Chapter 2: Electrochemistry at nanoelectrodes

The electrochemical behaviour of nanoelectrodes is a topic of huge interest, not least because of the unique properties that set them apart from the macroscopic or microscopic equivalents. Nanoelectrodes find a wide range of applications in the modern world, from sensing of trace analytes to measurement of heterogeneous electron transfer kinetics, and exciting developments continue to be made in this field. In this chapter we review the most recent advances relating to electrochemistry at nanoelectrodes and their arrays. We begin with an examination of the critical theory underpinning nanoelectrochemical measurements and present major progress in the computational simulation of such systems. We then turn our attention to the latest experimental advances, beginning with the latest nanoelectrode fabrication technologies and subsequently focusing on key applications in the areas of fundamental electrochemistry, electroanalysis and electrochemical imaging.