Influence of chloride ion on zinc electrodeposition from choline chloride based deep eutectic solvent

Wang, Xiang; Xu, Cunying; Liu, Hai; Huang, Mengting; Ren, Xiangyu; Wang, Shuxian; Ye, Hua; Zhang, Qibo; Ru, Juanjian

doi:10.1007/s11581-019-03293-x

Cited by 20 publications

(11 citation statements)

References 25 publications

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“…This needs large work terms associated with bringing the uranium species to the equilibrium electron-transfer configuration at the electrode surface. Previous studies − reported that DES-based electrolyte systems show the lower values of the transfer coefficient (α < 0.5) of metal ions because of the solvent reorganizational effect, which can provide the asymmetry in the transitional configuration during the electron transfer with respect to the initial and final configurations and difference in the mechanism of electron transfer in the DES electrolyte from that of the aqueous solution. ,, In the present case, the values of transfer coefficients (α) of U matrices were also observed to be <0.5 (Table S4; taken n = 1) except for peak 1 of U 3 Si 2 , which is 0.539 and could be considered approximately as 0.5. The value of α ≤ 0.5 indicates the sluggish electron-transfer kinetics and corroborates the irreversibility of reduction waves of U matrices in Maline.…”

Section: Resultssupporting

confidence: 56%

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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Section: Resultssupporting

confidence: 56%

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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“…Moreover, the peculiarities of Zn 2+ coordination were found to result in unusual voltammetric behavior, characterized by a cathodic peak in the cathodic branch of the anodic-going scan. Generally, the mechanistic studies of Zn electrodeposition onto glassy carbon (GC) from DESs [ 20 , 21 , 22 , 23 , 24 , 25 ] have concluded that the metal is formed by the reduction of an intermediate Zn-containing species. Finally, the reactivity of choline chloride and ethylene glycol can impact coordination in that these species can be dehydrogenated at negative potential forming RO − , which can replace one or more chloride ligands in [ZnCl 4 ] 2− [ 20 , 21 , 23 ].…”

Section: Introductionmentioning

confidence: 99%

Zinc Electrode Cycling in Deep Eutectic Solvent Electrolytes: An Electrochemical Study

et al. 2023

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Among post-lithium ion battery technologies, rechargeable chemistries with Zn anodes bear notable technological promise owing to their high theoretical energy density, lower manufacturing cost, availability of raw materials and inherent safety. However, Zn anodes, when employed in aqueous electrolytes, suffer from hydrogen evolution, passivation, and shape changes. Alternative electrolytes can help tackle these issues, preserving the green and safe characteristics of aqueous-based ones. Deep eutectic solvents (DESs) are promising green and low-cost non-aqueous solvents for battery electrolytes. Specifically, the cycling of Zn anodes in DESs is expected to be reversible, chiefly owing to their dendrite-suppression capability. Nevertheless, apart from a few studies on Zn plating, insight into the cathodic–anodic electrochemistry of Zn in DESs is still very limited. In view of developing DES-based battery electrolytes, it is crucial to consider that a potential drawback might be their low ionic conductivity. Water molecules can be added to the eutectic mixtures by up to 40% to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature. In this study, we address the electrochemistry of Zn in two different hydrated DESs (ChU and ChEG with ~30% H2O). Fundamental electrokinetic and electrocrystallization studies based on cyclic voltammetry and chronoamperometry at different cathodic substrates are completed with a galvanostatic cycling test of Zn|Zn symmetric CR2032 coin cells, SEM imaging of electrodes and in situ SERS spectroscopy. This investigation concludes with the proposal of a specific DES/H2O/ZnSO4-based electrolyte that exhibits optimal functional performance, rationalized on the basis of fundamental electrochemical data, morphology evaluation and modeling of the cycling response.

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“…[7,14,18,21,[36][37][38][39] In addition, the effect of additives on the zinc deposit, for example NaCl, dimethyl sulfoxide,ZnO and various Zn 2+ salt anions was studied in detail. [20,[39][40][41][42][43] Furthermore,t he influence of varying amounts of water in the IL to alter the deposition behavior,aswell as the density,viscosity and conductivity was examined. [9,20,38,[43][44][45][46][47] Them ain aspect, however, is that for dendrite free zinc deposition especially the concentration of water in the electrolyte appeared to be the critical parameter.…”

Section: Introductionmentioning

confidence: 99%

“…This could already be achieved by many research groups with the focus on the varying deposition behavior from different ILs with selected anion and cation combinations [7, 14, 18, 21, 36–39] . In addition, the effect of additives on the zinc deposit, for example NaCl, dimethyl sulfoxide, ZnO and various Zn 2+ salt anions was studied in detail [20, 39–43] . Furthermore, the influence of varying amounts of water in the IL to alter the deposition behavior, as well as the density, viscosity and conductivity was examined [9, 20, 38, 43–47] .…”

Section: Introductionmentioning

confidence: 99%

Electrodeposition of Zinc onto Au(111) and Au(100) from the Ionic Liquid [MPPip][TFSI]

et al. 2021

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The improvement of rechargeable zinc/air batteries was a hot topic in recent years. Predominantly, the influence of water and additives on the structure of the Zn deposit and the possible dendrite formation were studied. However, the effect of the surface structure of the underlying substrate was not focused on in detail, yet. We now show the differences in electrochemical deposition of Zn onto Au(111) and Au(100) from the ionic liquid N‐methyl‐N‐propylpiperidinium bis(trifluoromethanesulfonyl)imide. The fundamental processes were initially characterized via cyclic voltammetry and in situ scanning tunnelling microscopy. Bulk deposits were then examined using Auger electron spectroscopy and scanning electron microscopy. Different structures of Zn deposits are observed during the initial stages of electrocrystallisation on both electrodes, which reveals the strong influence of the crystallographic orientation on the metal deposition of zinc on gold.

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Influence of chloride ion on zinc electrodeposition from choline chloride based deep eutectic solvent

Cited by 20 publications

References 25 publications

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

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

Zinc Electrode Cycling in Deep Eutectic Solvent Electrolytes: An Electrochemical Study

Electrodeposition of Zinc onto Au(111) and Au(100) from the Ionic Liquid [MPPip][TFSI]

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