Multivalent Ion-Modulated Electron Transfer Processes in Carbon Nanopipettes.

Conductive nanopipettes with both an electroactive interface and a pipet geometry have been recognized as powerful multifunctional probes in various electrochemical sensing and imaging applications. As confined inside the nanopipette, the excess surface charges at the solid/solution interface would then play a dominant role in the resulting charge transport processes. Herein, the effects of a multivalent ion on the resulting electron transfer (ET) processes in the carbon nanopipettes are investigated with both experimental and simulation methods. The multivalent cations (i.e., Ca2+, Mg2+, Co2+, and Ni2+) are shown to strongly adsorb at the negatively charged carbon surface and attract more Fe(CN)64- ions inside the cavity, as indicated by the increasing ET current responses. In addition to elucidating the fundamental charge transport processes in conductive nanopipettes to afford better usage as electrochemical probes, these results could also help in the development of new sensing methods for measuring the non-electroactive ions in biological or environmental systems.