Novel water-soluble aromatic bisdiglycolamide masking agents for the separation of trivalent americium over lanthanides by NTAamide(n-Oct) extractant

He, Lanlan; Wang, Xueyu; Li, Qiuju; Xiao, Xiao; Li, Fengfeng; Luo, Fang; Pan, Qing‐Jiang; Ding, Songdong

doi:10.1016/j.jece.2023.109536

Cited by 10 publications

(10 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…NMR Spectroscopy and 1 H NMR Titration. The 1 H NMR (400 MHz, nuclear magnetic resonance) and 13 C NMR (100 MHz) spectra of the hydrophilic masking agents, lipophilic extractants, and 1 H NMR titration experiments were collected on a Varian Mercury-400 spectrometer. In the titration experiments, 2OH-DAPhen solutions (L-2, 1.0 mM in CD 3 OD) were placed in a series of NMR tubes, and then different volumes of LaCl 3 (25 mM in CD 3 OD) or LuCl 3 (25 mM in CD 3 OD) solutions were added.…”

Section: Extraction Experimentsmentioning

confidence: 99%

“…9−11 In order to improve the long-term management safety of nuclear waste, the partitioning-transmutation strategy (P&T) was emerged and recognized as a viable global option. 12,13 The proposed P&T initially partitioned the transuranic elements and longlived fission products by the PUREX process using solvent extraction, 14,15 and they were subsequently subjected to neutron bombardment for transmutation into short-lived nuclides. 16 For the realization of the P&T strategy, the initial separation of Ln(III) from An(III) is an inevitable prerequisite.…”

Section: Introductionmentioning

confidence: 99%

“…The increasing demand of carbon-neutral and low-cost energy has caused nuclear energy to become an essential element in the overall composition of the current global power supply. − Accompanied by the high-speed development of nuclear energy, the environmental problems associated with used nuclear fuel have aroused great attention. − Of the spent fuel produced by modern light water reactors, over 98.5% of the components are mainly composed of U, Pu, and lanthanides (Ln) . However, it still contains less than 1 wt % of minor actinides (MA) including Am, Np, and Cm, which are responsible for long-standing radiotoxicity. − In order to improve the long-term management safety of nuclear waste, the partitioning-transmutation strategy (P&T) was emerged and recognized as a viable global option. , The proposed P&T initially partitioned the transuranic elements and long-lived fission products by the PUREX process using solvent extraction, , and they were subsequently subjected to neutron bombardment for transmutation into short-lived nuclides . For the realization of the P&T strategy, the initial separation of Ln(III) from An(III) is an inevitable prerequisite .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

Wu,

Hao,

Liu

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

Adding hydrophilic ligands into aqueous solutions for the selective binding of actinides(III) is acknowledged as an advanced strategy in Ln(III)/ An(III) separation. In view of the recycling and radioactive waste disposal of the minor actinide, there remains an urgent need to design and develop the appropriate ligand for selective separation of An(III) from Ln(III). Herein, four novel hydrophilic ligands with hard−soft hybrid donors, derived from the pyridine and phenanthroline skeletons, were designed and synthesized as masking agents for selective complexation of An(III) in the aqueous phase. The known N,N,N′,N′-tetraoctyl diglycolamide (TODGA) was used as lipophilic extractant in the organic phase for extraction of Ln(III), and a new strategy for the competitive extraction of An(III) and Ln(III) was developed based on TODGA and the above hydrophilic ligands. The optimal hydrophilic ligand of N,N′-bis(2hydroxyethyl)-2,9-dicarboxamide-1,10-phenanthroline (2OH-DAPhen) displayed exceptional selectivity toward Am(III) over Ln(III), with the concentrations of HNO 3 ranging from 0.05 to 3.0 M. The maximum separation factors were up to 1365 for Eu/Am, 417.66 for Eu/Cm, and 42.38 for La/Am. The coordination mode and bonding property of 2OH-DAPhen with Ln(III) were investigated by 1 H NMR titration, UV−vis spectrophotometric titration, luminescence titration, FT-IR, ESI-HRMS analysis, and DFT calculations. The results revealed that the predominant species formed in the aqueous phase was a 1:1 ligand/metal complex. DFT calculations also confirmed that the affinity of 2OH-DAPhen for Am(III) was better than that for Eu(III). The present work using a competitive extraction strategy developed a feasible alternative method for the selective separation of trivalent actinides from lanthanides.

show abstract

Section: Extraction Experimentsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

