high loading capacity for TcO4− under high acidic medium. The interactions of the ligands with Tc(VII)/Re(VII) have been investigated in detail using FT-IR, 1H NMR titration, UV-Vis spectrophotometric titration, ESI-HRMS and DFT simulations. The extraction mechanism affected by the protonation of ligand was elucidated under different acidity. BisDODGA-DAPy (L1) demonstrated the ultra-selective extraction ability for TcO4− from simulated spent nuclear fuel. The maximum SFTc/U and SFTc/Pu values were up to 1.29 × 104 and 5.08 × 103, respectively. In the presence of 9 × 104-fold excess of NO3−, the extraction of TcO4− was almost unaffected. Moreover, the good radiolytic stability further highlights the promising potential of this ligand for 99Tc separation. DFT calculation revealed the dominant role of DAPy and DODGA in TcO4− extraction, providing the theoretical evidence for BisDODGA-DAPy (L1) to selectively bind TcO4− over NO3−.

Extractive Mass Transfer of Zr(IV) into a Hydrophobic Ionic Liquid Medium Containing Diglycolamide Extractant: Solvent Extraction and Spectroscopic Analysis.

Solvent extraction of Zr(IV) in ionic liquid (IL) medium is less known and Zr(IV) - IL chemistry indeed needs exploration to realize the coordination approach of Zr(IV) in IL phase. In view of this, in the present work, a strongly hydrophobic imidazolium based IL: 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) as the medium containing a diglycolamide (DGA) extractant: N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) was opted to understand the extraction behavior of Zr(IV) from nitric acid medium. Different experimental parameters such as the concentration of initial nitric acid, initial feed metal concentration, equilibration time and ligand concentration were tuned to unravel the extraction efficiency of the proposed IL phase towards Zr(IV). The extraction scenario was completely dependent on the hydrophobicity of IL diluent and increasing extraction trend with an increase in feed acidity along with the coordination of two TODGA molecules ensured Zr(IV) - complex formation in a neutral solvation mechanistic pathway. The extraction trend of Zr(IV) was compared with molecular diluent (n-dodecane (n-DD)) containing TODGA and a phase modifier: N,N-dihexyloctanamide (DHOA). The coordination aspect of Zr(IV) with ligand in IL phase was ascertained spectroscopically to validate Zr(IV) loading in IL phase. Thermodynamics of Zr(IV) extraction revealed the nature of the extraction process and the complex formation.

The mechanism insight into the cooperative coordination of Aza-18-crown-6 ether with diglycolamide by p-benzyl as linkers enhancing the selectivity for heavy REEs(III)

The development of new ligands is crucial for the functional application of REEs(III), because the coordination compounds of rare-earth elements (REEs) have many important applications in pharmaceuticals and nuclear medicine. In this paper, a novel ligand (Cr6-Bz-DGA) with the aza-crown ether and diglycolamide (DGA) units was designed to coordinate with light, medium, and heavy REEs(III). It was found that M/L = 2:2 species (aza-crown ether-REEs(III)-DGA connection) was the thermodynamically stable complex. The stability constants of Nd(III), Eu(III), and Ho(III) complexes were determined by UV–Vis and fluorescence titration, respectively, which were logβNd = 7.49 ± 0.019, logβEu = 7.10 ± 0.013 and logβHo = 8.27 ± 0.032. The variation of fluorescence lifetime suggested that the Eu(III) ion was exclusively coordinated by the ligand with coordination number 9 in the inner sphere of the Eu(III) ion. The shifts of 1H NMR revealed that there are different coordination between the ligand and REEs(III). For larger ionic radii La(III), three O atoms of the DGA unit and five O and one N atoms of the aza-crown ether unit were supplied. While, for Y(III)/Lu(III) with smaller ion radii, the ligand supplied three O atoms from the DGA and one N atom and only two O atoms from the aza-crown ether. The displacement experiment of REEs(III) combined with ligand and the fitted stability constants prove that the smaller ionic radii REEs(III) more strongly bind with ligand than larger ionic radius REEs(III). These results may help understand the coordination behavior of REEs(III) and expand their potential applications.

