ABSTRACT
Most scanning electrochemical microscopy (SECM) experiments are conducted in the amperometric mode, yet microelectrodes have long been used as potentiometric devices. In this chapter, the authors present the background necessary to understand the differences between amperometric and potentiometric SECM applications, report the progress made in the field of potentiometric microelectrodes, consider the issues specific to the potentiometric mode of SECM and highlight some of the studies involving potentiometric SECM tips. Starting with an historical perspective, they highlight the key discoveries that facilitated the development and applications of micropotentiometric probes and include recent improvements in detection limits. The authors review fabrication recipes and cover basic theoretical principles, properties and technical operational details. They discuss SECM potentiometric applications and emphasize differences with the conventional amperometric mode.
