Direct dissolution of uranium oxides in deep eutectic solvent: An insight using electrochemical and luminescence study

Gupta, Ruma; Gamare, Jayashree; Gupta, Santosh K.; Kumar, Sachin

doi:10.1016/j.molstruc.2020.128266

Cited by 25 publications

(20 citation statements)

References 27 publications

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“…1 Since the discovery of deep eutectic solvents, DESs have shown excellent potential in a wide variety of applications, 2 for example, separation, 3,4 catalysis, 5 synthesis, 6 preparation of special materials, 7 biological and pharmaceutical applications, 8 electrochemical, 9 and dissolution of uranium oxide as a nuclear raw material. 10 As a new class of ionic liquids (ILs) analogs, DESs not only share some of the desirable characteristics of ILs, such as low volatility, low flammability, biological tunability, low toxicity but also address some critical limitations of ILs, for example, time-consuming, labor and cost-intensive preparation process. Therefore, DESs, as "green" solvents have the potential to gradually replace conventional volatile solvents used in industrial applications.…”

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confidence: 99%

Group and group‐interaction contribution method for estimating the melting temperatures of deep eutectic solvents

Hou

et al. 2021

AIChE Journal

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Deep eutectic solvents (DESs) are mixtures of two or more components that have lower melting temperatures compared to their constituting components. DESs possess many advantages, for example, low volatility, low flammability, and low toxicity, which make them promising alternatives to traditional organic solvents. The melting temperature, one of the important physical properties, is of essential importance for industrial applications. In this work, a group and group-interaction contribution method was proposed to estimate the melting temperatures of DESs using an extensive database (1528 DESs, 1541 data points). The average absolute relative deviation (%AARD) between the estimated and experimental values of the melting temperature was 5.67% for binary DESs. Subsequently, this method was also extended to estimate the melting temperature of ternary DESs, with the AARD of 6.13%. The results indicate the high accuracy and broad applicability of the method and pave the way for the rational design of task-specific DESs.

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confidence: 99%

Group and group‐interaction contribution method for estimating the melting temperatures of deep eutectic solvents

Hou

et al. 2021

AIChE Journal

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“…The presence of protons in Maline, acting as an oxygen acceptor, supports dissolution through the water-forming reaction with oxygen atoms of metal oxides. Therefore, in the present case, the choice of Maline as a solvating media for direct and quantitative sequestration of U matrices without any additives is beneficial over the additives and other solvating media used in the previous studies, − ,, owing to the bidentate coordination mode of Maline (obtained by EXAFS; described later) which offers strong interaction for U and hence more solvating potential than the urea and PTSA.…”

Section: Resultsmentioning

confidence: 90%

“…The thermodynamic stability and energetics of interaction provide crucial inputs to understand the basic chemistry behind the dissolution and then the affinity of uranyl (UO 2 2+ ) with Maline. Previous studies 62,63 have not shown how DESs will interact with the uranium ion at the molecular level. In the present case, the interaction of uranyl with Maline was probed with absorption spectrophotometry and isothermal titration calorimetry.…”

Section: ■ Results and Discussionmentioning

confidence: 94%

“…63 Moreover, the dissolution of other uranium matrices such as Rb 2 (U(SO 4 ) 3 ), uranium metal powder, U 3 Si 2 , (U, Pu)O 2 , and PuO 2 has not been explored in their studies. 62,63 Previous literature reports 44,64 imply that the urea (reline) and paratoluene sulphonic acid (PTSA) act as monodentate ligands via the oxygen atom. Hence, it was anticipated that these ligands are unable to offer very strong interactions for the U metal ion.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Abbott et al. , reported that Maline has a higher solvation potential for hardly soluble metal oxides than the reline and ethaline. Gupta et al have described the dissolution of uranyl nitrate and uranium oxides with higher stoichiometric DESs urea/ChCl (2:1) (reline) and PTSA/ChCl (1:2), respectively . Moreover, the dissolution of other uranium matrices such as Rb 2 (U(SO 4 ) 3 ), uranium metal powder, U 3 Si 2 , (U, Pu)O 2 , and PuO 2 has not been explored in their studies. , Previous literature reports , imply that the urea (reline) and para-toluene sulphonic acid (PTSA) act as monodentate ligands via the oxygen atom.…”

Section: Resultsmentioning

confidence: 99%

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New Greener and Sustainable Methodology for Direct Sequestering and Analysis of Uranium Using a Maline Supramolecular Scaffold and Mechanistic Understanding through Speciation and Interaction Studies

Srivastava

Dumpala

Sahu

et al. 2021

ACS Sustainable Chem. Eng.

