Effect of Field Direction on Electrowetting in a Nanopore

We manifest a significant influence of field direction and polarity on surface wetting, when the latter is tuned by application of an external electric field. Thermodynamics of field-induced filling of hydrocarbon-like nanopores with water is studied by open ensemble molecular simulation. Increased field strength consistently results in water-filling and electrostriction in hydrophobic nanopores. A threshold field commensurate with surface charge density of about one elementary charge per 10 nm2 suffices to render prototypical paraffin surfaces hydrophilic. When a field is applied in the direction perpendicular to the confining walls, the competition between orientational polarization and angle preferences of interfacial water molecules relative to the walls results in an asymmetric wettability of opposing surfaces (Janus interface). Reduction of surface free energy observed upon alignment of confinement walls with field direction suggests a novel mechanism whereby the applied electric field can operate selectively on water-filled nanotubes while empty ones remain unaffected

Electrokinetic flow of aqueous electrolyte in amorphous silica nanotubes

We study the pressure-driven flow of aqueous NaCl in amorphous silica nanotubes using nonequilibrium molecular dynamics simulations featuring both polarizable and non-polarizable molecular models. Different pressures, electrolyte concentrations and pore sizes are examined. Our results indicate a flow that deviates considerably from the predictions of Poiseuille fluid mechanics. Due to preferential adsorption of the different ionic species by surface SiO! or SiOH groups, we find that a significant electric current is generated, but with opposite polarities using polarizable vs. fixed charge models for water and ions, emphasizing the need for careful parameterization in such complex systems. We also examine the influence of partial deprotonation of the silica surface, and we find that much more current is generated in a dehydrogenated nanopore, even though the overall efficiency remains low. These findings indicate that different methods of nanopore preparation, which can produce a range of surface properties, should be examined more closely in the related experimental methods to generate electrokinetic current

Field exposed water in a nanopore: liquid or vapour?

We study the behavior of ambient temperature water under the combined effects of nanoscale confinement and applied electric field. Using molecular simulations we analyze the thermodynamic causes of field-induced expansion at some, and contraction at other conditions. Repulsion among parallel water dipoles and mild weakening of interactions between partially aligned water molecules prove sufficient to destabilize the aqueous liquid phase in isobaric systems in which all water molecules are permanently exposed to a uniform electric field. At the same time, simulations reveal comparatively weak field-induced perturbations of water structure upheld by flexible hydrogen bonding. In open systems with fixed chemical potential, these perturbations do not suffice to offset attraction of water into the field; additional water is typically driven from unperturbed bulk phase to the field-exposed region. In contrast to recent theoretical predictions in the literature, our analysis and simulations confirm that classical electrostriction characterizes usual electrowetting behavior in nanoscale channels and nanoporous materials.Comment: 20 pages, 6 figures + T.O.C. figure, in press in PCC

Dynamic Control of Nanopore Wetting in Water and Saline Solutions under an Electric Field

Field-induced nanopore wetting by aqueous solutions, including electrolytes, provides opportunities for a variety of applications. Con!icting porosity requirements have so far precluded direct implementations of a two-way control: the pores have to be su ciently wide to allow water in#ltration at experimentally relevant voltages but should not exceed the kinetic threshold for spontaneous expulsion in the absence of the #eld. Applicable widths are restricted below a few nanometers. Only a narrow window of #elds and pore geometries can simultaneously satisfy both of the above requirements. Accurate accounts of wetting equilibria and dynamics at nanoscale porosity require molecular level descriptions. Here we use molecular dynamics simulations to study dynamic, #eld-controlled transitions between nanocon#ned liquid and vapor phases in contact with an unperturbed aqueous or electrolyte environment. In nanopores wetted by electrolyte solutions, we observe depletion of salt compared to the bulk phase. The application of a local electric #eld enhances the uptake of water and ions in the con#nement. In systems prone to capillary evaporation, the process can be reversed at su cient strength of the electric #eld. For alternating displacement #eld, we identify the conditions where O (ns) responses of the reversible in#ltration/ expulsion cycle can be secured for experimentally realizable #eld strengths, porosity, and salinity of the solution

Reversible electrowetting transitions on superhydrophobic surfaces

Electric field applied across the interface has been shown to enable transitions from Cassie to Wenzel state on superhydrophobic surfaces with miniature corrugations. Molecular Dynamics (MD) simulations manifest the possibility of reversible cycling between the two states when narrow surface wells support spontaneous expulsion of water in the absence of the field. With approximately 1 nm sized wells between the surface asperities, response times to changes of electric field are of O(0.1) ns, allowing up to GHz frequency of the cycle. Because of orientation preferences of interfacial water in contact with the solid, the phenomenon depends on the polarity of the field normal to the interface. The threshold field strength for the Cassie-to-Wenzel transition is significantly lower for the field pointing from the aqueous phase to the surface, however, once in the Wenzel state, the opposite field direction secures tighter filling of the wells. Considerable hysteresis revealed by the delayed water retraction at decreasing field strength indicates the presence of moderate kinetic barriers to expulsion. Known to scale approximately with the square of the length scale of the corrugations, these barriers preclude the use of increased corrugation sizes while the reduction of the well diameter necessitates stronger electric fields. Field-controlled Cassie-to-Wenzel transitions are therefore optimized by using superhydrophobic surfaces with nanosized corrugations. Abrupt changes indicate a high degree of cooperativity reflecting the correlations between wetting states of interconnected wells on the textured surface

High-Pressure Infiltration−Expulsion of Aqueous NaCl in Planar Hydrophobic Nanopores