Wu,

Hao,

Liu

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…Ligand design principles were largely unknown. Currently, the most reported hydrophilic ligands are being constructed by solubilizing the corresponding lipophilic ligands through sulfonation. ,,− High water-soluble ligands with an unexpected superior separation factor (around 1000) could be achieved with the desired metal cation distributions . However, the hash reaction condition, incomplete combustibility, and low radiochemical stability hindered their further industrial implementation .…”

Section: Introductionmentioning

confidence: 99%

Amine-Terminated Phenanthroline Diimides as Aqueous Masking Agents for Am(III)/Eu(III) Separation: An Alternative Ligand Design Strategy for Water-Soluble Lanthanide/Actinide Chelating Ligands

Cao,

Kang,

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

Selective actinide coordination (from lanthanides) is critical for both nuclear waste management and sustainable development of nuclear power. Hydrophilic ligands used as masking agents to withhold actinides in the aqueous phase are currently highly pursued, while synthetic accessibility, water solubility, acid resistance, and extraction capability are the remaining problems. Most reported hydrophilic ligands are only effective at low acidity. We recently proved that the phenanthroline diimide skeleton was an efficient building block for the construction of highly efficient acid-resistant hydrophilic lanthanide/actinide separation agents, while the limited water solubility hindered the loading capability of the ligand. Herein, amine was introduced as the terminal solubilizing group onto the phenanthroline diimide backbone, which after protonation in acid showed high water solubility. The positively charged terminal amines enhanced the ligand water solubility to a large extent, which, on the other side, was believed to be detrimental for the coordination and complexation of the metal cations. We showed that by delicately adjusting the alkyl chain spacing, this intuitive disadvantage could be relieved and superior extraction performances could be achieved. This work holds significance for both hydrophilic lanthanide/actinide separation ligand design and, concurrently, offers insights into the development of water-soluble lanthanide/actinide complexes for biomedical and bioimaging applications.

show abstract

“…An alternative Lns(III)/Ans(III) separation strategy was to extract both Lns(III) and Ans(III) unselectively with a diglycolamide such as TODGA , followed by selective back-extraction of Ans(III) using a delicate-designed hydrophilic ligands as demonstrated in the Innovative Selective Actinide Extraction ( i -SANEX) process, trivalent actinide lanthanide separation with phosphorus-reagent extraction from aqueous komplexes (TALSPEAK), process, and group actinides extraction (GANEX) process. ,− The sulfonated multidentate N -donor ligands ( SO 3 -Ph-BTP , TS-BTPhen2 , and DS-Ph-DAPhen , as shown in Scheme S1) were among the most explored hydrophilic ligands. ,,− The separation factors for Eu(III) and Am(III) (SF Eu/Am ) of these sulfonated ligands could reach as high as 10 3 in acid and the selectivity was reported to be closely related to the number of sulfonate groups . Drawbacks of these ligands included harsh reaction conditions for the introduction of sulfonate groups and the secondary waste generated by sulfur, conflicting with the CHON concept.…”

Section: Introductionmentioning

confidence: 99%

A Simple yet Efficient Hydrophilic Phenanthroline-Based Ligand for Selective Am(III) Separation under High Acidity

et al. 2023

View full text Add to dashboard Cite

Highly selective hydrophilic ligands were believed to be an efficient way to overcome the massive amount of hazardous organic solvent used in the liquid−liquid extraction process and stood as a new frontier in the Lns(III)/Ans(III) partition. Current reported hydrophilic ligands suffer from harsh preparation conditions, inferior extraction performances, limited available chemical structures, and inability to carry out extraction under high acidity. In this article, we report a simple yet efficient carboxylic group modified phenanthroline-diimide ligand which displayed unexpected Lns(III)/Ans(III) and Ans(III)/Ans(III) separation capabilities in 1.5 M HNO 3 . Unique dimeric architectures for Eu(III) complexes were observed, which could be the origin of the outperforming selectivity and acid resistance. We believe this crystal engineering approach could inspire a renaissance in searching for new functional groups and coordination modes for efficient, highacid-tolerance Lns(III)/Ans(III) separation ligands.

show abstract

Novel water-soluble aromatic bisdiglycolamide masking agents for the separation of trivalent americium over lanthanides by NTAamide(n-Oct) extractant

Cited by 10 publications

References 72 publications

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

Amine-Terminated Phenanthroline Diimides as Aqueous Masking Agents for Am(III)/Eu(III) Separation: An Alternative Ligand Design Strategy for Water-Soluble Lanthanide/Actinide Chelating Ligands

A Simple yet Efficient Hydrophilic Phenanthroline-Based Ligand for Selective Am(III) Separation under High Acidity

Contact Info

Product

Resources

About