Nanostructure of a deep eutectic solvent at solid interfaces

Elbourne, Aaron; Meftahi, Nastaran; Greaves, Tamar L.; McConville, Christopher F; Bryant, Gary; Bryant, Saffron J.; Christofferson, Andrew J.

doi:10.1016/j.jcis.2021.01.089

Cited by 31 publications

(39 citation statements)

References 96 publications

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“… 69 However, the presence of a neutrally charged graphite interface, which could cause similar effects in the solvent structure to those induced by the hydrophobic surfactant tails, only prompts subtle short-range changes in the molecular ordering of 1:2 choline chloride:glycerol. 70 At the surfactant concentrations investigated here, these local changes are not expected to alter the bulk behavior of the DES, as correlations between the solvent components are relatively resilient. 11 , 71 Also, the trends observed in intermicellar interactions and the unchanged micelle morphology in the concentration range investigated here suggest that no significant changes in the behavior of the solvent occur when increasing the surfactant content.…”

Section: Discussionmentioning

confidence: 85%

Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

et al. 2021

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While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion–ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.

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Section: Discussionmentioning

confidence: 85%

Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

et al. 2021

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“…They found that Au (111) surface reconstructs in ethaline when it is negative charged, and this reconstruction may be due to the water in ethaline DES. Elbourne et al 25 (as shown in Figure 1). Decanoic acid 6,46 is one of the hydrogen donors, and menthol and thymol 43 are used as common hydrogen acceptors for hydrophobic DESs.…”

Section: Introductionmentioning

confidence: 91%

“…However, the DES-aqueous liquid-liquid interface may present a non-zero dipole moment since the molecules are likely to show a preferential orientation at the interface. 5,24,25 32 showed that the good water stability of the hydrophobic DESs is critical for their extraction ability. Kaul et al 33 studied the partitioning of n-alkanols and benzene derivatives in hydrophobic DES and water.…”

Section: Introductionmentioning

confidence: 99%

“…The bulk DES and aqueous phases shall present zero in dipole since the molecules could orient in any direction evenly. However, the DES‐aqueous liquid–liquid interface may present a non‐zero dipole moment since the molecules are likely to show a preferential orientation at the interface 5,24,25 . Such dipole fluctuation could contribute to the nonbulk features of the interface.…”

Section: Introductionmentioning

confidence: 99%

“…They found that Au (111) surface reconstructs in ethaline when it is negative charged, and this reconstruction may be due to the water in ethaline DES. Elbourne et al 25 investigated the heterogeneous DES–solid interfaces via the combination of high‐resolution amplitude‐modulated atomic force microscopy and MD simulations (DES: choline chloride: glycerol and solid surface: mica and a single layer of graphene surface). Their result shows that DES is highly ordered by polar interactions at the mica interface, whereas DES formed a distinct apolor‐driven row‐like structure at the graphene surface.…”

Section: Introductionmentioning

confidence: 99%

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Structure and hydrogen bonds of hydrophobic deep eutectic solvent‐aqueous liquid–liquid interfaces

et al. 2021

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Hydrophobic deep eutectic solvents (DESs) emerge as candidates to extract organic substrates from aqueous solutions. The DES-aqueous liquid-liquid interface plays a vital role in the extraction ability of DESs because the nonbulk structure of interfacial molecules could cause thermodynamic and kinetic barriers. One question is how the DES compositions affect the structural features of the interface. We investigate the density profile, dipole moment, and hydrogen bonds of eight hydrophobic DESaqueous interfaces using molecular dynamics simulations. The eight DESs are composed of four organic compounds: decanoic acid, menthol, thymol, and lidocaine. The results show the variations of dipole moment and hydrogen bond structure and dynamics at the interfaces. These variations could influence the extraction ability of DES through adjusting the partition and kinetics of organic substrates in the DESaqueous biphasic systems. We also analyze the relationship between the variation of these interfacial features and the size and hydrophobicity of DES components.

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Mapping the Three‐Dimensional Nanostructure of the Ionic Liquid–Solid Interface Using Atomic Force Microscopy and Molecular Dynamics Simulations

Elbourne

Dupont²,

Kariuki

et al. 2023

Adv Materials Inter

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an IL was a pure salt with melting point below 100 °C, [1][2][3][4][5][6][7][8] however, this definition has expanded in recent years to include ionic solvents which have salt concentrations substantially greater than conventional electrolytes. [9,10] ILs can be broadly characterized into sub-classes based on their chemical structure or synthesis procedure, such as protic [8,11] and aprotic ILs, [12,13] among other classes. [14][15][16] ILs can be tailored to be highly thermally or chemically stable, have large electrochemical windows and/or negligible-volatility. [6,8,11,[17][18][19] These properties have made them interesting solvent candidates for a range of applications, including organic reaction media, [20][21][22][23] lubrication, [24,25] electrodeposition, [26][27][28][29][30] materials extraction, [31][32][33][34] catalysis, [35][36][37] and materials chemistry. [38][39][40][41][42][43] ILs are often nanostructured on the molecular length scale, both in the bulk liquid [3,[44][45][46][47] and at an interface. [48][49][50][51][52][53][54][55][56] Bulk IL nanostructure has been studied using numerous scattering techniques [44,45,[57][58][59][60][61][62][63][64][65] (X-rays, neutron, etc.) and a variety of computational approaches. [66][67][68][69][70] Together, these studies have suggested that many ILs form a self-assembled, heterogeneous Ionic liquids (ILs) are a widely investigated class of solvents for scientific and industrial applications due to their desirable and "tunable" properties. The IL-solid interface is a complex entity, and despite intensive investigation, its true nature remains elusive. The understanding of the IL-solid interface has evolved over the last decade from a simple 1D double layer, to a 2D ordered interface, and finally a liquid-specific, complex 3D ordered liquid interface. However, most studies depend solely on one technique, which often only examine one aspect of the interfacial nanostructure. Here, a holistic study of the protic IL-solid interface is presented, which provides a more detailed picture of IL interfacial solvation. The 3D nanostructure of the ethylammonium nitrate (EAN)-mica interface is investigated using a combination of 1D, 2D, and 3D amplitude modulated-atomic force microscopy and molecular dynamics simulations. Importantly, it is found that the EAN-mica interface is more complex than previously reported, possessing surface-adsorbed, near-surface, surface-normal, and lateral heterogeneity, which propagates at relatively large distances from the solid substrate. The work presented in this study meaningfully enhances the understanding of the IL-solid interface.

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Nanostructure of a deep eutectic solvent at solid interfaces

Cited by 31 publications

References 96 publications

Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

Structure and hydrogen bonds of hydrophobic deep eutectic solvent‐aqueous liquid–liquid interfaces

Mapping the Three‐Dimensional Nanostructure of the Ionic Liquid–Solid Interface Using Atomic Force Microscopy and Molecular Dynamics Simulations

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