Understanding the separation of trivalent lanthanides and actinides using multiple diglycolamide-containing ligands: a review

Abstract The complexation and separation behaviour of trivalent actinides and lanthanides with various multiple diglycolamide (DGA) group-containing ligands are compiled in the present review. The DGA arms are anchored on various scaffolds, viz., C- and N-pivot tripodal backbones, benzene-centred tripodal backbones, calix[4]arene, pillar[5]arene and azamacrocycle scaffolds. Dendrimers of different generations having DGA arms were also evaluated for the extraction and complexation studies of trivalent actinide and lanthanide ions. The extraction efficiency of the DGA units increases significantly when they are grouped together on a single backbone/scaffold. Furthermore, the selectivity was found to improve in many cases, particularly with respect to the UO2 2+ ion. This is very important for the development of suitable ligands for the extraction/separation of the actinide and lanthanide ions. Combined experimental, luminescence and DFT studies on the complexation of trivalent actinides and lanthanides with these DGA-based ligands are quite useful to understand their extraction and separation behaviour and this review article gives a critical analysis of the results available in the literature.

Application of diglycolamide extractant in rare-earth extraction

Diglycolamide (DGA) extractant is a kind of rare-earth extractant with promising applications that has the advantages of high extraction capacity, ease of synthesis, good thermal stability and good radiation stability. It is a green extractant that contains only four elements, C, H, O and N, and produces no residue after incineration. The properties of DGAs containing branched N,N′-alkyl substituents have been much studied in recent years, and it has been shown that branched side chains lead to better separation. The introduction of structurally rigid elements in DGA provides new possibilities for separation of rare earth elements (REEs). Owing to the tiny differences in the chemical properties of adjacent REES, the simple use of DGA extractant cannot meet all separation requirements, and a masking agent is added to the aqueous phase to improve the separation by coextraction to meet the requirements of different processes. This review presents the structural analysis of the complexes and crystals of diglycolamide extractants with rare-earth ions through different characterization means, and the effects of different structural extractants, solvents, nitric acid and phase modifiers on extraction behavior are reviewed. This review pays special attention to the effect of the side chain structure of diglycolamide on extraction behavior, which provides a theoretical basis and guiding direction for the field of separation of the REEs by diglycolamide extractants.

Modified Diglycolamide Resin: Characterization and Potential Application for Rare Earth Element Recovery

Rare earth elements (REEs) are crucial for green energy applications due to their unique properties, but their extraction poses sustainability challenges because the global supply of REEs is concentrated in a few countries, particularly China, which produces 70% of the world’s REEs. To address this, the study investigated TK221, a modified extraction chromatographic resin featuring diglycolamide (DGA) and carbamoyl methyl phosphine oxide (CMPO), as a promising adsorbent for REE recovery. The elemental composition and functional groups of DGA and CMPO on the polystyrene-divinylbenzene (PS-DVB) support of TK221 were confirmed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The adsorption kinetics of neodymium (Nd), yttrium (Y), cerium (Ce), and erbium (Er) followed the pseudo-second-order kinetic model and Langmuir isotherm, indicating monolayer chemisorption. Furthermore, iron (Fe) adsorption reached apparent equilibrium after 360 min, with consistent Fe adsorption observed at both 360 min and 1440 min. The inclusion of Fe in the study is due to its common presence as an impurity in most REE leachate solutions. The Fe adsorption isotherm results are better fitted with the Langmuir isotherm, implying chemisorption. Maximum adsorption capacities (qmax) of the resin were determined as follows: Nd (45.3 mg/g), Ce (43.1 mg/g), Er (35.1 mg/g), Y (15.6 mg/g), and Fe (12.3 mg/g). ATR-FTIR analysis after adsorption suggested that both C=O and P=O bands shifted from 1679 cm−1 to 1618 cm−1 and 1107 cm−1 to 1142 cm−1 for Y, and from 1679 cm−1 to 1607 cm−1 and 1107 cm−1 to 1135 cm−1 for Ce, implying possible coordination with REEs. These results suggest that TK221 has a huge potential as an alternative adsorbent for REE recovery, thus contributing to sustainable REE supply diversification.

