ion-exchange-membranes-for-fabrication-reverse-electrodialysis

Ion-Exchange Membranes for the Fabrication of Reverse Electrodialysis Device

Reverse electrodialysis (RED) is an effective way to generate power by mixing two different salt concentrations in water using cation-exchange membranes ...

Energy Engineering Lab, Sogang University

We propose a new type of micro/nano fluidic mixer based on non-equilibrium electrokinetics and demonstrate its mixing performance. We fabricate the device with two-step reactive ion etching, one for nanochannels and one for microchannels. Mixing is achieved by strong vortex structures formed near the micro/nano channel interface. We expect the proposed device to be beneficial in the development of micro total analysis systems, since it is simple in its design with minimal fabrication complications.

Non-equilibrium electrokinetic micro/nano fluidic mixer.

We report molecular dynamics simulation results of high-ionic-strength electroosmotic flows inside uncharged nanochannels. The possibility of this unusual electrokinetic phenomenon has been discussed by Dukhin et al. [A. Dukhin, S. Dukhin, P. Goetz, Langmuir 21 (2005) 9990]. Our computed velocity profiles clearly indicate the presence of a net flow with a maximum velocity around 2 m/s. We found the apparent zeta potential to be -29.7+/-6.8 mV, using the Helmholtz-Smoluchowski relation and the measured mean velocity. This value is comparable to experimentally measured values in Dukhin et al. and references therein. We also investigate the orientations of water molecules in response to an electric field by computing polarization density. Water molecules in the bulk region are oriented along the direction of the external electric field, while their near-wall orientation shows oscillations. The computation of three-dimensional density distributions of sodium and chloride ions around each individual water molecule show that chloride ions tend to concentrate near a water molecule, whereas sodium ions are diffusely distributed.

High-ionic-strength electroosmotic flows in uncharged hydrophobic nanochannels.

Clean and sustainable energy generation from ambient environments is important not only for large scale systems, but also for tiny electrical devices, because of the limitations of batteries or external power sources. Chemical concentration gradients are promising energy resources to power micro/nanodevices sustainably without discharging any pollutants. In this paper, an efficient microplatform based on reverse electrodialysis, which enables high ionic flux through three dimensional nanochannel networks for high power energy generation, is demonstrated. Highly effective cation-selective nanochannel networks are realized between two microfluidic channels with geometrically controlled in situ self-assembled nanoparticles in a cost-effective and simple way. The nano-interstices between the assembled nanoparticles have a role as collective three-dimensional nanochannel networks and they allow higher ionic flux under concentration gradients without decreasing diffusion potential, compared to standard one-dimensional nanochannels. An in-depth experimental study with theoretical analysis shows that the electrical power of the presented system can be flexibly tuned or further optimized by changing the size, material, and shape of the assembled nanoparticles or by the geometric control of the microchannel. This microfluidic power generation system can be readily integrated with existing lab on a chip systems in the near future and can also be utilized to investigate nanoscale electrokinetics. 

Tunable reverse electrodialysis microplatform with geometrically controlled self-assembled nanoparticle network.

This paper proposes a novel method to form ion-selective nanochannel networks between two microfluidic channels using geometrically controlled in situ self-assembled nanoparticles. We present a thorough experimental and theoretical analysis of nanoscale electrokinetics using the proposed microplatform. The nano-interstices between these assembled nanoparticles serve as the nanopores of ion-selective membranes with equivalent pore size. Its inherent characteristics (compared with the conventional one-dimensional nanochannels) are a high ionic flux and a low fluidic resistance because these nanopore clusters have a role as collective three-dimensional nanochannel networks, which result in a highly efficient performance beneficial for various applications. Another uniqueness of our system is that the electrical characteristics (such as ion transport through the nanochannel networks and the decrease in the limiting current region) can be tuned quantitatively or even optimized by changing the geometry of the microchannel and the pH condition of the working solution or by appropriately selecting the size and materials of the assembled nanoparticles. The correlation between these tuning parameters and nanoscale electrokinetics is deeply investigated with carefully designed experiments and their mechanism is thoroughly examined by a theoretical study. We expect that the presented system and methodology can contribute to opening new application fields, such as biomolecule separation/filtering/accumulation/analysis, bioelectronics, and energy generation. 

