Laser-Assisted Scalable Pore Fabrication in Graphene Membranes for Blue-Energy Generation.

The osmotic energy from a salinity gradient (i. e. blue energy) is identified as a promising non-intermittent renewable energy source for a sustainable technology. However, this membrane-based technology is facing major limitations for large-scale viability, primarily due to the poor membrane performance. An atomically thin 2D nanoporous material with high surface charge density resolves the bottleneck and leads to a new class of membrane material the salinity gradient energy. Although 2D nanoporous membranes show extremely high performance in terms of energy generation through the single pore, the fabrication and technical challenges such as ion concentration polarization make the nanoporous membrane a non-viable solution. On the other hand, the mesoporous and micro porous structures in the 2D membrane result in improved energy generation with very low fabrication complexity. In the present work, we report femtosecond (fs) laser-assisted scalable fabrication of µm to mm size pores on Graphene membrane for blue energy generation for the first time. A remarkable osmotic power in the order of µW has been achieved using mm size pores, which is about six orders of magnitudes higher compared to nanoporous membranes, which is mainly due to the diffusion-osmosis driven large ionic flux. Our work paves the way towards fs laser-assisted scalable pore creation in the 2D membrane for large-scale osmotic power generation.

Electrodiffusioosmosis induced negative differential resistance in micro-to-millimeter size pores through a graphene/copper membrane.

Negative differential resistance (NDR) is one of the nonlinear transport phenomena in which ionic current decreases with the increase in electromotive potential. Electro-osmosis, diffusio-osmosis, and surface charge density of pores are the driving forces for observing NDR in nanoscale ion transport. Here, we report electrodiffusioosmosis induced NDR using micro to millimeter size pores in a two-dimensional (2D) graphene-coated copper (Gr/Cu) membrane. Along with NDR, we also observed ion current rectification (ICR), in which there is preferential one-directional ion flow for equal and opposite potentials. The experimentally observed NDR effect has been validated by performing ion transport simulations using Poisson-Nernst-Planck (PNP) equations and Navier-Stokes equations with the help of COMSOL Multiphysics considering salinity gradient across the membrane. Charge polarization induced electro-osmotic flow (EOF) dominates over diffusio-osmosis, causing the backflow of low concentration/conductivity solution into the pore, thereby causing NDR. This finding paves the way toward potential applications in ionic tunnel diodes as rectifiers, switches, amplifiers, and biosensors.

Design and development of an automated experimental setup for ion transport measurements.

The ion transport measurements using various ion-exchange membranes (IEMs) face several challenges, including controllability, reproducibility, reliability, and accuracy. This is due to the manual filling of the solutions in two different reservoirs in a typical diffusion cell experiment with a random flow rate, which results in the diffusion through the IEM even before turning on the data acquisition system as reported so far. Here, we report the design and development of an automated experimental setup for ion transport measurements using IEMs. The experimental setup has been calibrated and validated by performing ion transport measurements using a standard nanoporous polycarbonate membrane. We hope that the present work will provide a standard tool for realizing reliable ion transport measurements using ion-exchange membranes and can be extended to study other membranes of various pore densities, shapes, and sizes.

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 [Formula: see text] potassium chloride (KCl) solution. A total of [Formula: see text] million atoms are simulated with a total simulation time of [Formula: see text] over [Formula: see text] 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 ([Formula: see text]) 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.

Asymmetric-Fluidic-Reservoirs Induced High Rectification Nanofluidic Diode.