Surface structure regulating of silica adsorbent for the selective adsorption of heavy rare earth

Rare earth element (REE) is a strategic metal resource, heavy REE owns higher economic and strategic value compared with light rare earth elements. However, it is a great challenge for the separation of heavy rare earth ion efficiently in the solution with mixed rare earth ions due to the similar physicochemical properties of heavy and light REE. In this paper, the diglycolamide (DGA) modified silica adsorbents were prepared and applied to the selective adsorption of heavy earth ion Dy3+. The structure of DGA on the silica surface was regulated during the modifying processes to obtain DGAb-SiO2 and DGAs-SiO2 adsorbent, which was verified by FTIR and NMR characterization results. The adsorption results showed that the DGAb-SiO2 adsorbent owned a much higher distribution coefficient (Kd) value for the selective adsorption of Dy3+ than the DGAs-SiO2 adsorbent. The higher adsorption selectivity is likely due to the fixed carbon chain of the DGA group on the surface of DGAb-SiO2 adsorbent formed rigid spatial structures of the oxygen atoms, which will be favorable for the selective coordination of Dy3+. Besides its effectiveness in adsorption behavior, the DGAb-SiO2 adsorbent displayed excellent stability. The Kd value of DGAb-SiO2 for Dy3+ selective adsorption maintained a high level after four successive recycling runs. The adsorption kinetics results displayed that the adsorption of Dy3+ followed pseudo-second-order kinetic, and the adsorption process fitted the Langmuir isotherm model. Additionally, the same adsorption rules for the rare earth ions were observed over DGA-KIT-6 adsorbent, indicating the high universality of the surface modification to the adsorbent support, which will provide an intentional reference for the surface modification to other adsorbent support.

Cyclohexyl substituted diglycolamide ligands for highly efficient separation of strontium: Synthesis, extraction and crystallography studies

A series of novel diglycolamide (DGA) ligands containing cyclohexyl substituent on the amidic N atom were investigated for their solvent extraction and complexation ability toward Sr2+ in HNO3 solution. Compared with the most commonly used N,N,N′,N′-tetraoctyldiglycolamide (TODGA), the introduction of cyclohexyl substituent into the DGA skeleton can significantly enhance the extractability toward Sr2+ in the case of toluene as the diluent. And the more cyclohexyl substituents there are, the more significant the effect is. About 8−80 fold increase of the Sr2+ distribution value for LI−LVI ligands can be achieved than that for TODGA at 2.0 mol/L HNO3. The extractability of these cyclohexyl substituted DGA ligands follows the order of LI ≈ LIII > LII > LIV > LV > LVI > > TODGA. Meanwhile, for the DGA ligands with the same number of cyclohexyl substituents, LIII with moderate alkyl chain length (n-butyl) has higher extractability than LII with short chain (n-ethyl) and LIV with long chain (n-octyl). Slope analysis reveals the formation of 1:3 metal-ligand extracted species during the extraction process, which is also confirmed by the results obtained from ESI-MS, FT-IR and single-crystal X-ray diffraction analyses. Furthermore, the single crystal of DGA ligand with Sr(NO3)2 was obtained for the first time, and the analysis of its structure indicates that each DGA molecule participates in the complexation with the 9-fold coordinated Sr2+ through two amide carbonyl O atoms and one ether O atom, accompanied by two free NO3− in the outer coordination sphere. The extraction of Sr2+ by the novel DGA ligand is a spontaneous and exothermic process of increasing entropy, and follows neutral complexing extraction model. In addition, an extraction test of Sr2+ from simulated high level liquid waste was also carried out and demonstrates a highly efficient and selective separation of Sr2+ over the other co-existing ions.

