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.