Vishal V. R. Nandigana

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.

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.

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.