An electrokinetic study on tunable 3D nanochannel networks constructed by spatially controlled nanoparticle assembly.

We report an active micromixer which utilizes vortex generation due to non-equilibrium electrokinetics near the interface between a microchannnel and a nanochannel networks membrane (NCNM), constructed from geometrically controlled in situ self-assembled nanoparticles. A large interfacing area where it is possible to generate vortices can be realized, because nano-interstices between the assembled nanoparticles are intrinsically collective three-dimensional nanochannel networks, which may be compared to typical silicon-based 2D nanochannels. The proposed mixer shows a 2-fold shorter mixing time (~0.78 ms) and a 34-fold shorter mixing length (~7.86 μm) compared to conventional 2D nanochannels. 

Non-equilibrium electrokinetic micromixer with 3D nanochannel networks.

In this study, molecular dynamics (MD) simulations are used to examine the water transport properties through asymmetric hourglass-shaped pores in multilayer nanoporous graphene with a constant interlayer separation of 6 Å. The properties of the tested asymmetric hourglass-shaped pores [with the models having long cone (l, -P) and short cone (l, +P) entrances] are compared to a symmetric pore model. The study findings indicate that the water occupancy increases across the asymmetric pore (l, -P) compared to (l, +P), because of the length effect. The asymmetric pore, (l, -P), yields higher flux compared to (l, +P) and even the symmetric model, which can be attributed to the increase in the hydrogen bonds. In addition, the single-file water molecules across the narrowest pore diameter inside the (l, +P) pore exhibit higher viscosity compared to those in the (l, -P) pore because of the increase in the water layering effect. Moreover, it is found that the permeability inside the multilayer hourglass-shaped pore depends on the length of the flow path of the water molecules before approaching the layer with the smallest pore diameter. The probability of dipole orientation exhibits wider distribution inside the (l, -P) system compared to (l, +P), implying an enhanced formation of hydrogen bonding of water molecules. This results in the fast flow of water molecules. The MD trajectory shows that the dipole orientation across the single-layer graphene has frequently flipped compared to the dipole orientation across the pores in multilayer graphene, which is maintained during the whole simulation time (although the dipole orientation has flipped for a few picoseconds at the beginning of the simulation). This can be attributed to the energy barrier induced by the individual layer. The diffusion coefficient of water molecules inside the (l, +P) system increases with pressure difference, however, it decreases inside the (l, -P) system because of the increase in the number of collisions. It was found that the velocity in the axial direction (z-direction) has a significant impact on the permeation ability of water molecules across the asymmetric nanopores examined in this study. Finally, the study results suggest that the appropriate design of an asymmetric hourglass-shaped nanopore in multilayer graphene can significantly improve the water permeation rate even compared to a symmetric structure.

Transport of water molecules through noncylindrical pores in multilayer nanoporous graphene.

Water transport through aquaporin water channels occurs extensively in cell membranes. Hourglass-shaped (biconical) pores resemble the geometry of these aquaporin channels and therefore attract much research attention. We assumed that hourglass-shaped nanopores are capable of high water permeation like biological aquaporins. In order to prove the assumption, we investigated nanoscale water transport through a model hourglass-shaped pore using molecular dynamics simulations while varying the angle of the conical entrance and the total nanopore length. The results show that a minimal departure from optimized cone angle (e.g., 9° for 30 Å case) significantly increases the osmotic permeability and that there is a non-linear relationship between permeability and the cone angle. The analysis of hydrodynamic resistance proves that the conical entrance helps to reduce the hydrodynamic entrance hindrance. Our numerical and analytical results thus confirm our initial assumption and suggest that fast water transport can be achieved by adjusting the cone angle and length of an hourglass-shaped nanopore.

Molecular Dynamics Simulation of the Effect of Angle Variation on Water Permeability through Hourglass-Shaped Nanopores.

We report on our investigation of a low Reynolds number non-equilibrium electrokinetic flow in a micro/nanochannel platform. Non-equilibrium electrokinetic phenomena include so-called concentration polarization in a moderate electric field and vortex formation in a high electric field. We conducted a spectral analysis of non-equilibrium electrokinetic vortices at a micro/nanochannel interface. We found that periodic vortices are formed while the frequency varies with the applied voltages and solution concentrations. At a frequency as high as 60 Hz, vortex generation was obtained with the strongest electric field and the lowest concentration. The power spectra show increasing frequency with increasing voltage or decreasing concentration. We expect that our spectral analysis results will be useful for micromixer developers in the micromachine research field.

