We present our electroanalytical characterization of coupled electron- and phase-transfer (CEPhT) reactions on a nanodroplet cell. A CEPhT reaction occurs at a multiphase interface. Two immiscible continuous phases, organic and aqueous, are placed into contact and an electrode is positioned between them with the help of a piezoelectric positioner, forming a three-phase boundary. The chemical species will transfer between phases depending on its net charge and partition coefficients. On the other hand, we can mediate the phase transfer by electron transfer since it generates different electroactive species with different reactivities and solubilities. This phase transfer is a non-equilibrium process. We used nano-diameter pipettes to explore the three-phase interface geometry on the CEPhT reactions. Specially, we aim to study the structural arrangement at the three-phase boundary, and the CEPhT mechanisms for electrochemical standards to later applied it to three-phase homogenous reactions. Briefly, the pipettes are filled with water containing supporting electrolyte and redox species. The nanodroplet cell is submerged in an organic solvent that also contains redox species. This type of study allows us to confine the domain of electrochemical cell to a nanodroplet surrounded by a large continuous media of organic solvent, which helps to elucidate the mechanism of CEPhT. The electrochemical results are supported by finite element simulations including (1) electron transfer, (2) phase transfer, and (3) homogenous reactions. Overall, we propose new strategies to improve the available characterization and later development of applications at these three phase interfaces.

Nano three-phase interface electrochemistry

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