We demonstrate a novel nanofluidic diode that produces rectification factors in excess of 1000. The nanofluidic diode consists of ion permselective nanopores that connect two reservoirs of different diameters- a micropore reservoir and a macropore reservoir. On the application of +100 V to the micropore, a low OFF state current is observed. The OFF state is caused by formation of the ion depleted zone in the micropore because the anions are prevented from entering the nanopores from the micropore and the cations are depleted in this region to maintain charge neutrality. On the application of -100 V, we observe a high ON state current. The ON state is caused by formation of the ion enriched zone in the microchannel because the anions cannot pass through the nanopores and accumulate in the microchannel. To maintain charge neutrality the cations also become enriched in the microchannel. The ratio of ON state current to the OFF state current gives the rectification of current. Here, plasma oxidation is used to achieve a nanopore with a large wall surface charge density of σn = -55 mC/m2 which yields a rectification of current on the order of 3500 that is nearly two orders of magnitude higher than those reported thus far. In contrast to the other nanofluidic diodes, this nanofluidic diode does not introduce asymmetry to the nanopore, but asymmetry is produced by having the nanopores join a micropore and a macropore. Introduction of asymmetry into the fluidic reservoirs which the nanopores connect is quite simple. Hence, the nanofluidic diode is easy to scale up to industrial level.

Avalanche effects near nanojunctions.

In this article, we perform a computational investigation of a nanopore connected to external fluidic reservoirs of asymmetric geometries. The asymmetry between the reservoirs is achieved by changing the cross-sectional areas, and the reservoirs are designated as the micropore reservoir and macropore reservoir. When an electric field is applied, which is directed from the macropore towards the micropore reservoir, we observe local nonequilibrium chaotic current oscillations. The current oscillations originate at the micropore-nanopore interface owing to the local cascade of ions; we refer to this phenomenon as the "avalanche effects." We mathematically quantify chaos in terms of the maximum Lyapunov exponent. The maximum Lyapunov exponent exhibits a monotonic increase with the applied voltage and the macropore reservoir diameter. The temporal power spectra maps of the chaotic currents depict a low-frequency "1/f"-type dynamics for the voltage chaos and "1/f^{2}"-type dynamics for the macropore reservoir chaos. The results presented here offer avenues to manipulate ionic diodes and fluidic pumps.

Controlling the ionic current rectification factor of a nanofluidic/microfluidic interface with symmetric nanocapillary interconnects.

The current rectification factor can be tailored by changing the degree of asymmetry between the fluid baths on opposite sides of a nanocapillary membrane (NCM). A symmetric device with symmetric fluid baths connected to opposite sides of the NCM did not rectify ionic current; while a NCM connected between fluid baths with a 32-fold difference in cross-sectional area produced a rectification factor of 75. The data suggests that the primary mechanism for the current rectification is the change in cross-sectional area of the fluid baths and the polarity dependent propagation of the enriched and depleted concentration polarization (CP) zones into these regions. An additional contribution to the increasing rectification factor with increasing bath asymmetry appears to be a result of electroconvection in the macropore, with inside diameters (IDs) of 625 and 850-µm. Power spectral density (PSD) analysis reveals chaotic oscillations that are consistent with electroconvection in the I-t data of the 625 and 850-µm ID macropore devices. In the ON state, current rectification keeps ionic transport toward the NCM high, increasing the speed of processes like sample enrichment. A simple means is provided to fabricate fluidic diodes with tailored current rectification factors.

Understanding anomalous current-voltage characteristics in microchannel-nanochannel interconnect devices.

The integration of a microchannel with a nanochannel is known to exhibit anomalous nonlinear current-voltage characteristics. In this paper, we perform detailed numerical simulations considering a 2-D nonlinear ion transport model, to capture and explain the underlying physics behind the limiting resistance and the overlimiting current regions, observed predominantly in a highly ion-selective nanochannel. We attribute the overlimiting current characteristics to the redistribution of the space charges resulting in an anomalous enhancement in the ionic concentration of the electrolyte in the induced space charge region, beyond a critical voltage. The overlimiting current with constant conductivity is predicted even without considering the effects of fluidic nonlinearities. We extend our study and report anomalous rectification effects, resulting in an enhancement of current in the non-ohmic region, under the application of combined AC and DC electric fields. The necessary criteria to observe these enhancements and some useful scaling relations are discussed.