Theoretical Insights on the Complexation of Americium(III) and Europium(III) with Diglycolamide- and Dimethylacetamide-Functionalized Calix[4]arenes

Separation of minor actinides from lanthanides is one of the biggest challenges in spent fuel reprocessing due to the similar physicochemical properties of trivalent lanthanides (Ln(III)) and actinides (An(III)). Therefore, developing ligands with excellent extraction and separation performance is essential at present. As an excellent pre-organization platform, calixarene has received more attention on Ln(III)/An(III) separation. In this work, we systematically explored the complexation behaviors of the diglycolamide (DGA)/dimethylacetamide (DMA)-functionalized calix[4]arene extractants for Eu(III) and Am(III) using relativistic density functional theory (DFT). These calix[4]arene-derived ligands were obtained by functionalization with two or four binding units at the narrow edge of the calix[4]arene platform. All bonding nature analyses suggested that the Eu-L complexes possess stronger interaction compared to Am-L analogues, resulting in the higher extraction capacity of the these calix[4]arene ligands toward Eu(III). Thermodynamic analysis demonstrates that these pre-organized ligands on the calix[4]arene platform with four binding units yield better extraction abilities than the single ligands. Although DMA-functionalized ligands show stronger complexation stability for metal ions, in acidic solutions, the calix[4]arene ligands with DGA binding units have better extraction performance for Eu(III) and Am(III) due to the basicity of the DMA ligand. This work enabled us to gain a deeper understanding of the bonding properties between supramolecular ligands and lanthanides/actinides and afford useful insights into designing efficient supramolecular ligands for separating Ln(III)/An(III).

Structural effects of benzene-centered tripodal diglycolamides on extraction of trivalent f-cations into a room temperature ionic liquid

A series of three benzene functionalized tripodal diglycolamide (DGA) extractants (abbreviated as Bz-T-DGA, and termed as LI, LII and LIII) were studied for their extraction abilities for Eu3+ and Am3+ ions. Extraction efficiencies of these ligands are distinctly dependent on: (i) the nature of alkyl substituents on amidic N atoms of DGA, (ii) alkyl chain length that connects the DGA moeties with the benzene ring, and (iii) the medium of extraction. Substitution of protons with iso-pentyl groups on DGA nitrogen atoms enhanced the ligand extraction efficiency many folds. At the same time, increasing the spacer atoms between the benzene platform and the DGA units reduced the ligand extraction efficiency. The distribution ratio of Eu3+ was higher than that of Am3+ with all the three ligands, but the separation factor between the two elements was less than 2. Solvent extraction mechanism was entirely different when the organic solvent changed from n-dodecane (a molecular solvent) to ionic liquid. DFT calculations revealed that the solvent extraction abilities of these ligands were primarily goverened by their complexation abilities for trivalent f-cations.

Highly Efficient Pertraction of Tetravalent Neptunium Ions Across a Flat Sheet Supported Liquid Membrane Containing Two Different Aza-Crown Ether-Based Multiple Diglycolamide Ligands

ABSTRACT Pertraction of Np(IV) across a PTFE membrane containing two different aza-crown ether-based multiple diglycolamide (DGA) ligands termed as L I (3 DGA arms) or L II (4 DGA arms) was investigated using nitric acid as feed solution. A few of the studies were also carried out with Pu(IV) for comparison purposes. The kinetics of the extraction of Np(IV) and Pu(IV) was fast at 3 M HNO3 and within 10 min reaches the equilibrium distribution (D) ratio with both ligands. However, the stripping kinetics was slower especially with ligand L II . The extraction and transport studies were carried out using 1.0 × 10−3 M ligand solution in 95% n-dodecane + 5% isodecanol. The transport rates were slower with ligand L II than with L I at higher nitric acid concentrations (>1 M HNO3) and the transport rates decreased with nitric acid concentration with both ligands. The effective diffusion coefficients (D eff) of Np(IV) were estimated using the lag-time method as 6.2 × 10−8 cm2 s−1 (L I ) and 4.6 × 10−8 cm2 s−1 (L II ). The stability data suggest that the L I containing supported liquid membrane (SLM) is comparatively more stable than that of L II and the transport flux remains the same up to nine days of operation in case of ligand L I .

Lanthanide and Actinide Ion Complexes Containing Organic Ligands Investigated by Surface-Enhanced Infrared Absorption Spectroscopy.

