The framework for deriving tensorial interfacial dielectric profiles from bound charge distributions is established and applied to molecular dynamics simulations of water at hydrophobic and hydrophilic surfaces. In conjunction with a modified Poisson-Boltzmann equation, the trend of experimental double-layer capacitances is well reproduced. We show that the apparent Stern layer can be understood in terms of the dielectric profile of pure water.
We report on the efficiency of electrical power generation in individual rectangular nanochannels by means of streaming currents, the pressure-driven transport of counterions in the electrical double layer. Our experimental study as a function of channel height and salt concentration reveals that the highest efficiency occurs when double layers overlap, which corresponds to nanoscale fluidic channels filled with aqueous solutions of low ionic strength. The highest efficiency of approximately 3% was found for a 75 nm high channel, the smallest channel measured. The data are well described by Poisson-Boltzmann theory with an additional electrical conductance of the Stern layer.
We theoretically evaluate the prospect of using electrokinetic phenomena to convert hydrostatic energy to electrical power. An expression is derived for the energy conversion efficiency of a two-terminal fluidic device in terms of its linear electrokinetic response properties. For a slitlike nanochannel of constant surface charge density, we predict that the maximum energy conversion efficiency occurs at low salt concentrations. An analytic expression for the regime of strong double-layer overlap reveals that the efficiency depends only on the ratio of the channel height to the Gouy-Chapman length, and the product of the viscosity and the counterion mobility. We estimate that an electrokinetic energy conversion device could achieve a maximum efficiency of 12% for simple monovalent ions in aqueous solution.
We derive the theoretical framework to calculate the dielectric response tensor and determine its components for water adjacent to hydrophilic and hydrophobic surfaces using molecular dynamics simulations. For the nonpolarizable water model used, linear response theory is found to be applicable up to an external perpendicular field strength of ∼2 V/nm, which is well beyond the experimental dielectric breakdown threshold. The dipole contribution dominates the dielectric response parallel to the interface, whereas for the perpendicular component it is essential to keep the quadrupole and octupole terms. Including the space-dependent dielectric function in a mean-field description of the ion distribution at a single charged interface, we reproduce experimental values of the interfacial capacitance. At the same time, the dielectric function decreases the electrostatic part of the disjoining pressure between two charged surfaces, unlike previously thought. The difference in interfacial polarizability between hydrophilic and hydrophobic surfaces can be quantized in terms of the dielectric dividing surface. Using the dielectric dividing surface and the Gibbs dividing surface positions to estimate the free energy of a single ion close to an interface, ion-specific adsorption effects are found to be more pronounced at hydrophobic surfaces than at hydrophilic surfaces, in agreement with experimental trends.
The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field.
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