Electrochemically induced phase separation and in situ formation of mesoporous structures in ionic liquid mixtures

Liquid-liquid phase separation is mainly dependent on temperature and composition. Electric fields have also been shown to influence demixing of binary liquid mixtures. However, a puzzling behavior that remains elusive is the electric field–induced phase separation in ion-containing solvents at low voltages, as predicted by Tsori and Leibler. Here, we report the first experimental study of such a phenomenon in ionic liquid–silane mixtures, which not only results in phase separation at the electrode-electrolyte interface (EEI) but also is accompanied by deposition of porous structures of micrometer size on the electrode. This multiscale phenomenon at the EEI was found to be triggered by an electrochemically induced process. Using several analytical methods, we reveal the involved mechanism in which the formation of new Si–N bonds becomes unstable and eventually decomposes into the formation of silane-rich and silane-poor phases. The deposition of porous structures on the electrode surface is therefore a realization of the silane-rich phase. The finding of an electrochemically induced phase separation not only brings a paradigm shift in understanding the EEI in ionic liquids but also provides alternative strategies toward designing porous surfaces.