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Research, based on the development of an economical innovative green technology, is the quintessential requirement for the advancement of the nuclear fuel cycle (NFC). The present studies show that Maline, with a preorganized supramolecular scaffold, would be considered as the workhorse for its potential efficacy in diverse facets of the NFC, specifically as an elegant metal hijacker for processing of uranium (U) matrices, designer solvent for green analysis of U, and a promising U chelator for a greener alternative for the cleanup of U contamination. Seven U matrices (UO3, UN, UO2, Rb2U(SO4)3, U metal, U3Si2, and (U, Pu)O2) were dissolved in Maline without any external additives and cyclic voltammetry was performed to investigate the redox speciation, viz., redox thermodynamics (E p and E f) and kinetic (D 0, k 0, and αn) parameters and mechanistic electron transfer of the dissolved U species. To get an insight into the molecular speciation, the structural analysis on UO3 dissolved in Maline was conducted by extended X-ray absorption fine structure, which indicates an interesting observation of the formation of UO2 2+ kind of species with malonic acid and H2O at equatorial coordination. Molecular dynamics and density functional theory simulations were carried out to acquire diffusion, optimized structure, binding energy, and molecular orbital diagram of U species in Maline, to corroborate the experimental results and to shed light on the hydrogen-bond network in Maline with aqueous dilution. The interaction of uranyl with Maline was probed by luminescence, absorption spectroscopy, and calorimetry titration. Green analysis methodology was developed based on Maline digestion followed by voltammetric determination of U in nuclear material samples. Green chemistry metrics were evaluated to authenticate the greener aspects of the present methodology. The present developed methodology of direct sequestration and analysis of U matrices represents an appropriate replacement of the existing method, viz., hazardous acidic processing of U matrices followed by biamperometry analysis.

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A Hydrophobic Deep Eutectic Solvent for Nuclear Fuel Cycle: Extraction of Actinides and Dissolution of Uranium Oxide

Gamare,

Vats

2023

Eur J Inorg Chem

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Hydrophobic Deep Eutectic Solvents (DESs) have been attracting attention for metal ion extraction in solvent extraction process due to their favorable properties. A Trioctyl phosphine oxide (TOPO) and Thenoyl trifluoroacetone (HTTA) based hydrophobic DES was synthesized and characterized by FTIR and NMR spectroscopy. Actinide ions ( UO22+, Pu4+ and Am3+ ) and Eu3+ extraction was carried out using the DES which shows that it extracts these metal ions from aqueous nitric acid medium depending upon the molarity of nitric acid. At higher molarity of nitric acid (>5 M) the extraction becomes insignificant only for trivalent metal ions and open up the possibility to selectively strip trivalent metal ions from tetravalent and hexavalent ions. This DES was also used for dissolution of uranium oxide (UO3). The dissolution kinetics was studied and it was shown that oxide was dissolved within an hour at 80°C. The maximum solubility of UO3 in DES was measured and found to be 130±5 mg/mL which is one of the highest reported solubility of UO3 in ILs and DES. The species of uranium which is formed insitu in DES was ascertained to be UO2(TTA)2.TOPO after dissolution of UO3 as supported by FTIR and NMR (1H and 31P) investigations.

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Direct dissolution of uranium oxides in deep eutectic solvent: An insight using electrochemical and luminescence study

Cited by 25 publications

References 27 publications

Group and group‐interaction contribution method for estimating the melting temperatures of deep eutectic solvents

Group and group‐interaction contribution method for estimating the melting temperatures of deep eutectic solvents

New Greener and Sustainable Methodology for Direct Sequestering and Analysis of Uranium Using a Maline Supramolecular Scaffold and Mechanistic Understanding through Speciation and Interaction Studies

A Hydrophobic Deep Eutectic Solvent for Nuclear Fuel Cycle: Extraction of Actinides and Dissolution of Uranium Oxide

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