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Dafna Amichay

Publications and source records attributed to Dafna Amichay.

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Bipotentiostatic Control Unlocks Flashing Ratchet Features in Ion Pumps

The selective separation of same-charge ions is a longstanding challenge in resource recovery, battery recycling, and water treatment. Theoretical studies have shown that ratchet-based ion pumps (RBIPs) can separate ions with the same charge and valance by driving them in opposite directions according to their diffusion coefficients. This process relies on frequency dependent current reversal, a unique feature of ratchets in which the particle current direction is inverted with the input signal frequency. Previous experimental demonstrations of RBIPs achieved ion pumping against electrostatic forces and water deionization, but lacked frequency-dependent current reversal and control of the asymmetry of the device. Here, we report the first experimental realization of these key functionalities by driving RBIPs with a bipotentiostat. Complementary input signals applied to RBIP contacts unlock a flashing ratchet-like behavior, and enhances the device performance by an order of magnitude compared to the prior floating-drive approach. The enhanced control of the electrostatic potential at the RBIP surfaces leads to frequency dependent current reversals, and the addition of a potential offset to the input signal enables tuning the amplitude asymmetry of the device. This flashing ratchet functionality provides a significant step towards the realization of ratchet driven selective ion separation systems.

physics.chem-ph

Tuning electrochemical reactions with ratchet-based ion pumps

Electrochemical reactions are highly sensitive to the physical and chemical environment near the electrodes. Thus, controlling the electrolyte ionic composition and the electrochemical potential of specific ions can modify the overpotential of electrochemical reactions and enhance their selectivity toward the desired products. Ratchet-based ion pumps (RBIPs) are membrane-like devices that utilize temporal potential modulation to drive a net ionic flux with no associated electrochemical reactions. RBIPs were fabricated by coating the surfaces of nanoporous alumina wafers with metals, forming nanoporous capacitors. Placing the RBIP between two electrolyte compartments and applying an alternating signal between the metal layers resulted in a voltage buildup across the membrane, leading to ion pumping. Here, we demonstrate that by modifying the electrochemical potential of ions, RBIPs can accelerate or inhibit electrochemical reactions on the surface of adjacent water-splitting electrodes according to the RBIP input signal. Proton pumping towards a water-splitting cathode prevented proton depletion due to the hydrogen evolution reaction and maintained the pH in the cathode compartment. The combination of ion pumping and ion selectivity can enable the electrolyte composition to be tuned near the electrodes, providing greater control over the electrochemical process.

physics.app-ph