Thin-film voltammetry and its analytical applications: A review

• Electrochemistry at immiscible liquid–liquid interfaces is fundamentally important.
• Methods for studying redox processes at liquid–liquid interfaces are reviewed.
• Thin-film voltammetry is simple in experimental operation and kinetic data analysis.
• Thin-film voltammetry’s analytical applications are prevailing and comprehensive.

Electrochemical reactions at the interfaces of immiscible electrolyte solutions (ITIES) are of fundamental importance in the fields of chemical, biological and pharmaceutical sciences. Four-electrode cell setup, scanning electrochemical microscopy (SECM) and thin-film voltammetry are the three most frequently used methods for studying the electrochemical processes at these interfaces. The principle, experimental design, advantages and challenges of the three methods are described and compared. The thin-film voltammetry is highlighted for its simplicity in experimental operation and kinetic data analysis. Its versatile analytical applications are discussed in detail, including the study of redox properties of hydrophobic compounds, evaluation of interfacial electron transfer kinetics, synthesis of nanoparticles/nanostructures, and illustration of cross-membrane ion transport phenomena.

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