Electrochemical and thermodynamic insights on actinide type (IV) deep eutectic solvent

Gupta, Ruma; Gamare, Jayashree; Sahu, Manjulata; Pandey, Kaushlendra; Gupta, Santosh K.

doi:10.1016/j.molliq.2021.115550

Cited by 20 publications

(7 citation statements)

References 78 publications

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“…These mixtures show unusually low viscosity and surface tensions and the presence of fluxional oligomeric polyanions and polycations, and were employed as reaction media in the combustion synthesis of oxides; more recently, actinide-based type IV DES (An-DES) were obtained by mixing uranyl nitrate hexahydrate UO 2 (NO 3 ) 2 ·6H 2 O (UNH) with urea in different ratios ( Figure 4 ), finding 0.2:0.8 to be the optimal UNH:urea mole fraction, with a quite low eutectic temperature of −5.2 °C. This liquid was employed to prepare UO 2 nanoparticles through an optimized electrosynthesis path [ 137 ]. Some examples of reactions in LADES are given in Table 2 .…”

Section: Lewis Acid Des (Lades)mentioning

confidence: 99%

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Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

et al. 2022

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Deep Eutectic Solvents have gained a lot of attention in the last few years because of their vast applicability in a large number of technological processes, the simplicity of their preparation and their high biocompatibility and harmlessness. One of the fields where DES prove to be particularly valuable is the synthesis and modification of inorganic materials—in particular, nanoparticles. In this field, the inherent structural inhomogeneity of DES results in a marked templating effect, which has led to an increasing number of studies focusing on exploiting these new reaction media to prepare nanomaterials. This review aims to provide a summary of the numerous and most recent achievements made in this area, reporting several examples of the newest mixtures obtained by mixing molecules originating from natural feedstocks, as well as linking them to the more consolidated methods that use “classical” DES, such as reline.

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Section: Lewis Acid Des (Lades)mentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

et al. 2022

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“…Our group also worked extensively on exploring DES media for speciation studies and dissolution of rare earth and actinide ions. 5,[30][31][32][33][34] Rare earth ions have found applications in several aspects associated with humankind, ranging from health, energy, and environments, making their presence felt everywhere, spanning mobile phones, televisions, laptops, luminescent materials, permanent magnets, etc. [35][36][37] In most of the applications, trivalent europium ions contribute highly photostable bright red emission originating from hypertensive electric dipole electronic transition (EDT) 5 D 0 -7 F 2 at ∼615 nm and orange emission from pure magnetic dipole transition (MDT) 5 D 0 -7 F 1 at ∼590 nm together with their longer excited state lifetime.…”

Section: Introductionmentioning

confidence: 99%

“…Our group also worked extensively on exploring DES media for speciation studies and dissolution of rare earth and actinide ions. 5,30–34…”

Section: Introductionmentioning

confidence: 99%

Understanding the excited state dynamics and redox behavior of highly luminescent and electrochemically active Eu(iii)–DES complex

Patil,

Agrawal,

Gupta

et al. 2023

Dalton Trans.

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“…The major obstacles to their use and scale-up progress for SNF reprocessing and recovery will be this understanding of the actinide behavior within them. Our previous experience with already known DESs with large electrochemical windows for solubilizing uranium oxides − enables their use for sequestering uranium/other actinide elements from primary or secondary resources to replace conventional acids and for electrodeposition to refine metals. Very recently, we have developed a low melting DES based on a heptylphosphonium bromide as a HBA and decanoic acid as a HBD and have applied it as a scintillator .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Approach to Reveal Interaction of Uranyl Ions in Alkyltriphenylphosphonium Bromide-Based Deep Eutectic Solvent

et al. 2022

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Speciation is known to control fundamental aspects of metal processing and electrochemical behavior such as solubility and redox potentials. Deep eutectic solvents (DESs) are an emerging class of green, low-cost and designer solvents and are being explored as alternatives for recycling nuclear fuel and critical materials. However, there is a lack of knowledge about the behavior of metals in them. Here, for the first time, we synthesized three new DESs based on alkyltriphenylphosphonium bromide (C n PPh3Br), with varied alkyl chain lengths (n), as the hydrogen-bond acceptor along with decanoic acid (DA) as the hydrogen-bond donor and explored the redox speciation of uranyl nitrate. The changes in the Fourier transform infrared and NMR spectra helped elucidate the formation of hydrogen bonds in DES. The absorption maxima of uranyl in DES was red-shifted by 10 nm compared to the free uranyl, with concomitant increase in intensity and luminescence lifetime, which suggested a strong interaction of uranyl nitrate with DES. Cyclic voltammetry was probed to understand the redox thermodynamics, transport properties, and heterogeneous electron transfer kinetics of the irreversible electron transfer of uranyl ions in the three DESs. Electrochemical and spectroscopic techniques together with density functional theory calculations unlocked microscopic insights into the solvation and speciation of UO2 2+ ions in three DESs and also the associated unusual trends observed in the physical properties of the DESs. The hydrogen-bonded structure of DES plays a crucial role in the redox behavior of the UO2 2+ ion due to its strong potent complexation with its components. The basic findings of the present work can have far-reaching consequences for the extraction, electrochemical separation, and future development of redox-based separation processes in the nuclear fuel cycle.

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Electrochemical and thermodynamic insights on actinide type (IV) deep eutectic solvent

Cited by 20 publications

References 78 publications

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

Recent Advances in the Synthesis of Inorganic Materials Using Environmentally Friendly Media

Understanding the excited state dynamics and redox behavior of highly luminescent and electrochemically active Eu(iii)–DES complex

Mechanistic Approach to Reveal Interaction of Uranyl Ions in Alkyltriphenylphosphonium Bromide-Based Deep Eutectic Solvent

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