A new technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, was used for the structural investigation of lanthanide (Ln) and actinide (An) complexes containing organic ligands. We synthesized thiol derivatives of organic ligands with coordination sites similar to those of 2-[N-methyl-N-hexanethiol-amino]-2-oxoethoxy-[N',N'-diethyl]-acetamide [diglycolamide (DGA)], Cyanex-272, and N,N,N',N'-tetrakis(2-pyridinylmethyl)-1,2-ethanediamine (TPEN), which have been used for separating Ln and An through solvent extraction. These ligands were attached on a gold surface deposited on an Si prism through S-Au covalent bonds; the gold surface enhanced the IR absorption intensity of the ligands. Aqueous solutions of Ln (Eu3+, Gd3+, and Tb3+) and An (Am3+) ions were loaded onto the gold surface to form ion complexes. The IR spectra of the ion complexes were obtained using Fourier transform infrared spectroscopy in the attenuated total reflection mode. In this study, we developed a new sample preparation method for SEIRA spectroscopy that enabled us to obtain the IR spectra of the complexes with a small amount of ion solution (5 μL). This is a significant advantage for the IR measurement of radiotoxic Am3+ complexes. In the IR spectra of DGA, the band attributed to C═O stretching vibrations at ∼1630 cm-1 shifted to a lower wavenumber by ∼20 cm-1 upon complexation with Ln and An ions. Moreover, the amount of the red shift was inversely proportional to the extraction equilibrium constant reported in previous studies on solvent extraction. The coordination ability of DGA toward Ln and An ions could be assessed using the band position of the C═O band. The Cyanex-272- and TPEN-like ligands synthesized in this report also showed noticeable SEIRA signals for Ln and An complexes. This study indicates that SEIRA spectroscopy can be used for the structural investigation of ion complexes and provides a microscopic understanding of selective extraction of Ln and An.

Sequestration of Np4+ and NpO22+ ions by using diglycolamide-functionalized azacrown ethers in C8mim·NTf2 ionic liquid: Extraction, spectroscopic, electrochemical and DFT studies

Complexation of Np4+ and NpO22+ ions was studied in a room temperature ionic liquid (C8mim•NTf2) using two multiple diglycolamide (DGA) ligands with three and four DGA arms tethered to the nitrogen atoms of the aza-9-crown-3 and -12-crown-4 scaffolds termed as LI and LII, respectively. The studies include solvent extraction, UV–visible spectrophotometry, cyclic voltammetry, and density functional theory (DFT). While the extraction of NpO22+ ion, as a function of the nitric acid concentration, resembled that of the ‘solvation’ mechanism, seen in case of neutral donor ligands in molecular diluent, an opposite trend was observed for the Np4+ ion suggesting a ‘cation-exchange’ mechanism often operating in the case of ionic liquid-based solvent systems. Slope analysis suggested formation of Np(NO3)]3+•L and NpO2(NO3)2•L extracted species for the extraction of Np4+ and NpO22+, respectively, in both the ligand systems. The complexation of the metal ions was supported by peak shifts in the UV–visible spectrophotometric as well as cyclic voltammetric studies. DFT studies were carried out to get structural information of the complexes.

A comparative study on the uptake of lanthanides from acidic feeds using extraction chromatography resins containing N,N,N’,N’-tetra-n-alkyl diglycolamides with varying alkyl chain lengths in an ionic liquid

