Quad-Barrel Multifunctional Electrochemical and Ion Conductance Probe for Voltammetric Analysis and Imaging

The fabrication and use of a multifunctional electrochemical probe incorporating two independent carbon working electrodes and two electrolyte-filled barrels, equipped with quasi-reference counter electrodes (QRCEs), in the end of a tapered micrometer-scale pipet is described. This "quad-probe" (4-channel probe) was fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barrelled pipet. After filling the open channels with electrolyte solution, a meniscus forms at the end of the probe and covers the two working electrodes. The two carbon electrodes can be used to drive local electrochemical reactions within the meniscus while a bias between the QRCEs in the electrolyte channels provides an ion conductance signal that is used to control and position the meniscus on a surface of interest. When brought into contact with a surface, localized high resolution amperometric imaging can be achieved with the two carbon working electrodes with a spatial resolution defined by the meniscus contact area. The substrate can be an insulating material or (semi)conductor, but herein, we focus mainly on conducting substrates that can be connected as a third working electrode. Studies using both aqueous and ionic liquid electrolytes in the probe, together with gold and individual single walled carbon nanotube samples, demonstrate the utility of the technique. Substrate generation-dual tip collection measurements are shown to be characterized by high collection efficiencies (approaching 100%). This hybrid configuration of scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) should be powerful for future applications in electrode mapping, as well as in studies of insulating materials as demonstrated by transient spot redox-titration measurements at an electrostatically charged Teflon surface and at a pristine calcite surface, where a functionalized probe is used to follow the immediate pH change due to dissolution.