ABSTRACT
The molecular nature of interfaces between two immiscible electrolyte solutions (ITIES) provides a well-defined framework for fundamental studies of heterogeneous electrontransfer processes (ET). The potential impact of this topic has been recognized even before carrying out comprehensive work. Outstanding contributions by Samec [1], Kharkats and Volkov [2], and Marcus [3-6] delivered basic descriptions of the ET dynamics involving two redox couples separated by a polarized liquid-liquid junction. Further developments including lattice-gas [7] and molecular dynamics modeling [8, 9] have complemented these initial steps. By contrast, experimental studies have been able to address electron-transfer kinetics across ITIES only in the last few years. Among these recent advances, photoinduced heterogeneous ET has provided some exciting insights into the elementary processes at dye-sensitized liquid-liquid interfaces. The present chapter reviews these contributions, not only highlighting the experimental aspects and establishing comparisons with existing ET models, but also analyzing new perspectives for areas of practical interest such as twophase catalysis and solar energy conversion.