A comparative study on the uptake of several rare earth element (REE) ions viz. La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III) and Dy(III) was carried out from nitric acid feeds using four extraction chromatography resins which contained the diglycolamide (DGA) ligands, N,N,N',N'-tetra-n-alkyldiglycolamide with n-pentyl (TPDGA), n-hexyl (THDGA), n-octyl (TODGA) and n-decyl (TDDGA) groups taken in a room temperature ionic liquid (C4mim·NTf2). The uptake of the lanthanides followed the trend: La(III) < Ce(III) < Pr(III) < Nd(III) < Sm(III) < Gd(III) < Dy(III), which is similar to their ionic potential values and the uptake trend of the resins was TPDGA > THDGA > TODGA > TDDGA. The uptake of the metal ions was very high (>104g/mL) for all the lanthanide ions and was found to increase with increasing nitric acid concentrations. Based on the encouraging batch data, column studies were carried out with all the four extraction chromatography resins with the lanthanide ions used in this work. The column studies were carried out with both individual lanthanide ions and their mixtures. While the loading studies were carried out with 80mg/L solutions of the metal ions (with respect to each of those) in the mixture of REEs, the elution studies were carried out using a solution of 0.05M EDTA in 1M guanidine carbonate. For the column studies involving individual REEs, 550mg/L solutions were used. The elution profiles appeared to be sharp as >95% elution of the metal ions was accomplished in only 3mL of the eluent which amounted to only 1.6 bed volumes which is highly impressive. When the studies were carried out with the mixture of the lanthanide ions, the breakthrough of Dy(III) was last while that of La(III) was seen at much lower volumes which was dependent on the nature of the extractant in the resins.

Liquid–Liquid Extraction and Supported Liquid Membrane Transport of Neptunium(IV) Across a Flat-Sheet Supported Liquid Membrane Containing a TREN-DGA Derivative

ABSTRACT Liquid–liquid extraction and liquid membrane transport behavior of tetravalent actinide ions viz. Th(IV), Np(IV), and Pu(IV) were investigated for the first time using a diglycolamide (DGA) based dendrimer with a tris(2-aminoethyl)amine (TREN) scaffold as the organic extractant. The generation of 1 dendrimer with six DGA pendent moieties (termed as TREN-G1-DenDGA) extracted Np(IV) more effectively than the other two ions, the trend being Np(IV) > Pu(IV) > Th(IV). The extraction studies of Np(IV) from 3 M HNO3 indicated a 1:1 (metal:ligand) species and the extraction efficiency increased with increasing nitric acid concentration (1–6 M). The transport efficiency of Np(IV) increased with the nitric acid concentration (1–6 M) as well as with the ligand concentration. A very low concentration of 5.75 × 10−4 M ligand, when used as the carrier, resulted in the transport of ca. 25% metal ion transport in 5 h, which increased to >85% with 4.4 × 10−3 M ligand. The transport efficiency of the metal ion across the SLM followed the trend Np(IV) > Th(IV) > Pu(IV). The membrane stability was not satisfactory as seen over a period of 5 days suggesting long-term use may require regular replenishment of the carrier solvent. The effective diffusion coefficient (D eff) of Np(IV)-TREN-G1-DenDGA were determined by the lag-time method and was found to be 5.1 × 10−8 cm2/s.

Multi-stage extraction and separation of Ln and An using TODGA and DTBA or DTPA accompanying pH adjustment with lactic acid and ethylenediamine

ABSTRACT The mutual separation of actinides (An) from lanthanides (Ln), using diethylenetriamine- N,N′,N″-pentaacetic acid (DTPA) or diethylenetriamine- N,N′,N″-triacetic acid-N,N″-bis(diethylacetamide) (DTBA) masking agents in the aqueous phase via diglycolamide (DGA) extraction is focused on the basis of Trivalent Actinide-Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes (TALSPEAK) method. We also obtained the same separation performance using the commercially available DTPA using DTBA. In this work, we selected lactic acid (LA) of pH buffer from 10 organic acids and ethylenediamine (ED) for the pH adjustment based on the salt-free system. Approximately same D and SF values are obtained in the following conditions: TODGA-DTPA-LA-NaOH, TODGA-DTPA-LA-ED, and TODGA-DTBA-LA, except for different pH conditions (DTPA: pH 1.7–1.71, DTBA: pH 1.15). Experimental results using batchwise multi-stage extractions showed average yields of Ln (La to Gd) and Am to be 3.73% and 98.1% in the aqueous phase using DGA-DTPA-LA-ED, 3.1% and 97.0% using DGA-DTPA-LA-NaOH, and 1.61% and 98.7% using DGA-DTBA-LA. The suitable pH condition for the multi-stage extraction, using DTBA to extract over 95% Am with under 5% coextraction of Ln was limited to 1.14–1.16 throughout this work.