Quantification of Vortex Generation Due to Non-Equilibrium Electrokinetics at the Micro/Nanochannel Interface: Spectral Analysis.

We describe a quantitative study of vortex generation due to non-equilibrium electrokinetics near a micro/nanochannel interface. The microfluidic device is comprised of a microchannel with a set of nanochannels. These perm-selective nanochannels induce flow instability and thereby produce strong vortex generation. We performed tracking visualization of fluorescent microparticles to obtain velocity fields. Particle tracking enables the calculation of an averaged velocity field and the velocity fluctuations. We characterized the effect of applied voltages and electrolyte concentrations on vortex formation. The experimental results show that an increasing voltage or decreasing concentration results in a larger vortex region and a strong velocity fluctuation. We calculate the normalized velocity fluctuation-whose meaning is comparable to turbulent intensity-and we found that it is as high as 0.12. This value is indicative of very efficient mixing, albeit with a small Reynolds number.

Quantification of Vortex Generation Due to Non-Equilibrium Electrokinetics at the Micro/Nanochannel Interface: Particle Tracking Velocimetry.

Using molecular dynamics simulations, herein, we illustrate that a bending structure shows different behaviors for fast water transport through aquaporin-mimicking membranes in multilayer graphene and tubular structures. This suggests that the bending structure enhances water transport through multilayer membranes, indicating the optimum state at θ = 45°. Disruption of the single-file water arrangement inside the membrane can contribute to promoting water transport in this system. However, a bending structure reduces the rate of water transport in tubular systems. Our results exhibit that a straight tubular membrane transfers water molecules faster than its non-straight counterpart. A stabilized form of the single-file water structure was observed in the membrane. Interestingly, we found that the tubular hourglass-shaped membranes possessed a lower free energy than the multilayer membranes with an hourglass shape. This can be attributed to the accommodation of the single-file water configuration in a confined space with hydrophobic characteristics. Accordingly, integrating an hourglass shape pore in a tubular structure in an impermeable membrane provides high water permeability compared with its multilayer counterpart. We also found that the wide variation in the dipole orientation of water molecules and the energy barrier have dominant effects in determining fast water transport through multilayer and tubular membranes, respectively. The contribution of interlayer spacing on fast water transport through multilayer membranes was also studied.

Article	Year
Non-equilibrium electrokinetic micro/nano fluidic mixer. Lab on a chip\| PubMed ID: 18369520	2008
High-ionic-strength electroosmotic flows in uncharged hydrophobic nanochannels. Journal of colloid and interface science\| PubMed ID: 19007939	2009
Tunable reverse electrodialysis microplatform with geometrically controlled self-assembled nanoparticle network. Lab on a chip\| PubMed ID: 25328008	2015
An electrokinetic study on tunable 3D nanochannel networks constructed by spatially controlled nanoparticle assembly. Lab on a chip\| PubMed ID: 25407418	2015
Non-equilibrium electrokinetic micromixer with 3D nanochannel networks. Lab on a chip\| PubMed ID: 25710479	2015
Transport of water molecules through noncylindrical pores in multilayer nanoporous graphene. Physical chemistry chemical physics : PCCP\| PubMed ID: 28740979	2017
Molecular Dynamics Simulation of the Effect of Angle Variation on Water Permeability through Hourglass-Shaped Nanopores. Materials (Basel, Switzerland)\| PubMed ID: 28793636	2015
Quantification of Vortex Generation Due to Non-Equilibrium Electrokinetics at the Micro/Nanochannel Interface: Spectral Analysis. Micromachines\| PubMed ID: 30404283	2016
Quantification of Vortex Generation Due to Non-Equilibrium Electrokinetics at the Micro/Nanochannel Interface: Particle Tracking Velocimetry. Micromachines\| PubMed ID: 30404299	2016
Exploring fast water permeation through aquaporin-mimicking membranes. Physical chemistry chemical physics : PCCP\| PubMed ID: 31854415	2020

Daejoong Kim

Biography

JoVE Journal Publications

Other Publications