Redox-Driven Reversible Gating of Solid-State Nanochannels

The design of an electrochemically addressable nanofluidic diode is proposed, which allows tunable and nanofluidic operations via redox gating under electrochemical control. The fabrication process involves the modification of an asymmetric gold-coated solid-state nanopore with a thin layer of a redox polymer, poly(vinylferrocene) (PVFc). The composite nanochannel acts as a gate electrode by changing the electrochemical state and, consequently, the conversion/switching of ferrocene into ferricenium units upon the application of different voltages. It is shown that the electrochemical input accurately controls the surface charge density of the nanochannel walls with a predictable concomitant effect on the rectification properties. PVFc-based nanofluidic devices are able to discriminate the passage of anionic species through the nanochannel in a qualitative and quantitative manner by simply switching the redox potential of the PVFc layer. Experimental data confirmed that a rapid and reversible modulation of the ionic transport regimes can be easily attained by changing the applied potential. This applied potential plays the role of the gate voltage (Vg) in field-effect transistors (FET), so these nanofluidic channels behave as ionic FETs. Depending on the Vg values, the iontronic behavior can be switched between ohmic and diode-like regimes. We believe that this system illustrates the potential of redox-active polymers integrated into nanofluidic devices as plausible, simple, and versatile platforms to create electrochemically addressable nanofluidic devices for multiple applications.