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Specific ion effects at graphitic interfaces.

ABSTRACT: Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores. We confirm that adsorption energy increases with ionic radius, while being highly dependent on the pore size. In addition, in contrast with conventional electrochemical models, we find that interfacial charge transfer contributes non-negligibly to this interaction and can be further enhanced by confinement. We conclude that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.

SUBMITTER: Zhan C

PROVIDER: S-EPMC6813325 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Specific ion effects at graphitic interfaces.

Zhan Cheng C Cerón Maira R MR Hawks Steven A SA Otani Minoru M Wood Brandon C BC Pham Tuan Anh TA Stadermann Michael M Campbell Patrick G PG

Nature communications 20191024 1

Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and wit ...[more]

PMID: 31649261

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Project description:Ion-specific effects in aqueous solution, known as the Hofmeister effect, are prevalent in diverse systems ranging from pure ionic to complex protein solutions. The objective of this paper is to explicitly demonstrate how complex ion-ion and ion-water interactions manifest themselves in the Hofmeister effect based on a series of recent experimental observations. These effects are not considered in the classical descriptions of ion effects, such as the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, and therefore they fail to describe the origin of the phenomenological Hofmeister effect. However, given that models considering the basic forces of electrostatic and van der Waals interactions can offer rationalization for the core experimental observations, a universal interaction model stands a chance of being developed. In this perspective, we separately derive the contribution from ion-ion electrostatic interactions and ion-water interactions from second harmonic generation (SHG) data at the air-ion solution interface, which yields an estimate of the ion-water interactions in solution. The Hofmeister ion effect observed for biological solutes in solution should be similarly influenced by contributions from ion-ion and ion-water interactions, where the same ion-water interaction parameters derived from SHG data at the air-ion solution interface could be applicable. A key experimental data set available from solution systems to probe ion-water interactions is the modulation of water diffusion dynamics near ions in a bulk ion solution, as well as near biological liposome surfaces. This is obtained from Overhauser dynamic nuclear polarization (ODNP), a nuclear magnetic resonance (NMR) relaxometry technique. The surface water diffusivity is influenced by the contribution from ion-water interactions, both from localized surface charges and adsorbed ions, although the relative contribution of the former is larger on liposome surfaces. In this perspective, ion-water interaction energy values derived from experimental data for various ions are compared with theoretical values in the literature. Ultimately, quantifying ion-induced changes in the surface energy for the purpose of developing valid theoretical models for ion-water interactions will be critical to rationalizing the Hofmeister effect.

Project description:The structure of poly(sodium 4-styrenesulfonate) (NaPSS) polyelectrolytes at air-water interfaces was investigated with tensiometry, ellipsometry, and vibrational sum-frequency generation (SFG) in the presence of low and high CaCl2 concentrations. In addition, we have studied the foaming behavior of 20 mM NaPSS solutions to relate the PSS molecular structure at air-water interfaces to foam properties. PSS polyelectrolytes without additional salt exhibited significant surface activity, which can be tuned further by additions of CaCl2. The hydrophobicity of the backbone due to incomplete sulfonation during synthesis is one origin, whereas the effective charge of the polyelectrolyte chain is shown to play another major role. At low salt concentrations, we propose that the polyelectrolyte is forming a layered structure. The hydrophobic parts are likely to be located directly at the interface in loops, whereas the hydrophilic parts are at low concentrations stretched out into near-interface regions in tails. Increasing the Ca2+ concentration leads to ion condensation, a collapse of the tails, and likely to Ca2+ intra- and intermolecular bridges between polyelectrolytes at the interface. The increase in both surface excess and foam stability originates from changes in the polyelectrolyte's hydrophobicity due to Ca2+ condensation onto the PSS polyanions. Consequently, charge screening at the interface is enhanced and repulsive electrostatic interactions are reduced. Furthermore, SFG spectra of O-H stretching bands reveal a decrease in intensity of the low-frequency branch when c(Ca2+) is increased whereas the high-frequency branch of O-H stretching modes persists even for 1 M CaCl2. This originates from the remaining net charge of the PSS polyanions at the air-water interface that is not fully compensated by condensation of Ca2+ ions and leads to electric-field-induced contributions to the SFG spectra of interfacial H2O. A charge reversal of the PSS net charge at the air-water interface is not observed and is consistent with bulk electrophoretic mobility measurements.

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Specific ion effects at graphitic interfaces.

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Specific ion effects at graphitic interfaces.

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