We use molecular dynamics simulations of the primitive model of electrolytes to study the ionic structure in aqueous monovalent electrolyte solutions confined by charged planar interfaces over a wide range of electrolyte concentrations, interfacial separations, surface charge densities, and ion sizes. The investigations are inspired by recent experiments that have directly measured the increase in the decay length for highly concentrated electrolytes with an increase in concentration. The behavior of ions in the nanoconfinement created by the interfaces is probed by evaluating the ionic density profiles, net charge densities, integrated charges, and decay lengths associated with the screening of the charged interface. The results show the presence of two distinct regimes of screening behavior as the concentration is changed from 0.1M to 2.5M for a wide range of electrolyte systems generated by tuning the interfacial separation, surface charge density, and ionic size. For low concentrations, the integrated charge exhibits a monotonic decay to 0 with a decay length that decreases sharply with increasing concentration. For high concentrations (≳1M), the integrated charge has a non-monotonic behavior signaling charge inversion and formation of structured layers of ions near the interfaces. The decay length under these conditions rises with increasing concentration. To complement the simulation results, a variational approach is developed that produces charge densities with characteristics consistent with those observed in simulations. The results demonstrate the relation between the rise in the strength of steric correlations and the changes in the screening behavior.
more »
« less
Diffusion of multiple electrolytes cannot be treated independently: model predictions with experimental validation
We study the diffusion of multiple electrolytes in a one-dimensional pore. We model the scenario where an electrolyte is in contact with a reservoir of another electrolyte, such that the cation of the two electrolytes is common. The model reveals that several factors influence the ion concentration profiles: (i) relative diffusivities of the ions, (ii) ratio of the electrolyte concentrations in the pore and the reservoir, and (iii) the valence of the ions. We demonstrate that it is crucial to consider the interaction between ion fluxes as treating the electrolytes independently, as is sometimes proposed, does not completely capture the dynamics of ion transport. We validate our numerical predictions by conducting experiments with sodium fluorescein salt in the pore and sodium chloride/sodium sulphate/sodium hydroxide in the reservoir. Our visualization and results demonstrate that ion diffusivities and concentrations in the reservoir can influence the diffusion rates of fluorescein, which underscores that ion fluxes are coupled and that multiple electrolytes cannot be treated independently. These results should be useful to the wide range of situations where concentration variations are imposed on systems with an existing background electrolyte.
more »
« less
- Award ID(s):
- 1702693
- PAR ID:
- 10158677
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 15
- Issue:
- 48
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 9965 to 9973
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Recent experimental studies have utilized AC electric fields and electrochemical reactions in multicomponent electrolyte solutions to control colloidal assembly. However, theoretical investigations have thus far been limited to binary electrolytes and have overlooked the impact of electrochemical reactions. In this study, we address these limitations by analyzing a system with multicomponent electrolytes, while also relaxing the assumption of ideally blocking electrodes to capture the effect of surface electrochemical reactions. Through a regular perturbation analysis in the low-applied-potential regime, we solve the Poisson–Nernst–Planck equations and obtain effective equations for electrical potential and ion concentrations. By employing a combination of numerical and analytical calculations, our analysis reveals a significant finding: electrochemical reactions alone can generate asymmetric rectified electric fields (AREFs), i.e., time-averaged, long-range electric fields, even when the diffusivities of the ionic species are equal. This finding expands our understanding beyond the conventional notion that AREFs arise solely from diffusivity contrast. Furthermore, we demonstrate that AREFs induced by electrochemical reactions can be stronger than those resulting from asymmetric diffusivities. Additionally, we report the emergence of asymmetric rectified concentration fields (ARCFs), i.e., time-averaged, long-range concentration fields, which supports the electrodiffusiophoresis mechanism of colloidal assembly observed in experiments. We also derive analytical expressions for AREFs and ARCFs, emphasizing the role of imbalances in ionic strength and charge density, respectively, as the driving forces behind their formation. The results presented in this article advance the field of colloidal assembly and also have implications for improved understanding of electrolyte transport in electrochemical devices.more » « less
-
null (Ed.)Sustained release and replenishment of the drug depot are essential for the long-term functionality of implantable drug-delivery devices. This study demonstrates the use nanoporous gold (np-Au) thin films for in-plane transport of fluorescein (a small-molecule drug surrogate) over large (mm-scale) distances from a distal reservoir to the site of delivery, thereby establishing a constant flux of molecular release. In the absence of halides, the fluorescein transport is negligible due to a strong non-specific interaction of fluorescein with the pore walls. However, in the presence of physiologically relevant concentration of ions, halides preferentially adsorb onto the gold surface, minimizing the fluorescein–gold interactions and thus enabling in-plane fluorescein transport. In addition, the nanoporous film serves as an intrinsic size-exclusion matrix and allows for sustained release in biofouling conditions (dilute serum). The molecular release is reproducibly controlled by gating it in response to the presence of halides at the reservoir (source) and the release site (sink) without external triggers (e.g., electrical and mechanical).more » « less
-
null (Ed.)Nanopore probing of molecular level transport of proteins is strongly influenced by electrolyte type, concentration, and solution pH. As a result, electrolyte chemistry and applied voltage are critical for protein transport and impact, for example, capture rate ( C R ), transport mechanism ( i.e. , electrophoresis, electroosmosis or diffusion), and 3D conformation ( e.g. , chaotropic vs. kosmotropic effects). In this study, we explored these using 0.5–4 M LiCl and KCl electrolytes with holo-human serum transferrin (hSTf) protein as the model protein in both low (±50 mV) and high (±400 mV) electric field regimes. Unlike in KCl, where events were purely electrophoretic, the transport in LiCl transitioned from electrophoretic to electroosmotic with decreasing salt concentration while intermediate concentrations ( i.e. , 2 M and 2.5 M) were influenced by diffusion. Segregating diffusion-limited capture rate ( R diff ) into electrophoretic ( R diff,EP ) and electroosmotic ( R diff,EO ) components provided an approach to calculate the zeta-potential of hSTf ( ζ hSTf ) with the aid of C R and zeta potential of the nanopore surface ( ζ pore ) with ( ζ pore – ζ hSTf ) governing the transport mechanism. Scrutinization of the conventional excluded volume model revealed its shortcomings in capturing surface contributions and a new model was then developed to fit the translocation characteristics of proteins.more » « less
-
Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)2], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.more » « less
An official website of the United States government

