Overlimiting current near a nanochannel a new insight using molecular dynamics simulations

In this paper, we report for the first time overlimiting current near a nanochannel using all-atom molecular dynamics (MD) simulations. Here, the simulated system consists of a silicon nitride nanochannel integrated with two reservoirs. The reservoirs are filled with $${0.1} \, \hbox {M}$$ 0.1 M potassium chloride (KCl) solution. A total of $${\sim } 1.1$$ ∼ 1.1 million atoms are simulated with a total simulation time of $${\sim } 1 {\mu s}$$ ∼ 1 μ s over $${\sim }$$ ∼ 30000 CPU hours using 128 core processors (Intel(R) E5-2670 2.6 GHz Processor). The origin of overlimiting current is found to be due to an increase in chloride ($${Cl^-}$$ C l - ) ion concentration inside the nanochannel leading to an increase in ionic conductivity. Such effects are seen due to charge redistribution and focusing of the electric field near the interface of the nanochannel and source reservoir. Also, from the MD simulations, we observe that the earlier theoretical and experimental postulations of strong convective vortices resulting in overlimiting current are not the true origin for overlimiting current. Our study may open up new theories for the mechanism of overlimiting current near the nanochannel interconnect devices.

Pulsed Electric Field-Assisted Overlimiting Current Enhancement through a Perm-selective Membrane

Overlimiting current through a perm-selective membrane has been actively researched not only for the fundamental advancement of electrokinetics but also for energy-/environmental- applications such as electrodialysis and fuel cell, etc....

Transitions and Instabilities in Imperfect Ion-Selective Membranes

Numerical investigation of the underlimiting, limiting, and overlimiting current modes and their transitions in imperfect ion-selective membranes with fluid flow through permitted through the membrane is presented. The system is treated as a three layer composite system of electrolyte-porous membrane-electrolyte where the Nernst–Planck–Poisson–Stokes system of equations is used in the electrolyte, and the Darcy–Brinkman approach is employed in the nanoporous membrane. In order to resolve thin Debye and Darcy layers, quasi-spectral methods are applied using Chebyshev polynomials for their accumulation of zeros and, hence, best resolution in the layers. The boundary between underlimiting and overlimiting current regimes is subject of linear stability analysis, where the transition to overlimiting current is assumed due to the electrokinetic instability of the one-dimensional quiescent state. However, the well-developed overlimiting current is inherently a problem of nonlinear stability and is subject of the direct numerical simulation of the full system of equations. Both high and low fixed charge density membranes (low- and high concentration electrolyte solutions), acting respectively as (nearly) perfect or imperfect membranes, are considered. The perfect membrane is adequately described by a one-layer model while the imperfect membrane has a more sophisticated response. In particular, the direct transition from underlimiting to overlimiting currents, bypassing the limiting currents, is found to be possible for imperfect membranes (high-concentration electrolyte). The transition to the overlimiting currents for the low-concentration electrolyte solutions is monotonic, while for the high-concentration solutions it is oscillatory. Despite the fact that velocities in the porous membrane are much smaller than in the electrolyte region, it is further demonstrated that they can dramatically influence the nature and transition to the overlimiting regimes. A map of the bifurcations, transitions, and regimes is constructed in coordinates of the fixed membrane charge and the Darcy number.

Reasons for the Formation and Properties of Soliton-Like Charge Waves in Membrane Systems When Using Overlimiting Current Modes

The study of ion transport in membrane systems in overlimiting current modes is an important problem of physical chemistry and has an important application value. The influence of the space charge on the transport of salt ions under overlimiting current modes was first studied in the work of Rubinstein and Shtilman and later in the works of many authors. The purpose of this research is to study, using the method of mathematical modeling, the reasons of formation and properties of the local maximum (minimum) space charge in membrane systems under overlimiting current conditions. It is shown that, in the diffusion layer of the cation-exchange membrane (CEM), the local maximum of the space charge appears due to the limited capacity (exchange capacity) of the membrane at a given potential jump, i.e., the local maximum of space charge appears due to the presence of a local minimum of space charge at the surface of the CEM. The local maximum of the space charge moves as a single soliton-like wave into the depth of the solution. Unlike real solitons, this charged wave changes its size and shape, albeit quite slowly. In the section of the desalination channel, the situation is completely different. First, the space charge of the anion-exchange membrane (AEM) has a negative value, so we should be talking about the local minimum (or the maximum of the absolute value of the charge). However, this is an insignificant clarification. Secondly, the space charge waves of different signs begin to interact, which leads to a new effect, namely the effect of the breakdown of the space charge. The dependence of the local maximum on the input parameters—the cation diffusion coefficient, the growth rate of the potential jump, and the initial and boundary concentrations—is studied.

How Overlimiting Current Condition Influences Lactic Acid Recovery and Demineralization by Electrodialysis with Nanofiltration Membrane: Comparison with Conventional Electrodialysis

Acid whey is the main co-product resulting from the production of fresh cheeses and Greek-type yogurts. It generally goes through a spray-drying process prior to valorization, but it needs to be deacidified (lactic acid recovery) and demineralized beforehand to obtain a powder of quality with all the preserved compounds of interest such as lactose and proteins. Electrodialysis (ED) is a process actually used for acid whey treatment, but scaling formation at the surface of the ion-exchange membrane is still a major problem. In this work, a combination of two new avenues of ED treatment has been studied. First, the integration of a nanofiltration (NF) membrane in an ED conventional stack was compared to a classical ED stack with an anion-exchange membrane in a standard current condition. Secondly, both configurations were tested in the overlimiting current condition to study the impact of electroconvective vortices on process efficiency. The combined effects of the NF membrane and overlimiting current condition led to a higher lactic acid recovery rate of acid whey (40%), while the conventional ED stack in the overlimiting current condition led to a higher demineralization (87% based on the total cation concentration). Those effects were related to the conductivity, pH, global resistance, and energy consumption of each treatment that are influenced by water splitting phenomenon, which was decreased in the overlimiting condition.