Galvani Potential-Dependent Single Collision/Fusion Impacts at Liquid/Liquid Interface: Faradic or Capacitive?

A new subtype of nano-impacts by emulsion droplets via reorganization of the electric double layer (EDL) at the liquid/liquid interface (LLI) is reported. This subtype shows anodic, bipolar, and cathodic transient currents with a potential of zero charge (PZC) dependence, revealing the non-faradic characteristic of single fusion impacts. In addition, the absolute integrated mean charge is proportional to the Galvani potential at the ITIES, indicating that the EDL at the LLI may obey the discrete Helmholtz model. The exact PZC point is interpolated from the fitting curve, and the droplet size distribution is estimated from the integrated charge distribution. Moreover, the different values of Epzc between single fusion impacts of MgCl2 droplets and pure water droplets is due to the specific absorption between Mg2+ and antagonistic anion in the organic phase. The influence of the concentration of the supporting electrolyte is also investigated. The above work gives physicochemical insights into the EDL at the micropipette-supported LLI and provides potential application to measure micro/nanoscale heterogeneous media without catalytic, reactive, or charge-transfer activity via impact experiments at LLI.