Chapter 9: Electrochemistry in supercritical fluids

Electrochemistry in supercritical fluids is both interesting and challenging. Interesting because supercritical fluids can offer a wide accessible potential range, the ability to tune solvent properties with the temperature and pressure, zero surface tension, increased mass transport rates and the opportunity to work in volatile solvents at elevated temperatures. Challenging because the high temperatures and pressures require specialised cells and equipment, introduce safety issues, and necessitate different approaches to the fabrication of electrodes. In this chapter, we review the field of supercritical fluid electrochemistry focussing on the choice of fluids, the choice of electrolytes, the design of cells and electrodes, and some of the basic electrochemical studies of conductivity, double layer, redox reactions and mass transport reported in the literature.