Phase Behavior and Electrochemical Properties of Highly Asymmetric Redox Coacervates.

This work reports the phase behavior and electrochemical properties of liquid coacervates made of ferricyanide and poly(ethylenimine). In contrast to the typical polyanion/polycation pairs used in liquid coacervates, the ferricyanide/poly(ethylenimine) system is highly asymmetric because poly(ethylenimine) has approximately 170 charges per molecule, while ferricyanide has only 3. Two types of phase diagrams were measured and fitted with a theoretical model. In the first type of diagram, the stability of the coacervate was studied in the plane given by the concentration of poly(ethylenimine) versus the concentration of ferricyanide for a fixed concentration of added monovalent salt (NaCl). The second type of diagram involved the plane given by the concentration of poly(ethylenimine) vs the concentration of the added monovalent salt for a fixed poly(ethyleneimine)/ferricyanide ratio. Interestingly, these phase diagrams displayed qualitative similarities to those of symmetric polyanion/polycation systems, suggesting that coacervates formed by a polyelectrolyte and a small multivalent ion can be treated as a specific case of polyelectrolyte coacervate. The characterization of the electrochemical properties of the coacervate revealed that the addition of monovalent salt greatly enhances charge transport, presumably by breaking ion pairs between ferricyanide and poly(ethylenimine). This finding highlights the significant influence of added salt on the transport properties of coacervates. This study provides the first comprehensive characterization of the phase behavior and transport properties of asymmetric coacervates and places these results within the broader context of the better-known symmetric polyelectrolyte coacervates.