No abstract

A nanoelectrode with a controllable area was developed using commercial atomic force microscopy and a hydrogel. Although tremendous advantages of small electrodes from micrometer scale down to nanometer scale have been previously reported for a wide range of applications, precise and high-throughput fabrication remains an obstacle. In this work, the set-point feedback current in a modified scanning ionic conductance microscopy system controlled the formation of electrodes with a nanometer-sized area by contact between the boron-doped diamond (BDD) tip and the agarose hydrogel. The modulation of the electroactive area of the BDD-coated nanoelectrode in the hydrogel was successively investigated by the finite element method and cyclic voltammetry with the use of a redox-contained hydrogel. Moreover, this nanoelectrode enables the simultaneous imaging of both the topography and electrochemical activity of a polymeric microparticle embedded in a hydrogel.

The structure of an electrical double layer (EDL) at the interface of electrode/electrolyte or air/electrode/electrolyte is a fundamental aspect, however not fully understood. The potential of zero charge (PZC) is one of the clues to dictate the EDL, where the excess charge on the electrode surface is zero. Here, a nanoscale configuration of immersion method was proposed by integrating an electrochemical system into conductive atomic force spectroscopy under the amplitude modulation (AM) mode and agarose gel as the solid–liquid electrolyte. The PZC of boron-doped diamond was determined to be at 0.2 V (vs Ag/AgCl). By AM spectroscopy, the capacitive force shows remote electrification without direct electrode/electrolyte contact, which is dependent on the population of ions at the air/electrolyte interface. The surface potential by alignment of water is also evaluated. Prospectively, our study could benefit applications such as PZC measurement and non-electrode electrochemical processes at the air/electrolyte interface.