Ion structure controls ionic liquid near-surface and interfacial nanostructure

Elbourne, Aaron; Voïtchovsky, Kislon; Warr, Gregory G.; Atkin, Rob

doi:10.1039/c4sc02727b

Cited by 97 publications

(180 citation statements)

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“…It is produced by propylammonium cations electrostatically bound to the oxygen triads 47 associated with negatively charged mica surface sites. 33,36,37 are apparent for each system. This is because the propylammonium cation binds electrostatically to negatively charged adsorption sites on the mica, and the n-alkanols are unable to compete; n-alkanols can adsorb to oxygens on the mica surface via hydrogen bonds, but hydrogen bonds are typically an order of magnitude lower energy than electrostatic interactions.…”

Section: Resultsmentioning

confidence: 97%

“…44 Figure 1 A is consistent with images for the pure PAN -mica interface we have reported previously. 33 A well-defined lattice structure is clear, obscured in some areas by interference from near surface features.…”

Section: Resultsmentioning

confidence: 99%

“…31,32 Recently, we have used amplitude modulated atomic force microscopy (AM-AFM) imaging to examine the lateral IL-solid interface in contact with a bulk IL. A rich library of nanostructures were observed both adsorbed onto [33][34][35][36][37] and near 33,36 solid interfaces, which revealed that previous descriptions based on data normal to the IL-solid interface were far too simplistic. [38][39][40][41] The nanostructure of the ion layer in contact with the substrate is strongly affected by the registry between the ions and surface adsorption sites, 13,[33][34][35][36][37] except when the cation is large and sterically hindered.…”

Section: Introductionmentioning

confidence: 95%

“…[38][39][40][41] The nanostructure of the ion layer in contact with the substrate is strongly affected by the registry between the ions and surface adsorption sites, 13,[33][34][35][36][37] except when the cation is large and sterically hindered. 33 As in the bulk, near surface nanostructure is sensitive to both cation and anion type. For propylammonium nitrate (PAN), the bicontinuous, isotropic bulk sponge structure becomes flatter near a mica surface.…”

Section: Introductionmentioning

confidence: 99%

“…As the distance from the surface is increased, these large polar regions decay to the smaller, more highly-curved bulk structure. 33 In this study the nanostructure of binary mixtures of PAN with butanol, octanol and dodecanol near a mica surface are investigated using AM-AFM as a function of composition. This reveals how the near surface nanostructure varies with liquid composition and n-alkanol alkyl chain length, with particular focus on the near surface region.…”

Section: Introductionmentioning

confidence: 99%

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Near surface properties of mixtures of propylammonium nitrate with n-alkanols 1. Nanostructure

Elbourne

Cronshaw

Voïtchovsky

et al. 2015

Phys. Chem. Chem. Phys.

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Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. * Corresponding author AbstractIn situ amplitude modulated -atomic force microscopy (AM-AFM) has been used to probe the nanostructure of mixtures of propylammonium nitrate (PAN) with n-alkanols near a mica surface. PAN is a protic ionic liquid (IL) which has a bicontinuous sponge-like nanostructure of polar and apolar domains in the bulk, which becomes flatter near a solid surface. Mixtures of PAN with 1-butanol, 1-octanol, and 1-dodecanol at 10 -70 vol% n-alkanol have been examined, along with each pure n-alkanol, to reveal the effect of composition and n-alkanol chain length. At low concentrations the butanol simply swells the PAN nearsurface nanostructure, but at higher concentrations the nanostructure fragments. Octanol and dodecanol first lower the preferred curvature of the PAN near-surface nanostructure because, unlike n-butanol, their alkyl chains are too long to be accommodated alongside the PAN cations. At higher concentrations, octanol and dodecanol self-assemble into n-alkanol rich aggregates in a PAN rich matrix. The concentration at which aggregation first becomes apparent decreases with n-alkanol chain length.2

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Near surface properties of mixtures of propylammonium nitrate with n-alkanols 1. Nanostructure

Elbourne

Cronshaw

Voïtchovsky

et al. 2015

Phys. Chem. Chem. Phys.

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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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Ionogels with Carbon and Organic Polymer Matrices for Electrochemical Systems

Ratajczak,

Béguin

2024

Advanced Sustainable Systems

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Ionogels (IGs) consisting of ionic liquids (ILs) confined in carbon and organic polymer matrices have recently emerged as promising materials for electrochemical systems. This perspective article explores how the structural, dynamic, and thermodynamic properties of ILs are modified by their confinement. It emphasizes the importance of combining various ILs and matrices to enhance IG properties through IL‐matrix interactions. Specifically, it highlights the significant downshift of IL melting point observed in certain porous carbons, as well as the enhanced ionic conductivity at sub‐ambient temperature in polymer networks. Accordingly, the suitability of these IGs for use in electrochemical systems operating at low temperature is discussed. Although significant progress has been made in the development and applications of carbon and polymer IGs, it is necessary to further explore the texture/structure of real host matrices, which may differ from model ones. Investigating the low‐temperature mobility of ions in IG‐based electrodes with micro/mesoporous carbons is an example of unexplored research area that may open new opportunities for increasing the energy and power density in energy storage applications. The suggested directions should facilitate innovative solutions to current and future challenges for electrochemical systems across a wide temperature range from −40 to 200 °C.

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Ion structure controls ionic liquid near-surface and interfacial nanostructure

Abstract: In situ amplitude modulated atomic force microscopy (AM-AFM) has been used to resolve the 3-dimensional nanostructure of five protic ILs at and near the surface of mica.

Cited by 97 publications

References 91 publications

Near surface properties of mixtures of propylammonium nitrate with n-alkanols 1. Nanostructure

Near surface properties of mixtures of propylammonium nitrate with n-alkanols 1. Nanostructure

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

Ionogels with Carbon and Organic Polymer Matrices for Electrochemical Systems

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