Pressure-driven permeation of water in a poorly wettable material results in a conversion of mechanical work into surface free energy representing a new form of energy storage, or absorption. When water is replaced by a concentrated electrolyte solution, the storage capacity of a nanoporous medium becomes comparable to high-end supercapacitors. The addition of salt can also reduce the hysteresis of the infiltration/expulsion cycle. Our molecular simulations provide a theoretical perspective into the mechanisms involved in the process, and underlying structures and interactions in compressed nanoconfined solutions. Specifically, we consider aqueous NaCl in planar confinements of widths of 1.0 nm and 1.64 nm and pressures of up to 3 kbar. Open ensemble Monte Carlo simulations utilizing fractional exchanges of molecules for efficient additions/removal of ions have been utilized in conjunction with pressure-dependent chemical potentials to model bulk phases under pressure. Confinements open to these pressurized bulk, aqueous electrolyte phases show reversibility at narrow pore sizes, consistent with experiment, as well as strong hysteresis at both pore size. The addition of salt results in significant increases in the solid/liquid interfacial tension in narrower pores and associated infiltration and expulsion pressures. These changes are consistent with strong desalination effects at the lower pore size observed irrespective of external pressure and initial concentration

Nanoconfined water under electric field at constant chemical potential undergoes electrostriction

Electric control of nanopore permeation by water and solutions enables gating in membrane ion channels and can be exploited for transient surface tuning of rugged substrates, to regulate capillary permeability in nanofluidics, and to facilitate energy absorption in porous hydrophobic media. Studies of capillary effects, enhanced by miniaturization, present experimental challenges in the nanoscale regime thus making molecular simulations an important complement to direct measurement. In a molecular dynamics (MD) simulation, exchange ofwater between the pores and environment requires modeling of coexisting confined and bulk phases, with confined water under the field maintaining equilibrium with the unperturbed environment. In the present article, we discuss viable methodologies for MD sampling in the above class of systems, subject to size-constraints and uncertainties of the barostat function under confinement and nonuniform-field effects. Smooth electric field variation is shown to avoid the inconsistencies of MD integration under abruptly varied field and related ambiguities of conventional barostatting in a strongly nonuniform interfacial system. When using a proper representation of the field at the border region of the confined water, we demonstrate a consistent increase in electrostriction as a function of the field strength inside the pore open to a field-free aqueous environment

Electrolyte pore/solution partitioning by expanded grand canonical ensemble Monte Carlo simulation

Using a newly developed grand canonical Monte Carlo approach based on fractional exchanges of dissolved ions and water molecules, we studied equilibrium partitioning of both components between laterally extended apolar confinements and surrounding electrolyte solution. Accurate calculations of the Hamiltonian and tensorial pressure components at anisotropic conditions in the pore required the development of a novel algorithm for a self-consistent correction of nonelectrostatic cut-off effects. At pore widths above the kinetic threshold to capillary evaporation, the molality of the salt inside the confinement grows in parallel with that of the bulk phase, but presents a nonuniform width-dependence, being depleted at some and elevated at other separations. The presence of the salt enhances the layered structure in the slit and lengthens the range of inter-wall pressure exerted by the metastable liquid. Solvation pressure becomes increasingly repulsive with growing salt molality in the surrounding bath. Depending on the sign of the excess molality in the pore, the wetting free energy of pore walls is either increased or decreased by the presence of the salt. Because of simultaneous rise in the solution surface tension, which increases the free-energy cost of vapor nucleation, the rise in the apparent hydrophobicity of the walls has not been shown to enhance the volatility of the metastable liquidinthepores

Salt and Water Uptake in Nanocon!nement under Applied Electric Field: An Open Ensemble Monte Carlo Study

Permeation of electrolytes in nanoporous materials underlies many applications in energy and materials technologies. Wetting of apolar nanopores can be enhanced by electric !eld, attracting water and ions from unperturbed electrolyte bath. We study absorption of water and NaCl in the pores by Expanded Ensemble Grand Canonical Monte Carlo simulation, which implements particle insertions and deletions through incremental changes in particles’ coupling with the system. We determine the uptake of water and ions in the pores, and concomitant changes in pore thermodynamics, as functions of !eld strength in the pore and salinity in the external bath. Pressure increase and reduction of wetting free energy, !, in the pore intensify near-quadratically with the !eld. Surprisingly, the in uence of bulk salinity on ! can change qualitatively with pore width and !eld strength. Conforming to Gibbs adsorption isotherm, narrow pores with salt molality below that of the bath experience an increase in ! with rising bulk salinity. The !eld can change salt depletion to excess and consequently reverse the salinity dependence of wetting free energy from increasing to declining function of bulk molality. Field polarity continues to play a role, leading to asymmetric wettability at opposing walls as we previously observed in the absence of ions

Wetting transparency of graphene in water

Measurements of contact angle on graphene sheets show a notable dependence on the nature of the underlying substrate, a phenomenon termed wetting transparency. Our molecular modeling studies reveal analogous transparency in case of submerged graphene fragments in water. A combined effect of attractive dispersion forces, angle correlations between aqueous dipoles, and repulsion due to the hydrogen-bond-induced orientation bias in polarized hydration layers acting across graphene sheet, enhances apparent adhesion of water to graphene. We show wetting free energy of a fully wetted graphene platelet to be about 8 mNm−1 lower than for graphene wetted only on one side, which gives close to 10◦ reduction in contact angle. This difference has potential implications for predictions of water absorption vs. desorption, phase behavior of water in aqueous nanoconfinements, solvent- induced interactions among graphitic nanoparticle and concomitant stability in aqueous dispersions, and can influence permeability of porous materials such as carbon nanotubes by water and aqueous solutions